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Atoms, Molecules

and Lasers
LECTURES PRESENTED AT THE INTERNATIONAL WINTER COLLEGE
TRIESTE
17 JANUARY - 10 APRIL 1973
ORGANIZED BY THE
INTERNATIONAL CENTRE
FOR THEORETICAL PHYSICS,

i m
I N T E R N A T I O N A L A T O M I C ENERGY A G E N C Y , V I E N N A , 1 9 7 4
ATOMS, MOLECULES AND LASERS
Winter College Lectures, Trieste, 1973

CORRIGENDA

Owing to postal difficulties outside the publisher's control, the


following corrections were received after the book had gone to press

RADIOFREQUENCY SPECTROSCOPY, by A. Kastler (pp. 175-211)

Page 177, heading of sub-section 2.3. At the end of the heading add: (Fig. 1)
Page 189, Fig. 15. The ellipses should be replaced by circles
Page 194, Fig. 18. The figure should be as follows:

Y У
X

Page 202, Fig. 24. Delete parts (b) and (c).


HEAVY-PARTICLE COLLISIONS, by R. McCarroIl (pp. 619-677)

Page 622, line above Eq.(1.15). For ( 1.15) read (1.14). 2m


Page 623, Eq. (1.18). Under the equation add: where u = -pp v
n
Page 623, Eq. (1.22). For J ^ read
Page 624, line below Eq. (1.30). For 0 < 0 < 7Г read 0 < в < tj
For if в is read if © is
Page 626, Eq. (1.41). For (tv z) read (t?,z)
Page 621, line 3 after Eq. (1.49). For exp(iq • kz) read exp(iq- kz)
Page 629, Eq. (1.71). The first F on the right-hand side of the equation should be
Page 629, Eq. (1.72) "1
Page 630, first line У For F read
Page 630, Eq. (1.73) J
Page 630, expression between (1.73) and (1.74). For h read h
Page 630, Eq. (1.74). For all h read h
Page 631, statement between Eqs (1.86) and (1.87). For the absolute value of the
average potential is read the absolute value of the average potential, it is
seen from formula (1.84) that
Page 634, caption to Fig. 3. For в read ©
Page 634, Eq. (1.95), The second equality sign should be replaced by a plus sign
Page 638, Eqs (1.111) to (1.114). For b read d
Page 639, Eq. (1.115). For ß(ß+2) read ß(ß+1)
Page 649, first line of sub-section 2.2. For 4 read 1,4
Page 649, Eq. (2.21). For Фр read Ф ь
Page 649, line below Eq. (2.21). For фа read фв
Page 650, end of first line of Eq. (2.25). For v 1 ^ ) read v 2 ^(2)
Page 651, line below Eq. (2.33). For у read m
Page 653, last paragraph of sub-section 2.2, first line. For 1.6 read 1.5
Page 654, first relation displayed. For vt read vt
Page 657, fifth hne from bottom. For intensive read extensive
Page 670, Eq. (3.19). For 2pa u read 2p7Tu'
ATOMS, M O L E C U L E S AND L A S E R S
INTERNATIONAL C E N T R E F O R T H E O R E T I C A L PHYSICS, T R I E S T E

ATOMS, MOLECULES AND LASERS

LECTURES PRESENTED AT
THE INTERNATIONAL WINTER C O L L E G E
A T T R I E S T E F R O M 17 JANUARY TO 10 A P R I L 197 3
ORGANIZED BY THE
INTERNATIONAL C E N T R E F O R T H E O R E T I C A L PHYSICS, T R I E S T E

INTERNATIONAL ATOMIC E N E R G Y AGENCY


VIENNA, 1974
THE INTERNATIONAL C E N T R E F O R T H E O R E T I C A L PHYSICS (ICTP)
in T r i e s t e w a s e s t a b l i s h e d by the I n t e r n a t i o n a l A t o m i c E n e r g y Agency
(IAEA) in 1964 u n d e r an a g r e e m e n t with t h e I t a l i a n G o v e r n m e n t , and with
t h e a s s i s t a n c e of t h e City and U n i v e r s i t y of T r i e s t e .
T h e IAEA and t h e United N a t i o n s E d u c a t i o n a l , S c i e n t i f i c and C u l t u r a l
O r g a n i z a t i o n (UNESCO) s u b s e q u e n t l y a g r e e d to o p e r a t e t h e C e n t r e jointly
f r o m 1 J a n u a r y 1970.
M e m b e r S t a t e s of both o r g a n i z a t i o n s p a r t i c i p a t e in t h e w o r k of t h e C e n t r e ,
t h e m a i n p u r p o s e of which is to f o s t e r , t h r o u g h t r a i n i n g and r e s e a r c h , t h e
a d v a n c e m e n t of t h e o r e t i c a l p h y s i c s , with s p e c i a l r e g a r d to t h e n e e d s of
developing countries.

ATOMS, M O L E C U L E S AND LASERS


IAEA, VIENNA, 1974
STI/PUB/356
ISBN 9 2 - 0 - 1 3 0 3 7 4 - 2

Printed by the IAEA in Austria


D e c e m b e r 1974
FOREWORD

The I n t e r n a t i o n a l C e n t r e f o r T h e o r e t i c a l P h y s i c s h a s m a i n t a i n e d an
i n t e r d i s c i p l i n a r y c h a r a c t e r in i t s r e s e a r c h and t r a i n i n g p r o g r a m m e s in
d i f f e r e n t b r a n c h e s of t h e o r e t i c a l p h y s i c s . In p u r s u a n c e of this o b j e c t i v e ,
the C e n t r e h a s o r g a n i z e d e x t e n d e d r e s e a r c h c o u r s e s with a c o m p r e h e n s i v e
and s y n o p t i c c o v e r a g e in v a r y i n g d i s c i p l i n e s . The f i r s t of t h e s e — on
P l a s m a P h y s i c s — was held in 1964; the s e c o n d , in 1965, was c o n c e r n e d with
the P h y s i c s of P a r t i c l e s . B e t w e e n then and 1972, eight c o u r s e s w e r e
o r g a n i z e d : t h r e e on N u c l e a r T h e o r y (1966, 1969, 1971), t h r e e on the P h y s i c s
of C o n d e n s e d M a t t e r (1967, 1970, 1972), one on C o m p u t i n g as a L a n g u a g e
of P h y s i c s (1971), and one on Global A n a l y s i s and Its A p p l i c a t i o n s (1972).
The p r o c e e d i n g s of all t h e s e c o u r s e s have b e e n p u b l i s h e d by the I n t e r n a -
t i o n a l A t o m i c E n e r g y A g e n c y . The p r e s e n t v o l u m e r e c o r d s the p r o c e e d -
i n g s of the e l e v e n t h c o u r s e , held f r o m 17 J a n u a r y to 10 A p r i l 1973, which
d e a l t with A t o m s , M o l e c u l e s and L a s e r s . G e n e r o u s g r a n t s f r o m the Swedish
I n t e r n a t i o n a l D e v e l o p m e n t A u t h o r i t y and f r o m the N a t h h o r s t F o u n d a t i o n a r e
g r a t e f u l l y a c k n o w l e d g e d . All who attended t h i s c o u r s e will r e m e m b e r the
a m o u n t of w o r k which P r o f e s s o r A. K a s t l e r did u n s e l f i s h l y to e n s u r e i t s
success.
The p r o g r a m m e of l e c t u r e s w a s o r g a n i z e d by P r o f e s s o r s A. K a s t l e r
( F r a n c e ) , B. E d l é n (Sweden), I. K o v á c s (Hungary), and B . L . M o i s e i w i t s c h
(United Kingdom).

Abdus S a l a m
EDITORIAL NOTE

The papers and discussions incorporated in the proceedings published


by the International Atomic Energy Agency are edited by the Agency's edi-
torial staff to the extent considered necessary for the reader's assistance.
The views expressed and the general style adopted remain, however, the
responsibility of the named authors or participants.
For the sake of speed of publication the present Proceedings have been
printed by composition typing and photo-offset lithography. Within the limi-
tations imposed by this method, every effort has been made to maintain a
high editorial standard; in particular, the units and symbols employed are
to the fullest practicable extent those standardized or recommended by the
competent international scientific bodies.
The affiliations of authors are those given at the time of nomination.
The use in these Proceedings of particular designations of countries or
territories does not imply any judgement by the Agency as to the legal status
of such countries or territories, of their authorities and institutions or of
the delimitation of their boundaries.
The mention of specific companies or of their products or brand-names
does not imply any endorsement or recommendation on the part of the
International Atomic Energy Agency.
CONTENTS

P a r t I. ATOMS AND L A S E R S

T h e o r y of a t o m i c s t r u c t u r e and t r a n s i t i o n p r o b a b i l i t i e s
(IAEA-SMR-12/21) 3
S. F e n e u i l l e
T h e o r y of a t o m i c s t r u c t u r e s , t r a n s i t i o n s , and m o l e c u l a r p o t e n t i a l
c u r v e s with e l e c t r o n c o r r e l a t i o n in ground and e x c i t e d s t a t e s
(IAEA-SMR-12/52) 57
0. Sinanoglu
O b s e r v e d s t r u c t u r e of a t o m i c s p e c t r a ( I A E A - S M R - 1 2 / 4 , 5) 93
B. E d l é n
L i n e width and line b r o a d e n i n g ( I A E A - S M R - 1 2 / 1 2 ) 133
W.R. H i n d m a r s h
Radiofrequency spectroscopy (IAEA-SMR-12/9) 175
A. K a s t l e r
N u c l e a r e f f e c t s in a t o m i c s p e c t r a ( I A E A - S M R - 1 2 / 7 ) 213
J. B a u c h e
Highly e x c i t e d a t o m s ( I A E A - S M R - 1 2 / 4 5 ) 241
1.C. Р е г с i v a l
A s t r o p h y s i c a l a p p l i c a t i o n s of a t o m i c p h y s i c s
( I A E A - S M R - 1 2 / 4 4 , 46, 48) 261
M.J. S e a t o n
L a s e r t h e o r y ( I A E A - S M R - 1 2 / 3 2 , 35) 283
H. H a k e n
L a s e r s : e x p e r i m e n t a l and a p p l i c a t i o n s ( I A E A - S M R - 1 2 / 3 1 , 32) 315
D.J. B r a d l e y

P a r t II. MOLECULES

F o u n d a t i o n of the t h e o r y of d i a t o m i c m o l e c u l e s
(IAEA-SMR-12/11) 377
I. К o v á с s
P e r t u r b a t i o n s in the s p e c t r a of d i a t o m i c m o l e c u l e s
(IAEA-SMR-12/42) 411
Hélène L e f e b v r e - B r i o n
Multiplet s t r u c t u r e of s p e c t r a of d i a t o m i c m o l e c u e s
( I A E A - S M R - 1 2 / 3 0 , 37) 449
L.Klynning

P a r t III. COLLISIONS

A t o m i c c o l l i s i o n t h e o r y (IAEA-SMR-12/14) 471
B.L. M o i s e i w i t s c h
A n a l y s i s of e l e c t r o n - a t o m s c a t t e r i n g and p h o t o i o n i z a t i o n
p r o c e s s e s ( I A E A - S M R - 1 2 / 1 7 , 19) 525
P.G. B u r k e
Collisions between electrons'and molecules
( I A E A - S M R - 1 2 / 2 6 , 27) 567
F.H. R e a d
H e a v y - p a r t i c l e c o l l i s i o n ( I A E A - S M R - 1 2 / 4 0 , 41) 619
R. M c C a r r o l l
Photionization (IAEA-SMR-12/50) 679
M. G a v r i l a

F a c u l t y and p a r t i c i p a n t s 703
P A R T I: A T O M S AND L A S E R S
IAEA-SMR-12/21

THEORY O F ATOMIC STRUCTURE


AND TRANSITION P R O B A B I L I T I E S

S. FENEUILLE
Université de Paris-Sud,
Orsay, France

Abstract

THEORY OF ATOMIC STRUCTURE AND TRANSITION PROBABILITIES.


1. G e n e r a l f e a t u r e s of a t o m i c structure theory: 1 . 1 . Introduction; 1 . 2 . Notations and a t o m i c
constants; 1 . 3 . A t o m i c H a m i l t o n i a n s and their s y m m e t r y properties'; 1 . 4 . A p p r o x i m a t i o n methods;
1 . 5 . Conclusion. 2. Elements of group theory: 2 . 1 . F u n d a m e n t a l properties; 2 . 2 . C o n j u g a t e e l e m e n t s -
classes; 2 . 3 . Matrix representations - characters; 2 . 4 . Kronecker product; 2 . 5 . W i g n e r - E c k a r t t h e o r e m .
3. The r o t a t i o n group in t h r e e dimensions: 3 . 1 . I n f i n i t e s i m a l rotations and angular m o m e n t a ; 3 . 2 . Classes
and i r r e d u c i b l e representations; 3 . 3 . Kronecker products - 3j symbols; 3 . 4 . Recoupling c o e f f i c i e n t s - n j symbols.
4 . Tensor operators: 4 . 1 . Definition of i r r e d u c i b l e tensor operators; 4 . 2 . W i g n e r - E c k a r t t h e o r e m ;
4 . 3 . C o u p l e d tensor operators; 4 . 4 . E l e m e n t a r y tensor operators; 4 . 5 . A t o m i c interactions under tensorial
f o r m . 5. Configurations of two e l e c t r o n s : 5 . 1 . L-S coupling; 5 . 2 . j - j coupling; 5 . 3 . Validity of various
couplings; 5 . 4 . Electrons in closed subshells. 6. A n t i s y m m e t r y problems: 6 . 1 . N o n - e q u i v a l e n t electrons;
6 . 2 . Equivalent electrons CPF; 6 . 3 . Second q u a n t i z a t i o n . 7. Static fields: 7 . 1 . U n i f o r m m a g n e t i c f i e l d -
Z e e m a n e f f e c t ; 7 . 2 . Uniform e l e c t r i c f i e l d - Stark e f f e c t ; 8. Field q u a n t i z a t i o n and r a d i a t i v e processes:
8 . 1 . Q u a n t i z e d f r e e e l e c t r o m a g n e t i c f i e l d ; 8 . 2 . G e n e r a l formulas for transition probabilities; 8 . 3 . O n e -
photon r a d i a t i v e processes. 9. E l e c t r i c dipole r a d i a t i v e tiansitions: 9 . 1 . Definitions; 9 . 2 . U n e a n d m u l t i p l e t
f a c t o r s ; 9 . 3 . Transition i n t e g r a l s . 10. Relativistic e f f e c t s in a t o m i c s p e c t r a : 1 0 . 1 . Dirac e q u a t i o n ;
1 0 . 2 . Electron in a c e n t r a l f i e l d ; 1 0 . 3 . Fouldy-Wouthuysen t r a n s f o r m a t i o n ; 1 0 . 4 . Breit i n t e r a c t i o n -
Breit-Pauli approximation.

FOREWORD

To give in f i f t e e n l e c t u r e s a g e n e r a l s u r v e y of the t h e o r y of a t o m i c
s t r u c t u r e and t r a n s i t i o n p r o b a b i l i t i e s is s o m e h o w a t a s k which cannot be
c o m p l e t e l y a c c o m p l i s h e d . F o r t u n a t e l y , t h e r e e x i s t m a n y e x c e l l e n t books
c o v e r i n g the f i e l d ; the m a i n o b j e c t of t h e s e l e c t u r e s was to help the r e a d e r
to u s e t h e m m o r e e a s i l y . Many p a r a g r a p h s a r e t a k e n f r o m v a r i o u s books
and d i f f e r only in d e t a i l f r o m the o r i g i n a l p r e s e n t a t i o n . M o r e o v e r , f o r
s o m e p a r t i c u l a r t o p i c s only r e f e r e n c e s a r e given.

1. G E N E R A L F E A T U R E S O F ATOMIC S T R U C T U R E THEORY

1.1. Introduction

T h e o b j e c t of the t h e o r y of a t o m i c s t r u c t u r e i s the s t u d y of s t a t i o n a r y
s t a t e s of i s o l a t e d a t o m s . At f i r s t s i g h t , t h i s study could a p p e a r to be p u r e l y
a c a d e m i c s i n c e an a t o m is n e v e r t o t a l l y i s o l a t e d and, in any c a s e , m u s t
i n t e r a c t with o t h e r p a r t i c l e s ( e s p e c i a l l y photons) in o r d e r to be o b s e r v e d .
H o w e v e r , in m a n y a t o m i c - p h y s i c s e x p e r i m e n t s (low p r e s s u r e , low photon
d e n s i t y ) the e f f e c t s of a t o m - a t o m and p h o t o n - a t o m i n t e r a c t i o n a r e weak
enough to be n e g l e c t e d , and m o s t of the e x p e r i m e n t a l d a t a c a n be i n t e r -
p r e t e d without t a k i n g t h e m into a c c o u n t .

3
4 FENEUILLE

The s t a t i o n a r y s t a t e s of an a t o m o r , in o t h e r w o r d s , its e n e r g y s p e c t r u m
and the c o r r e s p o n d i n g wave f u n c t i o n s depend on:
(a) the k i n e t i c e n e r g y of the v a r i o u s p a r t i c l e s of the a t o m s , e l e c t r o n s
and n u c l e u s , a n d , t h e r e f o r e , on t h e m a s s of t h e n u c l e u s ,
(b) i n t e r n a l i n t e r a c t i o n s a m o n g which it i s convenient to s e p a r a t e the
n u c l e u s - e l e c t r o n i n t e r a c t i o n and the i n t e r a c t i o n b e t w e e n the e l e c t r o n s . A
p r i o r i , the i n t e r a c t i o n b e t w e e n the n u c l e u s and the e l e c t r o n s d e p e n d s on:
(a) the c h a r g e of the n u c l e u s ,
(b) i t s s t r u c t u r e , i . e . i t s v o l u m e and t h e c h a r g e d i s t r i b u t i o n i n s i d e
this volume,
(c) the r e l a t i v e p o s i t i o n s and v e l o c i t i e s of the n u c l e u s and t h e e l e c t r o n s .
T h e i n t e r a c t i o n b e t w e e n the e l e c t r o n s d e p e n d s on the r e l a t i v e p o s i t i o n s and
v e l o c i t i e s of t h e v a r i o u s e l e c t r o n s .
T h e r e f o r e , in a c o m p l e t e l y g e n e r a l way, t h e p r o b l e m is e x t r e m e l y c o m -
p l i c a t e d and cannot be solved without a p p r o x i m a t i o n s . F i r s t , the n u c l e a r
m a s s i s m u c h l a r g e r t h a n the e l e c t r o n m a s s and t h e n u c l e u s i s m u c h s m a l l e r
t h a n t h e a t o m ; t h e n , in a f i r s t a p p r o x i m a t i o n , it is r e a s o n a b l e to c o n s i d e r
the n u c l e u s to be a point c h a r g e with i n f i n i t e m a s s . T h e n , the i n t e r a c t i o n
b e t w e e n the n u c l e u s and the e l e c t r o n s i s p u r e l y C o u l o m b . M o r e o v e r , the
l a r g e s t p a r t of the i n t e r a c t i o n b e t w e e n the e l e c t r o n s i s t h e e l e c t r o s t a t i c
C o u l o m b t e r m and one can e x p e c t that the r e l a t i v e v e l o c i t i e s of e l e c t r o n s
in a t o m s a r e s m a l l enough to be n e g l e c t e d . In f a c t , to r e p r o d u c e i m p o r t a n t
e x p e r i m e n t a l f e a t u r e s , it is n e c e s s a r y to i n t r o d u c e a m a g n e t i c t e r m : t h e
w e l l - k n o w n s p i n - o r b i t i n t e r a c t i o n . As r e g a r d s the r e m a i n i n g e f f e c t s , one
a s s u m e s in g e n e r a l t h a t t h e y a r e s m a l l enough to be i n t r o d u c e d by m e a n s
of p e r t u r b a t i o n t h e o r y . T h e y a r e , e s s e n t i a l l y , r e l a t i v i s t i c c o r r e c t i o n s and
h y p e r f i n e n u c l e a r e f f e c t s ( h y p e r f i n e s t r u c t u r e and i s o t o p e s h i f t ) . The n u c l e a r
e f f e c t s in a t o m i c s p e c t r a will be studied in a n o t h e r p a p e r and, t h e r e f o r e ,
we s h a l l not c o n s i d e r t h e m in t h i s p a p e r . The r e l a t i v i s t i c e f f e c t s , . o n the
o t h e r hand, will be i n v e s t i g a t e d only in a n o n - s o p h i s t i c a t e d way, e x c l u d i n g
quantum electrodynamics.

1.2. N o t a t i o n s and a t o m i c c o n s t a n t s

To avoid r e p e a t i n g m a n y t i m e s the n o t a t i o n s to be u s e d and to give


i m m e d i a t e l y the o r d e r of m a g n i t u d e of a t o m i c q u a n t i t i e s , we s h a l l i n t r o d u c e
t h e m r i g h t away:

ц ( m a s s of e l e c t r o n ) = 9.109 X 10" 2 8 g
-e ( c h a r g e of e l e c t r o n ) = 4.770 X 10" 10 e s u
ft (quantum c o n s t a n t ) = h/2-п = 1.055 X 10" 27 g - c m 2 - s _ 1
с (light v e l o c i t y ) = 2.99792 X 10 1 0 c m • s
a0 (Bohr r a d i u s ) = й 2 / й е 2 = 0.5292 X 10 _ 8 c m
a (fine s t r u c t u r e c o n s t a n t ) = e 2 / c f t = 1 / 1 3 7 . 0 3 6 0 8
R ( R y d b e r g c o n s t a n t ) = a 2 ß c 2 / 2 h c = 109737.31 c m " 1
ß (Bohr m a g n e t o n ) = e f t / 2 ^ c = 0.9274 X 10" 2 0 e r g • G _ 1 .

1.3. A t o m i c H a m i l t o n i a n s and t h e i r s y m m e t r y p r o p e r t i e s

If we u s e t h e a p p r o x i m a t i o n s defined in s u b s e c t i o n 1.1, the n o n - r e l a t i v i s t i c


H a m i l t o n i a n can be w r i t t e n a s
IAEA-SMR-12 / 2 1 5

i i> j
H e r e , Pj i s the l i n e a r m o m e n t u m of the e l e c t r o n i, r j i s the d i s t a n c e
b e t w e e n t h i s e l e c t r o n and the n u c l e u s situated at t h e o r i g i n of c o - o r d i n a t e s ,
r j j i s the d i s t a n c e b e t w e e n the e l e c t r o n s i and j, Ze i s the n u c l e a r c h a r g e ,
and the s u m s r u n o v e r the e l e c t r o n s .
F i r s t , it i s c l e a r t h a t H i s i n v a r i a n t u n d e r i n v e r s i o n with r e s p e c t to the
o r i g i n . T h e r e f o r e , t h e e i g e n s t a t e s of H NR have w e l l - d e f i n e d p a r i t y ; in o t h e r
w o r d s , p a r i t y i s a good q u a n t u m n u m b e r f o r a t o m i c s t a t e s .
Now, if we d e f i n e the t o t a l o r b i t a l a n g u l a r m o m e n t u m L (without
d i m e n s i o n ) by:

L = (l/fi){?i Xpi}
i
it i s e a s y to show t h a t

[HNR,£]=O .

s i n c e f o r any v a l u e of i and j:

[í*i,(Pj) 2 ] = 0

1 1 1
(let u s r e c a l l that Vj — = , V; — = - V, — = ). T h u s , (E,)2 and L z
r r r r r
i i ij ij ij
which c o m m u t e a r e c o m p a t i b l e i n v a r i a n t s f o r H NR and the e i g e n s t a t e s of
H NR c a n be a l s o e i g e n s t a t e s of t h e s e o p e r a t o r s ; the c o r r e s p o n d i n g e i g e n -
v a l u e s L ( L + 1) (in f a c t , one u s e s g e n e r a l l y L) and M L can be u s e d f o r
l a b e l l i n g the e i g e n f u n c t i o n s of H NR .
F u r t h e r m o r e , H ^ r d o e s not depend on spin v a r i a b l e s , and, t h e r e f o r e ,
the t o t a l spin S = ^ s, c o m m u t e s with H N R . T h u s , the e i g e n v a l u e s of (S)
i
(S(S + 1), but one u s e s g e n e r a l l y S) and S z (M s ) c a n be u s e d f o r l a b e l l i n g
the e i g e n s t a t e s of H NR .
F i n a l l y , the e i g e n s t a t e s of H NR can be w r i t t e n a s

P SMSLML>

w h e r e y c o n t a i n s a l l t h e i n f o r m a t i o n r e q u i r e d to d e f i n e s t a t e s u n a m b i g o u s l y
and p i s the p a r i t y n u m b e r e q u a l to + 1 (even s t a t e s ) o r - 1 (odd s t a t e s ) .
H o w e v e r , we have a l r e a d y noticed that, in o r d e r to r e p r o d u c e i m p o r t a n t
e x p e r i m e n t a l f e a t u r e s , it i s n e c e s s a r y to i n t r o d u c e s p i n - o r b i t i n t e r a c t i o n .
The c o r r e s p o n d i n g m a g n e t i c (or r e l a t i v i s t i c ) t e r m c a n be w r i t t e n a s
= J i )
'
6 FENEUILLE

a s we s h a l l s e e when we study r e l a t i v i s t i c e f f e c t s in d e t a i l . It is c l e a r t h a t
n e i t h e r П nor S c o m m u t e with V s o , s i n c e the t h r e e c o m p o n e n t s of (or Sj )
do not c o m m u t e with one a n o t h e r . T h e r e f o r e , f o r the e i g e n s t a t e s of H d e f i n e d
by
H = HNR+ v s o

S, M s , L , M L a r e no l o n g e r good q u a n t u m n u m b e r s . Now, if we d e f i n e the


t o t a l a n g u l a r m o m e n t u m J by J = S + L , we can show e a s i l y that i t s t h r e e
c o m p o n e n t s c o m m u t e with H. T h u s , the e i g e n s t a t e s of H can be l a b e l l e d
by the e i g e n v a l u e s of (J) 2 and J z and they can be w r i t t e n a s

I TP J M J >

s i n c e it i s o b v i o u s t h a t H i s s t i l l p a r i t y i n v a r i a n t . T h e s e i n v a r i a n c e p r o p e r -
t i e s a r e valid f o r any a t o m i c H a m i l t o n i a n , even f u l l y r e l a t i v i s t i c , a s long
a s the t o t a l a n g u l a r m o m e n t u m Ï of the n u c l e u s i s z e r o . If not, only
( F ) 2 = (! + J ) 2 and F z =I Z + J z c o m m u t e with t h e a t o m i c H a m i l t o n i a n ; in t h i s
c a s e , J and M j a r e no l o n g e r good q u a n t u m n u m b e r s . H o w e v e r ; n u c l e a r
p e r t u r b a t i o n is in g e n e r a l e x t r e m e l y s m a l l and u n d e r t h e s e c o n d i t i o n s ,
J and M j can s t i l l be c o n s i d e r e d as good q u a n t u m n u m b e r s . In t h e s a m e
way, t h e s p i n - o r b i t e n e r g y i s v e r y o f t e n r a t h e r s m a l l c o m p a r e d with the
d i s t a n c e s b e t w e e n n o n - r e l a t i v i s t i c e n e r g y l e v e l s ; t h e n , S and L r e m a i n
a p p r o x i m a t e q u a n t u m n u m b e r s and can be u s e d , but only a s an a p p r o x i m a t i o n ,
to l a b e l the e i g e n s t a t e s of H which r e a d in t h i s c a s e

ITPSLJMJ)

H o w e v e r , in m a n y c a s e s t h i s a p p r o x i m a t i o n i s not valid a s , e . g . f o r noble


g a s s p e c t r a w h e r e , a s we s h a l l s e e l a t e r , it i s p o s s i b l e to define o t h e r
a p p r o x i m a t e q u a n t u m n u m b e r s in o r d e r to l a b e l t h e s t a t e s .

1.4. A p p r o x i m a t i o n m e t h o d s

T h e p h y s i c a l a p p r o x i m a t i o n s defined in s u b s e c t i o n 1.1 a r e i n s u f f i c i e n t
to s o l v e (i.e. to d e t e r m i n e the e i g e n v a l u e s and e i g e n f u n c t i o n s ) the S c h r ö d i n g e r
equation f o r m a n y - e l e c t r o n a t o m s even in the n o n - r e l a t i v i s t i c c a s e . T h e r e -
f o r e , one of the m o s t i m p o r t a n t a c t i v i t i e s in the t h e o r y of a t o m i c s t r u c t u r e
w a s (and s t i l l i s ) to find m a t h e m a t i c a l a p p r o x i m a t i o n s ( s o m e t i m e s on a
p h y s i c a l b a s i s ) which allow u s to obtain a p p r o x i m a t e s o l u t i o n s to t h e a t o m i c
p r o b l e m . M o s t of t h e s e s t a r t with an i n d e p e n d e n t - p a r t i c l e m o d e l ; in t h i s
c h a p t e r we s h a l l study only the v a r i o u s ways of u s i n g s u c h a m o d e l and we
s h a l l exclude m o r e s o p h i s t i c a t e d t r e a t m e n t s , such a s c o n f i g u r a t i o n i n t e r -
actions or correlation effects.

1.4.1. C e n t r a l field a p p r o x i m a t i o n

The p r i n c i p l e of t h i s a p p r o x i m a t i o n i s v e r y s i m p l e : one t r i e s to
d e t e r m i n e a c e n t r a l p o t e n t i a l U ( r ) , whose e f f e c t s a r e c l o s e enough to t h o s e
of C o u l o m b i n t e r a c t i o n b e t w e e n all the p a r t i c l e s of t h e a t o m to p e r m i t a
c a l c u l a t i o n of r e s i d u a l i n t e r a c t i o n s by m e a n s of p e r t u r b a t i o n t h e o r y .
M a t h e m a t i c a l l y , t h i s m e a n s that we split the a t o m i c H a m i l t o n i a n into two
p a r t s of quite d i f f e r e n t o r d e r s of m a g n i t u d e :
IAEA-SMR-12 / 2 1 7

H = н0 +н1

Ho = ^ (Pj) 2 - e U ( r j )j- (principal Hamiltonian)

Ze2} e2
+ eU(r. ) - — — r + ) ~ + Vs0 (perturbing Hamiltonian)
1J
i i>j
The wave f u n c t i o n s and the e i g e n v a l u e s of Ho c a n be obtained e a s i l y s i n c e
a l l the c o - o r d i n a t e s can be s e p a r a t e d . We r e c a l l t h a t , f o r bound s t a t e s ,
the e i g e n v a l u e s of h, d e f i n e d by
h (p)2-eU(r)

a r e l a b e l l e d by the two q u a n t u m n u m b e r s n and Í ( i < n , i n t e g e r s ) while


the c o r r e s p o n d i n g wave f u n c t i o n s depend on the f i v e q u a n t u m n u m b e r s n , s ,
m s , I , nijf (or n , s , I , j, m j ) . M o r e p r e c i s e l y

h | n s m s i m , ) = e n{ | n s m s Í m {)>

I n s m s < i B ( ) = -i R n f ( r ) I s mj > \ i т { >

|üm { ]> = Y í r r ] í (6,9), ( s p h e r i c a l h a r m o n i c ) , | s m s ) > (spin f u n c t i o n )

d2 1(1 + 1) 2M
d r 2 ní r 2 ^ni"1" f j 2 t c
n{

F o r a C o u l o m b a t t r a c t i v e p o t e n t i a l U(r) = Z e / r ,
-Z2
e e q 2 c 2
ni = n = 2^2 ^

In any c a s e , ( n - i - 1 ) is t h e n u m b e r of n o d e s of R n i ( r ) excluding o r i g i n and


infinity.

E n e r g y l e v e l s of Ho. The d i s c r e t e e i g e n v a l u e s of H 0 can be w r i t t e n


as follows:

E 0 = ^ N(ni) e n t , ^ N ( n i ) = N ( n u m b e r of e l e c t r o n s )
ne ní
N(ní) b e i n g the n u m b e r of e l e c t r o n s in the s u b s h e l l ni. The P a u l i e x c l u s i o n
p r i n c i p l e i m p l i e s a s u p p l e m e n t a r y condition

N(nje) S (4Í +2)

Giving the n u m b e r s N(ni) i s e q u i v a l e n t to d e f i n i n g an e l e c t r o n c o n f i g u r a t i o n


which r e a d s
, 0 Мщк) , . .ВДМг)
(n x ii) (n2i2)
with a single e n e r g y l e v e l in z e r o - o r d e r a p p r o x i m a t i o n .
8 FENEUILLE

F o r n e u t r a l a t o m s , the g r o u n d c o n f i g u r a t i o n , i . e . t h a t of l o w e s t e n e r g y ,
i s g i v e n b y M a d e l u n g 1 s e m p i r i c a l r u l e w h i c h d e r i v e s f r o m a n a n a l y s i s of M e n d e l e e v ' s
t a b l e ; it c a n b e f o r m u l a t e d a s f o l l o w s : the e n e r g y of a o n e - e l e c t r o n o r b i t
i n c r e a s e s w i t h (n + i ) and if (n + i ) i s f i x e d , it g r o w s a s n i s g r o w i n g . T h u s
eis < e2s < e 2p< e 3s < e 3 p < e 4s < e 3 d - " • F o r h i g h l y i o n i z e d a t o m s , which a r e
n e a r l y h y d r o g e n i c , t h e a b o v e r u l e is not v a l i d and we s e e t h a t e n i i n c r e a s e s
with i n c r e a s i n g n a n d , f o r f i x e d n , with SL. T h e n , in p a r t i c u l a r , e 3 d < e 4 s .
T h e d i s c r e t e s p e c t r u m of l i g h t a t o m s c a n be u s u a l l y d e s c r i b e d by
o n e - e l e c t r o n e x c i t a t i o n s f r o m t h e h i g h e s t - e n e r g y s u b s h e l l of the g r o u n d
c o n f i g u r a t i o n . F o r e x a m p l e , the ground c o n f i g u r a t i o n of n e u t r a l s o d i u m
(Na I) i s I s 2 2 s 2 2p6 3 s and a l l t h e d i s c r e t e l e v e l s of t h e c o r r e s p o n d i n g
s p e c t r u m b e l o n g t o t h e c o n f i g u r a t i o n s I s 2 2 s 2 2 p 6 n i . We m u s t m e n t i o n
t h a t , f o r h i g h v a l u e s of n , the e n e r g i e s of t h e s e c o n f i g u r a t i o n s h a v e the
s a m e l i m i t , n a m e l y , the g r o u n d - s t a t e e n e r g y of Na + ; t h e r e f o r e , t h e r e a p p e a r
s o m e s t r u c t u r e s w h i c h a r e s i m i l a r to t h o s e e n c o u n t e r e d in t h e h y d r o g e n
s p e c t r u m and w h i c h a r e c a l l e d R y d b e r g s e r i e s . F o r h e a v i e r a t o m s , t h e
e n e r g y s e p a r a t i o n b e t w e e n t h e o u t e r m o s t s u b s h e l l b e c o m e s v e r y s m a l l with
r e s p e c t t o r e s i d u a l i n t e r a c t i o n s and s o m e d i s c r e t e l e v e l s o b s e r v e d b e l o n g
to configurations r e s u l t i n g f r o m t w o - e l e c t r o n excitations (configuration
4p 3d of C a I, f o r e x a m p l e ) . T h i s is a l w a y s t h e c a s e f o r t r a n s i t i o n e l e m e n t s ,
r a r e e a r t h s and a c t i n i d e s e s p e c i a l l y . On t h e o t h e r h a n d , t h e r e a r e m a n y
c o n f i g u r a t i o n s w h o s e e n e r g i e s a r e v e r y c l o s e to the g r o u n d e n e r g y and s o m e -
t i m e s M a d e l u n g ' s r u l e d o e s not apply a n y l o n g e r . F o r e x a m p l e , in n e u t r a l
r a r e e a r t h s p e c t r a , we o b s e r v e m a n y e n e r g y l e v e l s v e r y c l o s e to one a n o t h e r
which b e l o n g to t h e c o n f i g u r a t i o n s S s 2 4 f n , 6s 4 f n 5d, 6 s 2 4 f n " 1 6 p , and
6s 4f n " 1 5d 6p, r e s p e c t i v e l y . It i s obvious t h a t , in t h i s c a s e , the c o r r e s p o n d i n g
l i n e s p e c t r a h a v e no s i m p l e s t r u c t u r e s and u s u a l l y t h e r e a r e a l a r g e n u m b e r
of l i n e s i n s i d e a n a r r o w s p e c t r a l r a n g e : t h e s e a r e c o m p l e x s p e c t r a .
B e y o n d d i s c r e t e s t a t e s with e n e r g i e s l o w e r t h a n t h a t of t h e f i r s t
i o n i z a t i o n l e v e l , t h e r e a r e a c o n t i n u u m and d i s c r e t e s t a t e s with e n e r g i e s
higher than the f o r m e r s . T h e s e d i s c r e t e s t a t e s a r e auto-ionizing s t a t e s
s i n c e u s u a l l y , when a n a t o m i s in s u c h a s t a t e , i t l o s e s a n e l e c t r o n s p o n -
t a n e o u s l y . T h e o b s e r v e d a u t o - i o n i z i n g s t a t e s a r e u s u a l l y d u e to o n e - e l e c t r o n
e x c i t a t i o n of a l o w - l y i n g c o m p l e t e s u b s h e l l o r to t w o - e l e c t r o n e x c i t a t i o n
( I s 2 s 2 and I s 2p 2 of L i I, f o r e x a m p l e ) . We m u s t n o t e t h a t the l i n e s o b s e r v e d
i n X - r a y e m i s s i o n s p e c t r a a r e d u e t o t r a n s i t i o n s b e t w e e n l e v e l s of t h i s t y p e .
W a v e f u n c t i o n s of Hq_. In g e n e r a l , t h e e l e c t r o n c o n f i g u r a t i o n i s h i g h l y
d e g e n e r a t e . T h i s m e a n s t h a t i t can be d e s c r i b e d b y a l a r g e n u m b e r of
d i f f e r e n t q u a n t u m s t a t e s . T h e s e s t a t e s c a n be d e f i n e d by g i v i n g N a t o m i c
o r b i t s (an o r b i t b e i n g d e f i n e d b y ф = n s m s Î m^ ) and b y t a k i n g into a c c o u n t
P a u l i ' s a n t i s y m m e t r y p r i n c i p l e ; such a s t a t e c a n be r e p r e s e n t e d by a
Slater determinant
•Ml) <M 1)

{<í>i 0s «М -
•MS) <ys)

Фгт * (N)

S u b s c r i p t s l a b e l o r b i t s ; i n d i c e s within p a r e n t h e s e s l a b e l e l e c t r o n s . It i s
e a s y to s h o w t h a t t h e n u m b e r of d i s c r e t e s t a t e s c o r r e s p o n d i n g to the c o n -
figuration ( П ! ^ ) ^ " ! ^ (n2í2)N(nzt2) is equal to
IAEA-SMR-12 / 2 1 9

q_ g!
where С
P~ P'(Q-P)!

F o r e x a m p l e , the c o n f i g u r a t i o n I s 2 2s 2 2p 2 3s c o n t a i n s c f X c f X CÍj X С 2 = 30
discrete states.
H o w e v e r , in o r d e r to t a k e into account r e s i d u a l i n t e r a c t i o n s , we have
to d i a g o n a l i z e the m a t r i x of H 1 f o r the s t a t e s of the c o n f i g u r a t i o n c o n s i d e r e d ;
t h i s p r o b l e m can be l a r g e l y s i m p l i f i e d if we can u s e the s y m m e t r y p r o p e r t i e s
of the H a m i l t o n i a n . We know that in p a r t i c u l a r the m a t r i x of H 1 i s d i a g o n a l
with r e s p e c t to J and i n d e p e n d e n t of Mj b e c a u s e of s p h e r i c a l s y m m e t r y .
M o r e o v e r , t h e m a t r i x of t h e m o s t i m p o r t a n t p a r t of H 1 , i . e . the e l e c t r o -
s t a t i c p a r t , i s d i a g o n a l with r e s p e c t to S and L . U n f o r t u n a t e l y , S l a t e r d e t e r -
m i n a n t s a r e u s u a l l y not e i g e n f u n c t i o n s of S 2 , L 2 and J 2 ; only M s , M L and
Mj a r e well d e f i n e d . One p o s s i b l e way of s o l v i n g t h i s p r o b l e m is to u s e
s u c h l i n e a r c o m b i n a t i o n s of S l a t e r d e t e r m i n a n t s which a r e e i g e n f u n c t i o n s
of S 2 , L 2 and J 2 . H o w e v e r , though p o s s i b l e in p r i n c i p l e , t h i s m e t h o d b e c o m e s
e x t r e m e l y t e d i o u s , e s p e c i a l l y when t h e r e a r e s e v e r a l e q u i v a l e n t o r b i t s in
t h e c o n f i g u r a t i o n s t u d i e d . F o r t u n a t e l y , it i s p o s s i b l e c o m p l e t e l y to avoid
t h e c o n s t r u c t i o n of s u c h c o m b i n a t i o n s of S l a t e r d e t e r m i n a n t s by u s i n g a n g u l a r -
m o m e n t u m a l g e b r a and by d e f i n i n g the s t a t e s a s r e s u l t i n g f r o m a coupling
of the v a r i o u s individual a n g u l a r m o m e n t a . The r u l e s f o r coupling of two
d i s t i n c t a n g u l a r m o m e n t a a r e v e r y s i m p l e , but f o r e q u i v a l e n t o r b i t s the
p r o b l e m b e c o m e s m o r e c o m p l e x , s i n c e we have to t a k e into a c c o u n t the
a n t i s y m m e t r y p r i n c i p l e . An i m p o r t a n t p a r t of t h i s p a p e r will be devoted
to s t u d y i n g a n g u l a r - m o m e n t u m a l g e b r a t e c h n i q u e s and m e t h o d s allowing the
b u i l d - u p of w e l l - d e f i n e d s t a t e s f o r e q u i v a l e n t e l e c t r o n c o n f i g u r a t i o n s .

The e n e r g y m a t r i x . In a f i r s t a p p r o x i m a t i o n , the e n e r g y l e v e l s belonging


to a given c o n f i g u r a t i o n a r e obtained by d i a g o n a l i z i n g the m a t r i x of H j f o r
t h e s t a t e s of t h i s c o n f i g u r a t i o n . Such a d i a g o n a l i z a t i o n can be avoided if
V s 0 i s negligible with r e s p e c t to C o u l o m b i n t e r a c t i o n and if t h e r e i s only
one t e r m (SL) of a given type; g e n e r a l l y , h o w e v e r , in o r d e r to obtain a c c u r a t e
wave f u n c t i o n s , it i s n e c e s s a r y to p e r f o r m t h i s d i a g o n a l i z a t i o n . In any c a s e ,
we have to e v a l u a t e t h e m a t r i x e l e m e n t s of H j . T h e s e m a t r i x e l e m e n t s can
a l w a y s be w r i t t e n as a f i n i t e s u m of t e r m s which c o n s i s t s of a r a d i a l p a r t
and an a n g u l a r p a r t . The a n g u l a r p a r t can be c a l c u l a t e d without d i f f i c u l t y
by u s i n g a n g u l a r - m o m e n t u m a l g e b r a , but c o m p u t a t i o n of the r a d i a l p a r t
r e q u i r e s the knowledge of U ( r ) . We s h a l l not d i s c u s s t h i s p r o b l e m in d e t a i l
b u t , in f a c t , it i s s o m e t i m e s p o s s i b l e to avoid it by c o n s i d e r i n g the r a d i a l
p a r t s of the m a t r i x e l e m e n t s a s p a r a m e t e r s to be f i t t e d to e x p e r i m e n t a l
data. This s e m i - e m p i r i c a l method is p a r t i c u l a r l y useful f o r analysing
complex spectra.
If we a r e i n t e r e s t e d in obtaining a c c u r a t e r a d i a l wave f u n c t i o n s , and
if coupling i s n e a r l y p u r e (i.e. if we can avoid any d i a g o n a l i z a t i o n of H j ,
i . e . if we can n e g l e c t s p i n - o r b i t i n t e r a c t i o n ) , a convenient way i s to u s e
the v a r i a t i o n p r i n c i p l e and the s o - c a l l e d H a r t r e e - F o c k a p p r o x i m a t i o n which
we a r e going to d i s c u s s b r i e f l y in the next s e c t i o n .

1.4.2. Hartree-Fock approximation

The key idea of t h i s type of a p p r o x i m a t i o n is b a s e d on the f a c t that the


S c h r ö d i n g e r equation i s t h e d i f f e r e n t i a l equation c o r r e s p o n d i n g to a m i n i m u m
10 FENEUILLE

p r o b l e m in v a r i a t i o n a l c a l c u l u s . In f a c t , it i s e a s y to show t h a t •( ф
i s s t a t i o n a r y f o r |i/<)> in the neighbourhood of e a c h of the n o r m a l i z e d e i g e n -
f u n c t i o n s of H and that the s t a t i o n a r y v a l u e i s equal to the c o r r e s p o n d i n g
allowed v a l u e . T h e r e f o r e , i n s t e a d of s e e k i n g throug'h i t s S c h r ö d i n g e r
e q u a t i o n , one c a n t r y to r e p r e s e n t the unknown f u n c t i o n \фУ a s belonging
to a c l a s s of f u n c t i o n s and to apply the v a r i a t i o n a l p r i n c i p l e to t h i s c l a s s
of f u n c t i o n s . O b v i o u s l y , f o r h e a v y a t o m s with m a n y e l e c t r o n s , t h i s c l a s s
cannot be unbounded and, t h e r e f o r e , the m e t h o d y i e l d s only t h a t m e m b e r of
the f a m i l y which g i v e s the c l o s e s t f i t to t h e t r u e e i g e n f u n c t i o n and it i s only
an a p p r o x i m a t i o n . T h i s a p p r o x i m a t i o n d e p e n d s on the type of t r i a l f u n c t i o n
a d m i t t e d f o r |i//)>. The m o s t f a m o u s t r i a l f u n c t i o n and c e r t a i n l y t h e e a s i e s t
to w o r k with i s t h e H a r t r e e - P o c k f u n c t i o n .
F r o m c e n t r a l f i e l d a p p r o x i m a t i o n we know t h a t , in an i n d e p e n d e n t -
p a r t i c l e m o d e l , one can r e p r e s e n t an a t o m i c s t a t e by a S l a t e r d e t e r m i n a n t
b u i l t up f r o m a t o m i c o r b i t s of the type:

| n s i m s m i ) = -i R n i (r ) | s m s У | i m цУ

The H a r t r e e - P o c k f u n c t i o n is of the s a m e type and t h e r e f o r e only the r a d i a l


f u n c t i o n s R n j / r a r e s u b j e c t to v a r i a t i o n , but they a r e not s p e c i f i e d to be
s o l u t i o n s of a p a r t i c u l a r c e n t r a l field p r o b l e m . E s p e c i a l l y , the R n i ( r )
f u n c t i o n s depend on the p a r t i c u l a r c o n f i g u r a t i o n being c o n s i d e r e d a n d , a s a
c o n s e q u e n c e , the R n i ( r ) f u n c t i o n s obtained f o r the d i f f e r e n t c o n f i g u r a t i o n s
a r e not o r t h o g o n a l and, t h u s , cannot be m a d e the b a s i s f o r a c a l c u l a t i o n in
which c o n f i g u r a t i o n i n t e r a c t i o n i s t a k e n into a c c o u n t by p e r t u r b a t i o n t h e o r y .
H o w e v e r , it i s p o s s i b l e to i n t r o d u c e c o n f i g u r a t i o n i n t e r a c t i o n by u s i n g the
v a r i a t i o n a l p r i n c i p l e only. A s r e g a r d s the H a r t r e e - P o c k e q u a t i o n s , t h e y
will not be d i s c u s s e d in d e t a i l in a n o t h e r c h a p t e r , s i n c e we plan to d e s c r i b e
e s s e n t i a l l y the m e t h o d s allowing us to c a l c u l a t e the a n g u l a r p a r t of t h e
m a t r i x e l e m e n t s of H j .

1.4.3. L a y z e r expansion

If we change r into p = r Z , p b e c o m e s Ťr = ( l / Z ) p and t h e r e f o r e the n o n -


r e l a t i v i s t i c H a m i l t o n i a n t a k e s the f o r m

^[Zfe^-ÍKXÍ]
i i> j
a n d , if Z i s l a r g e , we can w r i t e , a c c o r d i n g to p e r t u r b a t i o n t h e o r y ,
E = Z 2 ( A 0 + A j Z " 1 + A 2 Z " 2 + ...)
Since t h e u n p e r t u r b e d H a m i l t o n i a n i s p u r e l y hydro g e n i e , A 0 d e p e n d s only
on the n u m b e r of e l e c t r o n s N(n) in e a c h s h e l l n. M o r e p r e c i s e l y

A0 = ^ N ( n ) { - « 2 M C 2 ^ }

To give the n u m b e r N(n) i s e q u i v a l e n t to t h e d e f i n i t i o n of a c o m p l e x


e x p r e s s i o n which r e a d s n ^ ^ n ^ " 2 ' ... , with a single e n e r g y l e v e l in z e r o -
order approximation.
IAEA-SMR-12 / 2 1 11

O b v i o u s l y , a c o m p l e x i s highly d e g e n e r a t e , s i n c e g e n e r a l l y it c o n t a i n s
m a n y c o n f i g u r a t i o n s and in o r d e r to obtain Aj^ we have to d i a g o n a l i z e t h e
m a t r i x of

i>j
f o r the s t a t e s of t h e c o n s i d e r e d c o m p l e x . C o n s e q u e n t l y , t h i s m e t h o d s e e m s
to be m o r e c o m p l i c a t e d than the u s u a l c e n t r a l f i e l d t h e o r y . H o w e v e r , it i s
p a r t i c u l a r l y well suited to study i s o e l e c t r o n i c s e q u e n c e s (since l / Z i s the
e x p a n s i o n p a r a m e t e r ) and s i n c e we w o r k with h y d r o g e n i c wave f u n c t i o n s ,
a l l t h e f o r m u l a s can be w r i t t e n in an a n a l y t i c a l f o r m . F o r n e u t r a l a t o m s ,
n e v e r t h e l e s s , the f i r s t two t e r m s p r o v i d e but a r a t h e r p o o r a p p r o x i m a t i o n
(which i s o b v i o u s f r o m M a d e l u n g ' s r u l e ) and t h e r e f o r e , s i n c e i s o e l e c t r o n i c
s e q u e n c e s will be studied in a n o t h e r p a p e r , we s h a l l not d e s c r i b e the L a y z e r
e x p a n s i o n in g r e a t e r d e t a i l .

1.5. C o n c l u s i o n and c o n t e n t s of the p a p e r

The m a i n p r o b l e m in the t h e o r y of a t o m i c s t r u c t u r e is to c a l c u l a t e the


m a t r i x e l e m e n t s . We have s e e n t h a t , in i n d e p e n d e n t - p a r t i c l e m o d e l s , t h e s e
m a t r i x e l e m e n t s can be s e p a r a t e d into a r a d i a l and an a n g u l a r p a r t . F i r s t ,
we s h a l l d e s c r i b e the g e n e r a l m e t h o d s allowing u s to obtain the a n g u l a r
p a r t , with s p e c i a l r e f e r e n c e to s y m m e t r y p r o p e r t i e s . T h e r e f o r e , we s h a l l
r e c a l l f i r s t the f u n d a m e n t a l p o i n t s of g r o u p t h e o r y , t h e n we s h a l l study
a n g u l a r m o m e n t u m a l g e b r a and t h e c o n c e p t of f r a c t i o n a l p a r e n t a g e which
i s e s s e n t i a l f o r the s t u d y of e q u i v a l e n t e l e c t r o n c o n f i g u r a t i o n s . C o n f i g u r a t i o n
i n t e r a c t i o n will be studied in a s e c o n d a p p r o x i m a t i o n by u s i n g second
q u a n t i z a t i o n t e c h n i q u e s . A f t e r w a r d s , the m o s t i m p o r t a n t f e a t u r e s a p p e a r i n g
in the c a l c u l a t i o n of t r a n s i t i o n p r o b a b i l i t i e s will be studied with s p e c i a l
r e f e r e n c e to i n t e r m e d i a t e coupling and c o n f i g u r a t i o n e f f e c t s and, f i n a l l y ,
the f u n d a m e n t a l a s p e c t s of r e l a t i v i s t i c t h e o r y will be d e s c r i b e d in an
elementary form.

2. E L E M E N T S OF GROUP THEORY

2.1. F u n d a m e n t a l p r o p e r t i e s

2.1.1. Group

A g r o u p i s a s e t (finite o r infinite) of e l e m e n t s R j ... R g ... which


s a t i s f y the following conditions:
(a) e v e r y p a i r of e l e m e n t s R Q , R p can be c o m b i n e d to a p r o d u c t R 0 R
which a l s o b e l o n g s to the s e t ;
(b) t h i s p r o d u c t i s a s s o c i a t i v e : R T ( R 0 R ) = ( R T R 0 ) R p ;
(c) the s e t c o n t a i n s an i d e n t i t y e l e m e n t I s u c h t h a t R 0 I = I R 0 = R 0 ;
(d) f o r e a c h e l e m e n t R 0 t h e r e e x i s t s an i n v e r s e e l e m e n t R - i belonging
to the s e t , i . e . R p R ; 1 = R ^ R , , = I.
12 FENEUILLE

2.1.2. Subgroup

If it i s p o s s i b l e to find a m o n g the e l e m e n t s of a g r o u p G a s u b s e t which


i s a g r o u p H, then H i s a s u b g r o u p of G, that i s

GDH

2.1.3. Direct product

If t h e e l e m e n t s of two g r o u p s G f R j R g ...) and G ' i R ' j R ^ ...) c o m m u t e


[R0RV = R ' T R 0 ] , t h e n the s e t of e l e m e n t s R v R 2 R ' j , R' 2 . . . , (R R' T ), ...
i s a g r o u p ; t h i s g r o u p i s the d i r e c t p r o d u c t of the two g r o u p s G and G 1 .
It r e a d s GXG'.

2.1.4. I s o m o r p h i s m and h o m o m o r p h i s m

Two g r o u p s G and H a r e said to be i s o m o r p h i c if a unique c o r r e s p o n d e n c e


can be d r a w n b e t w e e n the e l e m e n t s RJR2 ... of G and Р Х Р 2 ... of H s u c h
that

R 0 R p = RT if P 0 P p = PT

If the c o r r e s p o n d e n c e i s not unique, and if one and only one e l e m e n t


of G c o r r e s p o n d s to any a r b i t r a r y e l e m e n t of H, then H i s h o m o m o r p h i c
to G.

2.2. C o n j u g a t e e l e m e n t s — c l a s s e s

The e l e m e n t R T = R p R 0 R" p 1 i s said t o ' b e c o n j u g a t e to R 0 . A s e t of


e l e m e n t s which a r e c o n j u g a t e to one a n o t h e r i s called a c l a s s .
E a c h e l e m e n t belongs to one c l a s s and only to o n e . H e n c e , the e l e m e n t s
of a g r o u p can be subdivided into d i s t i n c t c l a s s e s .
The i d e n t i t y e l e m e n t a l w a y s f o r m s a c l a s s by i t s e l f .
If a g r o u p i s A b e l i a n , i . e . if all its e l e m e n t s c o m m u t e , e a c h e l e m e n t
f o r m s a c l a s s by i t s e l f .

2.3. M a t r i x r e p r e s e n t a t i o n s — c h a r a c t e r s
If a s e t of m a t r i c e s R x , R 2 ... f o r m a g r o u p which i s i s o m o r p h i c o r
h o m o m o r p h i c to a g r o u p G, t h e s e m a t r i c e s a r e said to f o r m a r e p r e s e n t a t i o n
of G.

T r a c e s of c o n j u g a t e m a t r i c e s a r e e q u a l .

Proof:
Tr(Rc) = ^ г й (ст)
i

Tr(R0RT) = ^ r ; j (d)r j i (T)= T r ( R p R 0 )


i, j
T r f R p R ^ ' 1 ) = Tr(R0)
IAEA-SMR-12 / 2 1 13

Such a t r a c e i s c a l l e d a " c h a r a c t e r " and it h a s the s a m e v a l u e a s all the


e l e m e n t s of a c l a s s . U s u a l l y it i s w r i t t e n a s xR(cO-
If u n d e r the o p e r a t i o n s of the g r o u p a f u n c t i o n s p a c e (cp) t r a n s f o r m s
such as

(Ф) - R0(q>)
the m a t r i c e s R 0 f o r m a r e p r e s e n t a t i o n of the g r o u p and the f u n c t i o n s cp a r e
said to f o r m a b a s i s f o r the r e p r e s e n t a t i o n .
If S i s a n o n - s i n g u l a r m a t r i x and if the m a t r i c e s R 0 f r o m a r e p r e s e n t a t i o n
r R of G, then so do t h e m a t r i c e s R 0 = S R 0 S _ 1 . The two r e p r e s e n t a t i o n s r R
and Г р a r e c a l l e d e q u i v a l e n t r e p r e s e n t a t i o n s .
A r e p r e s e n t a t i o n is said to be r e d u c i b l e if it i s p o s s i b l e to find a m a t r i x S,
so t h a t a l l t h e m a t r i c e s of the c o r r e s p o n d i n g equivalent r e p r e s e n t a t i o n a r e
of the f o r m :
0
1m
R'o Jr n

0 R "0

w h e r e m and n do not depend on ст.


If it is i m p o s s i b l e to find s u c h a m a t r i x S, the r e p r e s e n t a t i o n is i r r e d u c i b l e .
The d e c o m p o s i t i o n of the r e d u c i b l e r e p r e s e n t a t i o n into i t s i r r e d u c i b l e
c o n s t i t u e n t s is s y m b o l i z e d by

(Гк o c c u r s CR t i m e s in the d e c o m p o s i t i o n of T w ) and can be e x p r e s s e d


a l g e b r a i c a l l y by t h e e q u a t i o n

x W(a) C rX R(cO
R

f o r all ст.

Schures l e m m a (Weyl's f o r m )

(a) If R 0 and Q 0 f o r m two i n e q u i v a l e n t i r r e d u c i b l e m a t r i x r e p r e s e n t a -


t i o n s of a g r o u p , and if a m a t r i x A ( s q u a r e , if p o s s i b l e ) e x i s t s s u c h t h a t

R0A = AQ0

f o r a l l a , then A = 0.
(b) If the m a t r i c e s R o f o r m a n i r r e d u c i b l e r e p r e s e n t a t i o n of a g r o u p
and if

R0A = AR0
14 FENEUILLE

f o r a l l ст, t h e n A i s a c o n s t a n t m u l t i p l i e d by the unit m a t r i x . It f o l l o w s f r o m


(a) t h a t , if R c and Q 0 a r e u n i t a r y and f o r m two inequivalent m a t r i x r e p r e -
s e n t a t i o n s of a f i n i t e g r o u p ,

X rij(CT)qVCT) = 0 for a11


j' and k

It f o l l o w s f r o m (b) t h a t , ' i f a l l the m a t r i c e s of an i r r e d u c i b l e r e p r e s e n t a t i o n


of a f i n i t e g r o u p a r e u n i t a r y , t h e n

^гу(ст)г*к(ст) = 6 ( i , i ) 6 ( j , k ) | -
0

w h e r e g i s the n u m b e r of e l e m e n t s of the c o n s i d e r e d g r o u p and n r i s the


d i m e n s i o n of t h e m a t r i c e s R o .

O t h e r f u n d a m e n t a l p r o p e r t i e s of f i n i t e g r o u p s (without p r o o f )

The n u m b e r of i n e q u i v a l e n t i r r e d u c i b l e r e p r e s e n t a t i o n s is e q u a l to
the n u m b e r of d i s t i n c t c l a s s e s of the g r o u p c o n s i d e r e d . If we d e n o t e by
x t C i T j ) the c h a r a c t e r of the m a t r i c e s c o r r e s p o n d i n g to the c l a s s C t within
the r e p r e s e n t a t i o n F j , then

Y [х-ЧС^фхССкГ,)] = -щ à (i,к)
j

£ NixíCirpxíqr,) = ga(M)
1
Ni = n u m b e r of e l e m e n t s of the c l a s s It f o l l o w s that if

х (с;г{) ^ C j x í q r j )
i

then

Cj " ~ ^ x(Cir{ ) x*(C;rj )

2.4. K r o n e c k e r product

L e t u s s u p p o s e that the n f u n c t i o n s фг , фj, ... фп f o r m a b a s i s of a r e p r e


s e n t a t i o n F x and that the m f u n c t i o n s ф1 ..., фе ..., фт f o r m a b a s i s of a
r e p r e s e n t a t i o n Гу of a g r o u p G. T h e n the m n f u n c t i o n s ф^ф t f o r m a b a s i s
of a r e p r e s e n t a t i o n T w which i s c a l l e d the K r o n e c k e r p r o d u c t (or the d i r e c t
p r o d u c t ) of t h e r e p r e s e n t a t i o n s Г х and Г and which i s w r i t t e n a s

r
w=rxxry=ryXF x
IAEA-SMR-12 / 2 1 15

If u n d e r an o p e r a t i o n of the g r o u p

i V

(ff)
"l/U
j.í
T h e r e f o r e xw(CT) = Хх(ст) x y ( a )-
L e t u s now s u p p o s e that Г х and Гу a r e i r r e d u c i b l e , T w i s u s u a l l y
r e d u c i b l e and can be w r i t t e n a s

The b a s i s f u n c t i o n s of Г к can be w r i t t e n a s l i n e a r c o m b i n a t i o n s of the


mn functions ф2

pk(Fß) =^(ГХ

(the s y m b o l ß c h a r a c t e r i z e s t h e equivalent i r r e d u c i b l e r e p r e s e n t a t i o n s
if C s i s g r e a t e r than one). The i n v e r s e t r a n s f o r m a t i o n can be w r i t t e n a s

=
X(rs/3k|r*j; ryi)Pk(rsß)
к, s, ß

The c o e f f i c i e n t s ( ; |) a r e called C l e b s c h - G o r d a n c o e f f i c i e n t s . If the


f u n c t i o n s ф j , фе and pk(rsß) are normalized, they f o r m a unitary matrix
and:
( ; I) = (I ; )*
2.5. W i g n e r - E c k a r t t h e o r e m

T h i s t h e o r e m i s f u n d a m e n t a l in o r d e r to apply group t h e o r y to the


t h e o r y of a t o m i c s t r u c t u r e .
L e t u s s u p p o s e t h a t we have to evaluate the m a t r i x e l e m e n t

and t h a t the f o l l o w i n g conditions a r e s a t i s f i e d :


(1) t h e p f u n c t i o n s f o r m an o r t h o n o r m a l b a s i s f o r the i r r e d u c i b l e r e p r e -
s e n t a t i o n Г р of a g r o u p G;
(2) t h e q f u n c t i o n s tpj f o r m an o r t h o n o r m a l b a s i s f o r the i r r e d u c i b l e
r e p r e s e n t a t i o n r Q of G;
(3) t h e r f u n c t i o n s ву. f o r m an o r t h o n o r m a l b a s i s f o r the i r r e d u c i b l e
r e p r e s e n t a t i o n r R o f G;
16 FENEUILLE

(4) u n d e r the o p e r a t i o n of G, t h e q o p e r a t o r s h j t r a n s f o r m in a n i d e n t i c a l
m a n n e r to the b a s i s f u n c t i o n s ф : \

«л) - R f a H ^ ) (hjJ-RforHhjJRicr)-*

then

I h i I 9k ) = X A
ß <ГР ' Г 0 ' r R l r Q 3' r R k >
ß
3. T H E ROTATION G R O U P IN T H R E E DIMENSIONS

3.1. I n f i n i t e s i m a l r o t a t i o n s and a n g u l a r m o m e n t a

A l l the p o s s i b l e r o t a t i o n s w h i c h t u r n a s p h e r e into i t s e l f c a n be s t u d i e d ,
but f o r o u r p u r p o s e it i s s u f f i c i e n t t o c o n s i d e r i n f i n i t e s i m a l r o t a t i o n s (by
dee a b o u t a g i v e n a x i s Ç, f o r e x a m p l e ) . We d e f i n e the i n f i n i t e s i m a l r o t a t i o n a l
o p e r a t o r by

or

R ( d o , Ç) = 1 + idoTç +

Any f i n i t e r o t a t i o n about R ( a , f ) c a n be w r i t t e n in t e r m s of a and I In


fact

R ( a + d a , ? ) = R ( d a , ? ) R ( a , Ç)

= (1 + i d o ? ) R ( а , Ъ

t h u s 4- R ( q , ? ) = i I ,ь R ( S , П and t h e r e f o r e
da

R(e.?) = eial£

F I G . 1. D e f i n i t i o n o f l f - a x i s in t e r m s of a n g l e s 0 a n d tp.
IAEA-SMR-12 / 2 1 17

L e t u s now c o n s i d e r an i n f i n i t e s i m a l r o t a t i o n by do about t h i s a x i s can


be defined by t h e a n g l e s 0 and cp a s shown in F i g . l . We can e a s i l y s e e that

R ( d a , £ ) = R(do s i n 0 cos cp, x) R(da sin 0 s i n cp, y) R ( c o s 0 d « , z )

and t h u s

Iç = s i n 0 c o s cp I x + sin 0 sincp Iy + c o s 9 I z

So, t h e i n f i n i t e s i m a l o p e r a t o r s add like v e c t o r s and any r o t a t i o n can be


e x p r e s s e d in t e r m s of l x , ly and l z only.
We c o n s i d e r now a f i n i t e r o t a t i o n R(a, Çj), w h e r e Çj l i e s in the plane
(ÏÏy, Oz). F i g u r e 2 shows t h a t

Rfa.Çj) = R(0,i)R(a,z)R(-0,x)

Fig. 2. Finite rotation R(a, £,).

Then we have

1 + ia(I y s i n 0 + I z cos в) + 0 ( a 2 )

= [1 + i0 I x + O ( 0 2 ) ] [1 +ialz+ 0 (a 2 )] [1 - i 0 I x + O(0 2 )]

•whence i t f o l l o w s i m m e d i a t e l y t h a t

ily ~ Ixlz ~ I^^-X

and t h e r e f o r e

il x - I z I у - I y l z
18 FENEUILLE

o r , when we d e f i n e

I + = Ix + i l y , I. = I x - i l y

Uz.lJ = ± I±

[I + , I . ] = 2 I Z

CONCLUSION: The i n f i n i t e s i m a l o p e r a t o r s of t h e r o t a t i o n g r o u p in t h r e e
dimensions are angular momenta.

3.2. C l a s s e s and i r r e d u c i b l e r e p r e s e n t a t i o n s

The e i g e n f u n c t i o n s of I 2 and I z a r e

(Î) 2 | 7 I M > = 1(1+1) I 7 I M >


-I S M s I

Iz | 7 l M > = м | т 1 м >

I X | T I M > = a I 7 IM + 1 )> + b | 7 I M - l >

IУ 17 IM У = с I 7 IM + О + d | 7 I M - l >
Therefore

Ща, z ) | 7 I M > = e i a M | 7 l M >

B.(ß, î ) |7IM> = ^ a(/3, M') I 7IM 1 У


M'
T h u s , the (21 + 1) f u n c t i o n s I 7 I M ) f o r m a b a s i s of a r e p r e s e n t a t i o n f o r the
r o t a t i o n g r o u p in t h r e e d i m e n s i o n s . T h i s representation is irreducible
and denoted by D 1 .
B e f o r e d e t e r m i n i n g the c h a r a c t e r s of t h i s r e p r e s e n t a t i o n , we have to
find t h e c l a s s e s of the c o n s i d e r e d g r o u p . Figure 3 shows that

R(0,X) R ( a , f ) = R(a, R(0, A) Ç) R(0 Д )

and t h e r e f o r e

R(0,X)R(a, ?)R(-0,1) = Ř(J,X) where X = R(0,X)|

All r o t a t i o n s t h r o u g h the s a m e angle belong to one and the s a m e c l a s s ,


i r r e s p e c t i v e of t h e a x i s about which any of the r o t a t i o n s i s m a d e .
To find the c h a r a c t e r , it i s convenient to c h o o s e the z - a x i s . T h e n
the r o t a t i o n m a t r i x i s d i a g o n a l , with i t s t r a c e given by

i s i n í (21 + 1)
giaM= ^ = I
a
sin 2
IAEA-SMR-12 / 2 1 19

Fig. 3 . C l a s s e s of groups c o n s i d e r e d .

H e r e it i s i m p o r t a n t to s t r e s s t h e following: if we c o n s i d e r only s p a t i a l
t r a n s f o r m a t i o n , it i s obvious that xà = Xa+2ir I i s n e c e s s a r i l y an i n t e g e r ,
but if we c o n s i d e r spin t r a n s f o r m a t i o n , I c a n be h a l f - i n t e g e r and then
Xa = ~ X a+2rr* R o t a t i o n s about a given axis by a and a + 2it a r e no l o n g e r
identical.

F i n i t e g r o u p s including spin t r a n s f o r m a t i o n s a r e called double g r o u p s .

3.3. K r o n e c k e r p r o d u c t s — 3j s y m b o l s
We c o n s i d e r the (2Ii + l ) f u n c t i o n s | y i I i M i > and the (2I 2 +1) f u n c t i o n s
| y 2 I 2 M 2 > . The (2Ij + 1 ) ( 2 I 2 + 1) f u n c t i o n s | M j > | ъ Ч Щ , > f o r m a b a s i s f o r the
1 12
r e p r e s e n t a t i o n D ' X D which is g e n e r a l l y r e d u c i b l e . In o r d e r to r e d u c e
i t , we take into account that
x
a xa =
[ e x P ( ^ i a ) + ••• + e x p ( - i l i a ) ] [exp(il 2 a) + ... + e x p ( - i l 2 a ) l

= [exp(i(l! + I 2 ) a ) + ... + e x p f - i d i + I 2 ) o ) l

+ [ e x p W ^ + I g - l ) a ) + ... + e x p t - i f l j + I 2 - l)a)]

+ [exp(i I I j - I 2 I a) + ... + e x p ( - i | I j - I 2 | a)]

Therefore

D ^ X D * 2 = D Il + I2 + ... +DI I i _ I 2 I

The r u l e f o r r e d u c i n g K r o n e c k e r p r o d u c t s i s t h e s a m e a s the r u l e f o r
coupling angular m o m e n t a .
We c a n f o r m a b a s i s f o r an i r r e d u c i b l e r e p r e s e n t a t i o n D 1

f j I-Ц - I 2 I á I S +I2)) f r o m thé f u n c t i o n s | y 1 I 1 M 1 > | 72I2 M2 >


20 FENEUILLE

Formally:

|7III72I2IM> =^<I1M1,I2M2|IM>| 7 I I1M1>| 7 2 I2M2>


M l , M2

The C l e b s c h - G o r d a n c o e f f i c i e n t s •(, | > can be found by applying I z , I + and I .


to the two m e m b e r s of t h e p r e v i o u s e q u a t i o n ; the f i n a l r e s u l t i s

< IjMJ, I2M2 |lM> = 6(Mj +M2,M)

y f (21 + IXIT + I 2 - I ) ! ( I I - М Г ) ! ( 1 я - M 2 ) ! (I+ M) ! (I - M) ! V


Л
U l i + 1 2 + 1 + 1)1(1+1! - I 2 ) ! ( I + I 2 - I 1 ) ! ( I 1 + M 1 ) ! ( I 2 + M 2 ) ! j

v Vf (Ii + M i + x ) ! ( I 2 + I - M i - x ) !
L ' x ! (I - M - x) ! (I j - MJ - x)!(I 2 - I + M j + x ) !
x
T h i s e x p r e s s i o n i s r a t h e r c o m p l i c a t e d , but e x h i b i t s a high d e g r e e of
s y m m e t r y . By w r i t i n g x = I - M - y, f o r e x a m p l e , we o b t a i n

<I 1 M 1 I 2 M 2 |l 1 I 2 IM> = ( - D ^ V ' O a M j . I 1 M 1 |I 2 I 1 im>

and t h e r e f o r e

| I 2 I 1 I M > = (-1) 1 " 1 '" 1 2 | l ! l 2 I M >

In f a c t , it i s p a r t i c u l a r l y convenient to d e f i n e f r o m the C - G c o e f f i c i e n t s
n e w c o e f f i c i e n t s : the 3j s y m b o l s . T h e y a r e d e f i n e d by:

/ 3l 32 1з \ i - i .m -i
= ( - l ) J l Jz (2j3 + 1 ) Ч з х Г П ! , j2m2|j3-m3>
\ т ^ г т з /

F o r s y m m e t r y p r o p e r t i e s of 3j s y m b o l s s e e Ref.[6] , pp. 1 - 5 .

3.4. R e c o u p l i n g c o e f f i c i e n t s — n j s y m b o l s

See R e f . [ 6 ] , C h a p t e r 3 ( 1 , 2 , 3, 4).

MAIN P R O P E R T I E S O F 3 j - S Y M B O L S

h ^ h ) i-i-m, ,-1/2/. I. . . \
I I = (-1) Ij3 J <JlmlJ2m2lilJ2J3"m3>
\ mx m2 m3 /

i h h h \ / к Je 3i \ / 03 Ji к \

V m! m2 т 3 / \ m2 m3 m i / \ m 3 mi т г /
I A E A - S M R - 1 2/212 1

Jl J2 Jä i ,j / 32 Ji J3
I = J J1 + -12 + J3 I
m j m 2 m 3 / m 2 rri! m3

J1 J2 J 3 Jl J2 J3
Il + Jí + Js
(-1)
m -m-, -m, -m
l m
2 m
3 > q

Jl J2 J3 \ / Jl J2 Зз
[j 3 ] 5 ( m j , m ' j ) 5 (m^ , m ' 2 )
m mj m 2 m3/ \ m j1 m ; , m1 ,1
Х
з.
J3. 3

Jl 32 J3 Jl J2 J3
1
= [j3l <5 ( j 3 , j 3 ) 6 ( m 3 , m ^
m m m m m т
mi, m 2 > l 2 3/ l 2 'з>

MAIN P R O P E R T I E S O F 6 j - AND 9j-SYMBOLS

< ( J i j 2 ) j i 2 , j 3 , j Ij х-(J2J3) J23-J>

1/0 . . . . í J3 J J12
= Hji2nj23]}1/2(-l)Jl+)2+]s+J
1 J 2 J23 .

< (jiJ2)j12- (j3j4)j34,jl(j1j3)j13, (j2j4)j24,j>

JI J2 J 12

= Í[j 1 2 nj 3 4 ][j 1 3 ][j24n 1 / 2 j3 j4 j34

JJ J 2 J3 / J l h h

h h \ m
l m
2 Ml M2 Мз

ji je2 h J2 h h j3

, m
i ^2 / m
"Ml 2 Мз / \ M 1 2 m3 /

JL J2 J3 \ I 11 ^2 J3 \
т
. m
l m
3 M1 ~ß2 3 /

Jl J2 J3 h h £3 jl je 2 is

m
h hi -ßl m2 ц 3 l M2 -МЗ
22 FENEUILLE

ЗЗ •) Již J3 J J12
(W'tW • = 23^23 )
]2 J23 h Ьз
Jlz

J3 3 j12 J Г J1 3 J23 i3 J J12

J23 Ji J2 З23 J N 2 ^ 3 J31 J 2 Ói J31

a b c
= ( - l ) a + b + C {[b][c]}" 1/2
О с b

a b X
£ [x] (-1) ó(p,0)(-l) a + b {[a][b]} 1 / 2
b a p

a b x
2a + 2b
[x] (-1)
a b p

a b x с d x * e f x
£ ix](-l)X
с d p e f q b a r

p q r p q r

e a d .f b e

a f r
ra b X
1 Í e f x
2x
-l) Ы d q e
l с d Pj l a b r
p с b
a b x ' с d x ' e f x "J Г g h x
[x]
с d p e f q g h r J [ a b s

d q e 'h r e"

ly] p с b g b

a f у a
f У.

a f x" a f x

[x] [y] d q У d
q У = « ( р . р ' Ж с . с ' Щ р П с ] } -1
X.y
p с b p' c' b_
IAEA-SMR-12 / 2 1 23

' a f x
a f x с d X
2\
Tlx] d q e = (-1)
x e b X e f q
p с b

a b e
a b e
b+ c+ e+f
с d e (-1)' {[e][f]}" 1/2
d с f
f f 0

4. TENSOR O P E R A T O R S

4 . 1 . D e f i n i t i o n of i r r e d u c i b l e t e n s o r o p e r a t o r s

In the p r e v i o u s c h a p t e r we have s e e n t h a t t h e s t a t e s I Y I M ) have well-


d e f i n e d s y m m e t r y p r o p e r t i e s u n d e r the o p e r a t i o n s of the r o t a t i o n g r o u p in
t h r e e d i m e n s i o n s . H o w e v e r , this is i n s u f f i c i e n t f o r an a p p l i c a t i o n of t h e
W - E t h e o r e m , s i n c e the u s e of t h i s t h e o r e m r e q u i r e s o p e r a t o r s having
w e l l - d e f i n e d s y m m e t r y p r o p e r t i e s . One of t h e m o s t i m p o r t a n t c o n t r i b u t i o n s
of R a c a h has b e e n the d e f i n i t i o n of s u c h o p e r a t o r s .
I f , u n d e r the o p e r a t i o n s R 0 of a g r o u p , a f u n c t i o n ф b e c o m e s R 0 $ , an
o p e r a t o r T a c t i n g on ф b e c o m e s R 0 T R g 1 . We know a l s o that it i s s u f f i c i e n t
to s t u d y i n f i n i t e s i m a l r o t a t i o n s and we only have to find f o r o p e r a t o r s the
a n a l o g u e of the t r a n s f o r m a t i o n L ф. Since

il* . U m MfOLU
1 a
a-* n0
f o r o p e r a t o r s , t h i s equation t a k e s t h e f o r m
R(q
lim - f)TR(-g,f)-T = (l+ittIt)T(l-iaIE)-T = ,ц T]

a-» 0
So we s h a l l s e e that t h e ( 2 k + l ) o p e r a t o r s T<k) ( - k s q s k ) f o r m the c o m p o n e n t
of an i r r e d u c i b l e t e n s o r o p e r a t o r which t r a n s f o r m s as t h e i r r e d u c i b l e
r e p r e s e n t a t i o n D M (or of r a n k k) within t h e s p a c e defined b y T , if

[Iz,T<qk>] = q T ®

[ l i . T ® ] = [k(k + l ) - q ( q ± l ) ] 1 / 2 T ( q k ± > 1

T h e s e e q u a t i o n s a r e b a s i c f o r t h e t h e o r y of t e n s o r o p e r a t o r s .

4.2. Wigner-Eckart t h e o r e m

P o r the t h r e e - d i m e n s i o n a l r o t a t i o n g r o u p , the W - E t h e o r e m t a k e s a
v e r y s i m p l e f o r m , s i n c e we know t h a t D 1 d o e s not o c c u r m o r e o f t e n t h a n
24 FENEUILLE

once in the d e c o m p o s i t i o n of the K r o n e c k e r p r o d u c t D k X D 1 , T h e r e f o r e , we


can write

< o ' l ' M ' J T q k ' | a I M > =< I ' M ' | k q , I M > A ( a ' , I ' , k , a, I)

or
/к I Г \
< > ' I ' M ' | T ( q k ) | a I M > = (-1Г1+к - м ' [V]1^2 A

\q M -M'/

[x] = 2x + l

U s u a l l y we s e t
(•l)-I +k-I' [ Г ]1/2 А = < q , J , ||X(k)

w h e r e the f a c t o r ^ || || i s called a r e d u c e d m a t r i x e l e m e n t .
Thus t h e W - E t h e o r e m f o r t h e t h r e e - d i m e n s i o n a l r o t a t i o n g r o u p t a k e s
the f i n a l f o r m

.
<«ФМ'|Т<к>|в1М> = (-1)1_М
.( v k 1
\
<аЧ'||т№||о1>
\-M' q M /

We have- to m e n t i o n t h a t we can d e f i n e double t e n s o r o p e r a t o r s


Ck к }
^ Q i V having well-defined r a n k s kj and k 2 with r e s p e c t to two independent
a n g u l a r m o m e n t a I j and I 2 . The W - E t h e o r e m t e n s o r i s :

<a'r 1 I^M' 1 M^|T ( q k ' q k 2 ) | e I 1 I 2 M 1 M 2 > = ( - l ^ l + ^'-Mi-Mz


\
/ Г1 k l h \ / 4 k
2

\-M' M j \-Щ q 2 Щ/

4.3. Coupled t e n s o r o p e r a t o r s

F o r t h i s s e c t i o n , s e e Ref.[6], C h a p t e r 3.5, .6.

Fundamental formulas

1
x gC) = £ T(q ;!)U^)(k1q1,k2q2|k1k2KQ)

4l42

T (klk2)K = £ т ( к Л ) ( k i q i k 2 q 2 |klk2KQ)

4102
IAEA-SMR-12 / 2 1 25

Scalar product

(TOO.Utk)) = ^ ( ^ 1 ) - q T W u ( k ) = (_i)k [ k ]+V2 { T (k) u<k) }(0)

T (k-k) = (_l)k[ k ]l/2 T(kk)0

Matrix elements

If T ' k i ' and U(kz) a c t on p a r t s 1 and 2 of a s y s t e m , r e s p e c t i v e l y , then

к
'il il Г

< Í l Í 2 J l l X Q > l l i i ^ J , > = { [ J H J ' H K l } 1 7 ^ j2 jfe k 2

.J J' K.

x<j1||T(k.)||ji><j2||T(k2)|^>

F o r double t e n s o r s , t h i s f o r m u l a r e a d s

k
il i'l l

<7j1J2j||T^k^K||yj- = {[JHJ'HK]} 1 / 2 h i2 k
2

IJ J1 К .

x <7 U a l l T ^ J J I v j i i p

Important special cases

< j 1 j 2 J M J |(T<k> -U< k ))| j^jJjJ'MJ >

J
i'l Ъ
= (-l)ii' + i2+J 5 ( J , J ' ) 6(Mj, Mj' )
k
Í2 i l

X < j 1 | | T W | | j . > < j 2 IIUW | | j . >

F o r an o p e r a t o r a c t i n g only on p a r t 1 we c a n w r i t e

<j1j2j||T(K) ||j'j'J<> = 6(j2,j-)(-l)Ji + b+J,+k

J к J'
x{[J],[J']}1/2 <ill|TW||j-1>
J1 32 jj
26 FENEUILLE

[valid f o r T ( k 0 ) if we r e p l a c e the r e d u c e d m a t r i x e l e m e n t of the r i g h t - h a n d


s i d e of the equation by < y Í ^ II т ( к 0 ) II T'J'i^ ^ • F o r an o p e r a t o r U( k ') a c t i n g
only on p a r t 2 we have

Ü +ji + J + k'
< jlj2Jl|U(k,)||jiji,J'> = Ô ^ J ' ^ - l )

fJ k' J1 1
1/2
x{[J][J-]} <jJ|u(k')||j'>

[valid f o r T( o k ) if we r e p l a c e the r e d u c e d m a t r i x e l e m e n t on the r i g h t - h a n d


side of the equation by < y j || T«*) || y ^ j. >].

4.4. Elementary tensor operators

4.4.1. Angular momentum

JW
U = J &. J(D
1 = + J ( « = 2-1/2J

< J II J H J > = { J ( J + l ) ( 2 J + l)} 1 /2

4.4.2. Spherical harmonies


11/2
С(Ю = i - 4 7 r l v «
q 1 2k+ l j 4

£ к
0 | | c ( q k ) | U ' > = (-1){ШП1']}1/2
\ О 0 0 j

J IЛ-i' \ S к s и+Р)
[ к s a m e p a r i t y a s {£. + £.')

It i s s o m e t i m e s u s e f u l to r e p l a c e C^ k 'f(r) by
CO

C(qk)(ni,n'i') J Rnt(r)f(r)Rn,c,dr
0
ni.n'i'

where

< n a i a II СW ( n í , n'Г> ) II n b i b > = б (n, n a ) 6 ( i , 1 a ) б (n-, n b ) 6 (I '-, i b ) < i D C ( k ) II i ' >

4.4.3. Linear momentum

The g r a d i e n t v e c t o r is a t e n s o r o p e r a t o r of r a n k 1 a c t i n g on the o r b i t a l
s p a c e only; it can be r e p l a c e d by (see 4.5.3)
IAEA-SMR-12 / 2 1 27

X С « M , , , ) / R „ { ( r ) - ^ +
0
ni.n'i"

4 . 4 . 4 . Double t e n s o r s

It is s o m e t i m e s convenient to i n t r o d u c e the following t e n s o r o p e r a t o r s


W<xk> ( n i , n ' i ' ) and v W i n i . n ' i 1 ) d e f i n e d by

< n a s i a II w^xk' ( n i , n ' i ' ) II n b s i b ) = ó ( n a , n ) 6 ( í a , i ) 6 ( n b , n ' ) 5 ( j e b , i ' ) { k ] [ k ] } 1 / 2

V ( k > ( n i , n ' i ' ) = 2 1 / 2 W< 0 k >(n.e,n'i') .

4.5. Atomic interactions under tensorial f o r m

4.5.1. Coulomb i n t e r a c t i o n

e2
- V eo2 r< /r'k> • r (k) \
r
r / 7r Ш " 2 i
12 V >
к
t h i s o p e r a t o r c a n be r e p l a c e d by

R ( k > ( n i , n ' i ' ; n " i ' ' , n ' ' ' i ' ' ' ) ( C < k > ( n i , n " i " ) • Cř, k >(n'í',n'"i"'))
ni.n'i'
n"í",n",í"'

where

. R ( k ) ( n i , n ' i ' ; n " i " , n ' " i ' " ) = f f e2(RnCRn.r)i(RnTRn"i")2 7|Tdrldr2

U s u a l l y we w r i t e

R ( k ) ( n i , n ' i ' ; n i , n ' i ' ) = F ( k ) ( n i , n ' i ' ) ; R ( k ) ( n i , n ' i ' ; n'SL', n i ) = G ( k ) ( n í , n ' i ' )

4.5.2. Spin-orbit interaction

T h e s p i n - o r b i t i n t e r a c t i o n can be w r i t t e n a s

S(r)(s -1)

It can be r e p l a c e d by:

^ Ç(ni,n'i){i(i + i)(2í + l)/6}1/2W<bl>(ni,n'i)


ní,n'i'

where

Ç(ni,n'i) =J RníRn,^(r)dr
О
2 8 FENEUILLE

4.5.3. Exercise

Give in t e n s o r i a l f o r m :

(a) the magnetic spin-spin interaction

s x • s g _ 3(r 1 2 • s 1 ) ( r 1 2 - s 2 )
. 5
12 12

(b) t h e i n t e r a c t i o n b e t w e e n spin and a n o t h e r o r b i t

VI ( — )X Pl (s 1 + 2 s 2 ) + V
2 — JXp 2 (s 2 + 2 s x )
12 •12

Show t h a t

V = -(2)1/2±{C<W +|;C(1)

(illicooijoo j i . , = i ( i + 1 )
[ 2
k
k
(
(
k
2 i ;^ , + 1 )
( i ï C « ||i>)

5. CONFIGURATIONS WITH TWO E L E C T R O N S

5.1. L - S coupling

5.1.1. N o n - e q u i v a l e n t e l e c t r o n s

The b a s i c f u n c t i o n s a r e of the type

Iу(ИЛ') SLJM)>

o r , if we t a k e into account the p r i n c i p l e of a n t i s y m m e t r y

(l/2)1/2{|T(i1X^)SLJM> - lYtijû^SLJM»

= (l/2)1/2{|7(i1i^)SLJM> + (-l)s +L + í + r |7(íj,í2)SLJM>}

U s i n g the g e n e r a l f o r m u l a given in s u b s e c t i o n s 4 . 3 , 4 , 5 we obtain

e2
< y ( l V ) SLJM 7(4.2') S ' L ' J ' M ' ) = ô (J, J ' ) б (M, M1 ) 5 (S, S' )

£ £ к
X б (L, L ' ) J J ^) FF kk (( ií ,, £')
£') -j j (• ( - l ) L + { + r

V V L
l.k even < m i n ( 2 £ , 2£')

X<i||C(k) ||i>< V ||c(k) ||i'>


IAEA-SMR-12 / 2 1 29

[i i' к
Gk (i, V ( - l ) s < i | | c W ||i'>2
li i' К
same parity as (í + С')

T h e m a t r i x e l e m e n t s of the s p i n - o r b i t i n t e r a c t i o n

Л S(rj)(ij •/,) (i = l , 2 )
i

can be obtained in t h e s a m e way:

<7(ii') SLJMjA^ii'JS'L'J'M') = Ô(J, J') Ó(M,M') ( - l ) s ' + L + I + { + t ' + 1


S S' 1
J {[Ll[L'llSl[S<l}1/2JJ | ? i { i ( i + l ) ( 2 i + l ) 1 / 2 ( - l ) s ' + L'
.L' L J.

S 1 S'l fL 1 L'
X- + Ç s . { i ' ( i ' + l ) ( 2 i ' +l)}!/2 (-1 ) S + L
i2 i2 i
2 i i' i
S 1 S'l fL 1 L'

i 1 i i i'
2 2 2

where = Ç(ni,ni) and = Ç (n'i<, n'i').

5.1.2. Equivalent e l e c t r o n s

The m a t r i x e l e m e n t s a r e obtained in e x a c t l y the s a m e way a s in the


p r e v i o u s s e c t i o n , but now the b a s i c f u n c t i o n s r e a d

| T i 2 S L J M > = | { l + (-l)L+s}|7i1je2SLJM>

and we s e e i m m e d i a t e l y that S + L m u s t be e v e n . F i n a l l y we obtain


,2
< y i SLJM y i2 S'J'J'M' У = 6(J,J')6(M,M')6(S,S')6(L,L')
12
i i к
x £ P k (i)(-i) L I <i||c<k> ||i> 2
к <2í
i L
even

< 7 Í 2 S L J M | A | 7 Í 2 S ' L ' J ' M ' > = 26(J, J ' ) 6 ( M , M ' ) ( - 1 ) S ' + L + J + 1
30 FENEUILLE

X Ç i { [ L ] t L ' ] [ S ] [ S , ] } 1 / 2 { 3 / 2 i ( i + 1)(2Í + 1)} 1 / 2

js S' 1I f S 1 S' j Г L 1 L'


X
lb' L jJ [ H I J Ь i Jř
5.2. j - j c o u p l i n g

The c o r r e s p o n d i n g f o r m u l a s can be o b t a i n e d by m e a n s of the s a m e


t e c h n i q u e s a s u s e d f o r L - S c o u p l i n g . The b a s i c f u n c t i o n s a r e now of t h e
type

•yiji'j'JM) =-^||T(ij)1(jfj')2jM> -(-D^^'lTOe'j'M^JM)}-

|7(ij)2 JM> = H l + ( - l ) I } | 7 ( i j ) i f i j ) 2 J M >

a n d , f o r e x a m p l e , we o b t a i n

5 . 3 . V a l i d i t y of v a r i o u s c o u p l i n g s

T h i s q u e s t i o n w a s a l r e a d y d i s c u s s e d in c h a p t e r 1. In p a r t i c u l a r , if we
do not t a k e into a c c o u n t n u c l e a r e f f e c t s , we know t h a t t h e only good q u a n t u m
n u m b e r s a r e J , M and p a r i t y . M o r e o v e r , we s u p p o s e in t h i s s e c t i o n t h a t a
o n e - c o n f i g u r a t i o n m o d e l i s a p p l i c a b l e . T h e n , if the e f f e c t s of s p i n - o r b i t
i n t e r a c t i o n a r e s m a l l with r e s p e c t to t h o s e of C o u l o m b i n t e r a c t i o n , we c a n
c a l c u l a t e t h e e f f e c t s of Л f o r A given t e r m . In t h i s c a s e S and L a r e good
a p p r o x i m a t e q u a n t u m n u m b e r s and s i n c e t h e J - d e p e n d e n c e of
< 7 S L J M | a | 7 S L J M > i s c o n t a i n e d in

we c a n w r i t e :

E ( 7 S L J ) - E ( 7 S L J - 1) = J A ( a SL)

T h i s i s the w e l l - k n o w n L a n d é i n t e r v a l r u l e .
IAEA-SMR-12 / 2 1 31

On t h e o t h e r h a n d , if the e f f e c t s of C o u l o m b i n t e r a c t i o n a r e s m a l l with
r e s p e c t to t h o s e of s p i n - o r b i t i n t e r a c t i o n , j - j coupling i s a good a p p r o x i m a t i o n .
T h i s s i t u a t i o n i s e x t r e m e l y r a r e in a t o m i c s p e c t r a , but one e x a m p l e i s
p r o v i d e d by the c o n f i g u r a t i o n s 6 p 2 and 6 p 7 s of P b I.
U n f o r t u n a t e l y , v e r y o f t e n n e i t h e r L - S n o r j - j coupling a r e valid a p p r o x i -
m a t i o n s . In t h i s c a s e it is n e c e s s a r y to d i a g o n a l i z e the m a t r i x of C o u l o m b
i n t e r a c t i o n and s p i n - o r b i t a l i n t e r a c t i o n f o r e a c h v a l u e of J; the wave f u n c t i o n
i s a s u p e r p o s i t i o n of d i f f e r e n t b a s i c f u n c t i o n s : coupling is i n t e r m e d i a t e .
F o r noble g a s e s (one h o l e , one e l e c t r o n ) , h o w e v e r , a t h i r d type of coupling
p r o v i d e s a r a t h e r good a p p r o x i m a t i o n . T h i s i s j-k coupling which is d e f i n e d
by

|T(ij)i'k|JM>

(2{'*1) DOUBLETS

С
(2Í'«1) DOUBLETS

Fig. 4. j-k coupling.

[ 2 i -1)
TRIPLETS

( 2 ř «1)
С SINGLETS
TWO GROUPS OF (2i'»2) LEVELS

TWO GROUPS OF 2f LEVELS

>
L- S j-j
F i g . 5. L-S and j-j couplings.
32 FENEUILLE

O b v i o u s l y , t h i s coupling applies if

л(Я»<—»л(Л')

The c o r r e s p o n d i n g s p e c t r u m h a s the s h a p e shown in P i g . 4 (we a s s u m e


i ' S J i ) while the two o t h e r couplings would p r o v i d e the s c h e m e s shown in
Fig.5.

5.4. E l e c t r o n s in c l o s e d s u b s h e l l s

F o r t h i s s e c t i o n , s e e Ref.[4].

6. ANTISYMMETRY P R O B L E M S

6.1. N o n - e q u i v a l e n t e l e c t r o n s

L e t us c o n s i d e r , e . g . the c a s e of t h r e e e l e c t r o n s ( 1 , 2 , 3 ) in t h r e e d i s t i n c t
s u b s h e l l s (nj2)a , ( n i ) b , (n£) c :

m1/2
I a b с, тУ = "I "g г { | a i b 2 c 3 r> - b3 c2 т> + | a 2 b 3 C l r>

- | a 2 b 1 c 3 T > + | a 3 b j c 2 т > - | a 3 b 2 c x т > }

ill172

I a b с, т> = j g У { | a 1 ( b c ) 2 3 т> - | a 2 (bc) 1 3 т> + | a 3 (bc) 1 2 т>}

M o r e g e n e r a l l y we have

-|(a)"' (b)°Mc)"s ... O M C N ^ . . ^ 7 ( - l ) P x l ( a ) ; ; . . . i n (b)* ... т>


X
' 1 2
c
nn Nn n = —;—~t г » [N = ni1 + n 12 + . . . + nkk ]
i . 2 . ••• n k n ! n2 ! . . . n k !

p x i s the p a r i t y of t h e p e r m u t a t i o n P x given by

/ 1 2 N \
P =
k
••• ••• - V - nk,
P x = p r o d u c t of p x t r a n s p o s i t i o n s .

6.2. E q u i v a l e n t e l e c t r o n s — f r a c t i o n a l p a r e n t a g e c o e f f i c i e n t s

E l e c t r o n s in one and the s a m e s u b s h e l l can be indexed only if we s p e c i f y


all the q u a n t u m n u m b e r s d e f i n i n g the o r b i t , i . e . n, SL, m { , m s . In o t h e r w o r d s ,
IAEA-SMR-12 / 2 1 33

the wave f u n c t i o n s m u s t be w r i t t e n in t e r m s of Slater d e t e r m i n a n t s and we


a l r e a d y know t h a t t h i s p r o c e d u r e i s u s u a l l y v e r y t e d i o u s . In o r d e r to avoid
the e x p l i c i t i n t r o d u c t i o n of d e t e r m i n a n t - p r o d u c t s t a t e s , R a c a h i n t r o d u c e d
the concept of f r a c t i o n a l p a r e n t a g e . It is b a s e d on the f o l l o w i n g p r i n c i p l e :
We d e f i n e the s t a t e s of the c o n f i g u r a t i o n s i N , i N _ 1 and l by the s e t s
of q u a n t u m n u m b e r s

7 SL Ms M l = Г2

7 SL M s M L s Л

m s m^ = и

Since e v e r y d e t e r m i n a n t - p r o d u c t s t a t e f o r an N - e l e c t r o n s y s t e m i s a s u m
of t e r m s , e a c h of which involving an e i g e n f u n c t i o n ^ N ( s i m s m e ) of the N - t h
e l e c t r o n , we m a y w r i t e :

|П> = u|n> |fi>|uN>


Q, uj

6.2.1. M a t r i x e l e m e n t of a s i n g l e - p a r t i c l e o p e r a t o r

< П | р | Г 2 ' > = N < n | f n | r 2 ' >

< í 2 | F | f i ' > = N ^ < Í2 [?2; to> u 1 | f t ' > < u |f | u ' >

If we a s s u m e that the p h a s e s of the v a r i o u s s t a t e s i n t r o d u c e d have b e e n


c h o s e n to m a k e s u r e that the c o e f f i c i e n t s a r e r e a l , t h e n

< Q |?T;u> = < |n>

6.2.2. Two-particle operators

A m o n g the ^ N ( N - l ) c o m p o n e n t s gij ( i > j ) c o m p r i s i n g G, t h e r e a r e


2 ( N - l )(N-2) which do not involve the N - t h e l e c t r o n . Hence we obtain "

< = [N/(N-2)]<Q| ^ g j ß ' )


jci^N
Then:

n
< ^ gij l ' > = ^ < ŠT | ? 2 ; t o > < Г 2 " ; ш | Г2' > < ? T | G | ? T ' >

-» chain c a l c u l a t i o n .
34 FENEUILLE

6.2.3. Fractional-parentage coefficients

< y Š L M S M L ; £ m s m { \y S L M s M L > = < Š M S s m j š s S M s >

X<LM L lm,|Lf L ML>< y Š b|}£N 7 S L>

T h e l a s t t e r m i s t h e c o e f f i c i e n t of f r a c t i o n a l p a r e n t a g e . The c a l c u l a t i o n
of t h e s e c o e f f i c i e n t s f o r d and f e l e c t r o n s r e q u i r e s s o p h i s t i c a t e d t e c h n i q u e s
w h i c h we s h a l l not d e s c r i b e h e r e . In a n y c a s e , the c o e f f i c i e n t s have b e e n
t a b u l a t e d by N i e l s o n , C . W . and K o s t e r , G . F . in " S p e c t r o s c o p i c c o e f f i c i e n t s
f o r t h e p n , d n and f n c o n f i g u r a t i o n s " , M . I . T . P r e s s , C a m b r i d g e , M a s s . (1963).
F o r p N e l e c t r o n s , t h e s e c o e f f i c i e n t s c a n be e a s i l y o b t a i n e d f r o m the r e l a t i o n

L 1 L' S I S'
2
^<p S L | } p 3 s L>{[L][S]} V 2 -
SL
1 1 L

f o r odd S1 + IV

S i n c e the c o e f f i c i e n t s ; | У c a n be d e c o m p o s e d i n t o C - G c o e f f i c i e n t s and
C F P c o e f f i c i e n t s , we m a y w r i t e

|ÜN7 S L M s M l > = £ <£N"17SL|}£N7SL>


yŠL

X I 7 Š L , £N , i N 7 S L M s M L >

6.2.4. E x a m p l e s of a p p l i c a t i o n

S g i n - o r b i t i n t e r a c t i o n in ÜN - c o n f i g u r a t i o n s

^ (Si • ) =Л

N N
< Í 7 S L J M , |A|Í 7 ' S' L 1 M } > = Ó(J, J ' ) Ô ( M J , M , J ) ( - 1 ) S 4 L +J

'S S' 1
X - <ÍN 7 S L||W(u'||Ín 7' S' L - >

. L1 L J J

X ( < % S L ||W ( 1 1 ) | | i N 7' S' L 1 У


N 1
^ <£ " 7' S 1 L ' |} £ N 7 ' S ' L ' X tf S BIL^N-1 Y S L >
= N y Š L
y'S'L'

X<ín"17ŠL, íNJ £N 7 s LIIW^dIIín- 1 ^ š1 D.jlx? S- L > >


I A E A - S M R - 1 2 / 2 1 47

<i N " 1 T SL < i N 7S L j| W'}1' К i1**"1 7' S' L', i N У S'L'>


S 1 S' L 1 L'
= 35(7,7') e(S.S') ô(L,L')
_ s Š s i L i
S +
X (-1) Š^ + L + L + Í { [ s ] [ s , ] [ l ] 1 l , ] } 1/2

Coulomb i n t e r a c t i o n in mixed configurations of the_t^£e '

Definition of the coupling s c h e m e :

|I N
7 S L, V 7 S L J Mj >

T h r e e types of o p e r a t o r s :

G(i) = ^ F k ( i ) (C(k)(i,i) • C(k)('i,i))


i> j

G d (i,i') = ^ F k (i,i')(ci k )(i,i)-C( k )(i',i')+C( k )(i',i')-C( k )(i,i))


i> i

G e (í,í') = ^ G k (i,i') (C| k '(í,í') • Cf k '(i',i) + C( k )(i'.i)-C^)(i,i'))


i> J
N
|i 7 S L i ' S L J Mj>

= (
{ n T i F I "1)Pxl(# C
> l . . . x - l x + l . . . N + l n S L J M,>
X

= ШТЩ72 I ("D P x I < ^ 7 Š L|} 7 S L>


X y S L

X |[(iN-! ŤŠL)liiiHltli , Vl]ÍŠL, i- SL JMj>

Calculation of the exchange p a r t :

I K i N _ 1 7 Š L ) ! . . . N . l f i N ] y S L , I ' t l , S L J Mj >

= (S|)S, 1, s|§(| |)S,S><L(i,i')L L I (L i)L V L>


SL

X I [(i N _ 1 7 Š L) 1 N SLJM,)

< [ ( i N " 1 7 ' g- L ' ) ^ ^ , i N + 1 ] 7 ' S' L ' , S' L' J ' M'j I
36

< (S" j ) S1, S1 |S' (I | ) S ' S ' X (L1 i) L' £' L' |L'(Î V) L' L'>
S'L'

X (_1)S,+L'+1 + ( j e N-l-, g, L ' ) 1 i < î N . i . [ Î ' n Î j j ^ I S ' L ' . S ' L 1 J ' M

At.V) = ^ G k (i.i-) 2

Finally we have

< i N 7 ' S' L', V, 7' S' L' J' M'j |G e (i, V) | i N 7 S L, V, y S L J Mj >

= ^ G k ( í , i ' ) Ó(J, J ' ) ô ( M j . M J ) fi(S.S') 6 ( h , L ' )


к

X^ N <( 7 Š L | } £ N 7 S L>< i N y § ' L 4 | i N _ 1 7 § L>


ySL

S 2 ^1 fS 2 L 1 L L J L1
1 1/2
X ^ {[§'][§][L][L ]}
SL 2 S S J 12 SS Г L L,J L ' L L

i Л' к
X {[S][L]} - < i IIC® II i ' ) 2 (-IÝ
i V L.

^ G ( k ) (i, V) à (J, J ' ) ê ( M j , M j ) Ó(S, S') <5(L,L')


к
XN-jj < i N _ : L 7 Š L | } Í N 7 S L > < Í N 7 ' S1 L'{ | y § L>

L L l

X 6(S,S')Í L' L V <i||c< k > ||£'> 2 {[Ь][Ь']} 1/2 (-1) У

.t l' к

Exercise: determine z and y.

6.3. Second quantization

For this section see Ref.[8] .


Basic relations:
IAEA-SMR-12 / 2 1 37

=44 ... вТ|0> = {aß ...v}

< о | а и ... a ß а а = { a ß ... и}*

[at, a t]+ = О

[ a £ . a 4 ] + = 0 .

[ a y , a | ] + = <5(7,Л)

ay|0> =О

f =
p = X i Z
1
Ě . 7,

G = g = a
\ zL ij \ /L l a í aAaC < I 2 | g l 2 k l ^2 >
i/J E. T). £ . X.

7. STATIC F I E L D S

7 . 1 . U n i f o r m m a g n e t i c field

7.1.1. The G r o u p C„ . S y m m e t r y of t h e p r o b l e m

When the a t o m i n t e r a c t s with an e x t e r n a l u n i f o r m m a g n e t i c f i e l d , gť,


t h e s p e c i a l s y m m e t r y i s d e s t r o y e d and only the c y l i n d r i c a l s y m m e t r y (C œ )
r e m a i n s . The p a r i t y s t i l l is a good quantum n u m b e r , but J i s t h i s no l o n g e r :
only J z c o m m u t e s with t h e H a m i l t o n i a n and the e n e r g y l e v e l s can then be
c h a r a c t e r i z e d by M, an i n t e g r a l o r h a l f - i n t e g r a l e i g e n v a l u e of J z . The
l e v e l s a r e no l o n g e r d e g e n e r a t e (except s o m e t i m e s by a c c i d e n t ) . If the
m a g n e t i c field i s s u f f i c i e n t l y weak ( Z e e m a n e f f e c t ) , J can s t i l l be c o n s i d e r e d
a s a good q u a n t u m n u m b e r ; when t h e atom i n t e r a c t s with t h e m a g n e t i c f i e l d ,
e a c h l e v e l E y j i s s p l i t up into (2J + 1) l e v e l s E ? J M . E x p e r i m e n t a l l y , this
s p l i t t i n g p l a y s an i m p o r t a n t r o l e in the d e t e r m i n a t i o n of J of a given l e v e l .
In f a c t , t h i s m e t h o d was b a s i c to the d i s c o v e r y by S o m m e r f e l d of odd
m u l t i p l i c i t i e s in a t o m i c s p e c t r a and s t i l l i s f u n d a m e n t a l f o r the i n t r o d u c t i o n
of spin in o r d e r to i n t e r p r e t h a l f - i n t e g r a l v a l u e s of a n g u l a r m o m e n t u m .
When the m a g n e t i c field b e c o m e s s u f f i c i e n t l y s t r o n g , J is no l o n g e r an
a p p r o x i m a t e l y good q u a n t u m n u m b e r ( P a s c h e n - B a c k e f f e c t ) ; in o r d e r to
i n t e r p r e t the s t r u c t u r e s which a r e t h e n o b s e r v e d , it i s n e c e s s a r y to p e r f o r m
a quantitative analysis.

7.1.2. Quantitative a n a l y s i s

The H a m i l t o n i a n d e s c r i b i n g the i n t e r a c t i o n b e t w e e n an a t o m and the


m a g n e t i c field r e a d s

H
M =
38 FENEUILLE

w h e r e д м i s the m a g n e t i c m o m e n t of the atom and is given by,

- /3 (L + 2 S)

If we let the z - a x i s coincide with we obtain

H M = ( S ^ ( L Z + 2 S Z ) = ßgf(Jz +S Z )

In LS coupling, it i s p a r t i c u l a r l y e a s y to obtain the m a t r i x e l e m e n t s of


H M , since

< Q S L J M | J z | a ' S ' L ' J ' M ' > = M б (M, M') 5 (a, a' ) 6 (S, S' ) 6 (L, L 1 ) б (J, J 1 )

/ J 1 J' \
< a S L J M | S Z | a ' S ' L ' J ' M ' > = (-1) J " M
\ -M 0 M' /

X < o SLj||s||a'S'L'J'>

< a S L j | | s | | e ' S ' L ' J ' > = ô ( a , a ' ) 6 ( L , L ' ) é ( S , S')

f j 1 J 4
X (-1) L + S + I'+1 {[j][J.]}1/2 {S(S + 1)(2S+1)} 1 / 2 \ L
[ S L S J
If the m a g n e t i c field is sufficiently weak, we m a y use a f i r s t - o r d e r p e r t u r b a -
tion a p p r o x i m a t i o n and we have to c o n s i d e r only the c a s e of J = J ' . Then we
can w r i t e

/ J 1 J \
(-1) J " M = M{J(J + 1)(2J + 1)}" 1/2
\ - M 0 M /

J 1 J
_ , -, >s + L +j L(L + 1) - S(S+1) - J(J + 1)
1
' 2{J(J + l ) ( 2 J + l)}l/2 {S(S + l)(2S+l)}!/2
. S L S .

so that

< a S L J M l H M l a ' S ' L ' J ' M ' ) = б (M, M') б (а, а' ) 6 (S, S1 ) б (L, L' ) Xg(SLJ) M

w h e r e g(SLJ) i s the Landé f a c t o r :

_./ст T\ - -, , J ( J + 1) + S(S + 1) - L(L + 1)


g(SLJ) - 1 + 2J(J + 1 )

T h i s well-known r e s u l t could have been obtained in a m u c h l e s s s o p h i s t i c a t e d


way, e.g. f r o m the v e c t o r m o d e l , but t h i s model would not have yielded
the g e n e r a l f o r m u l a s p r e v i o u s l y obtained.
In the g e n e r a l c a s e , the wave functions | y J M ) > of a l e v e l E y j can be
written as
IAEA-SMR-12 / 2 1 39

|7JM> =^ ay(aSLJ)|aSLJM>

The e n e r g i e s of the Z e e m a n l e v e l s a r e then given by

EyJ + MgyJ ß g f

w h e r e the Landé f a c t o r i s e q u a l to

^ a 2 (a SLJ) g(SLJ)

Since g y J i s obtained d i r e c t l y f r o m t h e Z e e m a n s p e c t r u m it p r o v i d e s a t e s t
of the v a l i d i t y of LS coupling.
We c o n s i d e r now an LS m u l t i p l e t ; if ßg? is not n e g l i g i b l e with r e s p e c t
to A ( a S L ) , it i s n e c e s s a r y to d i a g o n a l i z e the m a t r i x of V s o + H M f o r a l l the
s t a t e s | a S L J M > . As we know t h a t M i s a good q u a n t u m n u m b e r it is s u f -
f i c i e n t to d i a g o n a l i z e t h e m a t r i c e s c o r r e s p o n d i n g to a given v a l u e of M.
If b e c o m e s m u c h m o r e i m p o r t a n t than A ( a S L ) , t h i s d i a g o n a l i z a t i o n can
be p a r t i a l l y avoided by u s i n g the b a s i s | a S L M s M L ) > within which H M i s
d i a g o n a l . V s o i s t h e n t r e a t e d by f i r s t - o r d e r p e r t u r b a t i o n t h e o r y ; the
c o r r e s p o n d i n g s t r u c t u r e i s a P a s c h e n - B a c k one.

Exercise:
Build up the m a t r i x of Vso + within the s t a t e s L S J M f o r a 2 P .
D i a g o n a l i z e t h i s m a t r i x . D e t e r m i n e the v a l u e of {ßgif/A(a SL)} f o r which
t h e r e a p p e a r s an a c c i d e n t a l d e g e n e r a c y (level c r o s s i n g ) .

7.2. U n i f o r m e l e c t r i c field

7.2.1. The g r o u p C „ r S y m m e t r y of the p r o b l e m

As in the p r e v i o u s c a s e , the s y s t e m a t o m plus field h a s no l o n g e r


s p h e r i c a l s y m m e t r y ; J is not a good q u a n t u m n u m b e r . H o w e v e r , the
s y m m e t r y i s not the s a m e a s in the p r e v i o u s c a s e ; i n s t e a d of c y l i n d r i c a l
s y m m e t r y , we have now c o n i c a l s y m m e t r y . The f i r s t c o n s e q u e n c e is that
p a r i t y i s no l o n g e r a good q u a n t u m n u m b e r . M o r e o v e r , we a r e going to
show that the i r r e d u c i b l e r e p r e s e n t a t i o n s of the c o r r e s p o n d i n g s y m m e t r y
g r o u p ( r o t a t i o n s about t h e field and r e f l e c t i o n s with r e s p e c t to an a r b i t r a r y
plane c o n t a i n i n g the f i e l d ) can be l a b e l l e d by the a b s o l u t e v a l u e s of M;
+M and - M being a s s o c i a t e d with a single r e p r e s e n t a t i o n , t h e n , f o r M ^ 0,
a double d e g e n e r a c y r e m a i n s .
L e t u s d e f i n e t, the r e f l e c t i o n o p e r a t i o n and R ^ , the r o t a t i o n about the
f i e l d . F i r s t it i s o b v i o u s that

M o r e o v e r we have

R„|7M> = e1M*|7M>

R | 7 -M> = е ш ? | 7 -M>
40 FENEUILLE

so t h a t

tRj TM> = R . ^ t I f M ) = eiMv | у М >

and

11 у м ) = | т -M>

It f o l l o w s that | t M ) > and | y - M ^ belong to the s a m e i r r e d u c i b l e


representation.
When t h e a t o m i n t e r a c t s with a u n i f o r m e l e c t r i c f i e l d , e a c h l e v e l E y j
i s s p l i t into (J + l ) S t a r k l e v e l s (if J i s an i n t e g e r ) o r into ( J + i ) S t a r k l e v e l s
(if J i s a h a l f - i n t e g e r ) .
We have a l r e a d y m e n t i o n e d that the p a r i t y i s no l o n g e r a good q u a n t u m
n u m b e r . We a r e going to show t h a t , b e c a u s e of t h i s f a c t , t h e f i r s t n o n - z e r o
t e r m in t h e p e r t u r b a t i o n e x p a n s i o n i s p r o p o r t i o n a l to the s q u a r e of the e l e c t r i c
f i e l d . H o w e v e r , t h i s i s not t r u e in the c a s e of a c c i d e n t a l d e g e n e r a c y a s in
the h y d r o g e n s p e c t r u m f o r e x a m p l e .

7.2.2. Q u a n t i t a t i v e a p p r o a c h of t h e S t a r k e f f e c t

The H a m i l t o n i a n d e s c r i b i n g the i n t e r a c t i o n b e t w e e n an a t o m and a


u n i f o r m e l e c t r i c field (in the dipole a p p r o x i m a t i o n ) r e a d s

H
E =
-е-Де

w h e r e ß e , the e l e c t r i c dipole m o m e n t of the a t o m , i s given by - e £ ) r j (the


s u m r u n s o v e r the e l e c t r o n s of t h e atom). In a f i r s t a p p r o x i m a t i o n the
p e r t u r b i n g e n e r g y i s given by

ee z < 7 J M | Z | 7 J M ' > {Z = £ z;}


i
F r o m p a r i t y c o n s i d e r a t i o n s we know that t h e s e m a t r i x e l e m e n t s a r e a l l z e r o .
It i s t h e r e f o r e n e c e s s a r y to c o n s i d e r the s e c o n d - o r d e r t e r m

e2 2 V < Y J M [ Z | Y ' J ' M > < Y 1J' M | Z I 7 J M )


L E(yJ) - E(y' J )
У'Г
H e r e the s u m r u n s o v e r a l l s t a t e s whose p a r i t y i s opposite to | y J M X
We s h a l l s e e t h a t the m a t r i x e l e m e n t s < Y J M | z | Y ' J ' M ' > a r e the s a m e
a s e n c o u n t e r e d in the p r o b l e m of e l e c t r i c dipole t r a n s i t i o n probabilities
and we s h a l l d i s c u s s t h e i r p r o p e r t i e s in the c o r r e s p o n d i n g chapter.

8. F I E L D QUANTIZATION AND RADIATIVE PROCESSES

8.1. Quantized f r e e e l e c t r o m a g n e t i c field

8.1.1. The c l a s s i c a l f i e l d

P o r a f r e e f i e l d , M a x w e l l ' s e q u a t i o n s can be w r i t t e n as
IAEA-SMR-12 / 2 1 41

H = VX A e = -V0---I-A
С dt

9 1 3
•V2</> - A | - ( V . A ) = 0
с dt

It i s p o s s i b l e to i m p o s e s i m u l t a n e o u s l y (V- Ä) = ф = 0 so that

^ = VXA
• A =0
- = i эА
e
" с 9t

A can be written in t e r m s of m o n o c h r o m a t i c t r a n s v e r s e plane waves

A = N"1/2^ {a(k,ü)U(k,ü)+a*(k,üj)U*(k,ü)}
kw

Ü(k,<3) = î ^ e ' ^ ^ , j - ^ a ( S , û ) + k 2 c 2 a(£,ü)} = О

[ e ® = polarization vector, linear or circular]

( k - e ® ) = 0

e = N" 1 / 2 > k(i a ( k , u ) U ( k , u ) + c.c.)


kra

'= N" 1 / 2 {i a (îc,u)[5x Ü(k,u)] + с.с.}

The field e n e r g y is

Ef i e 2 dT =
= b f f f f ä ^

{Volume of the cell in which the emf is localized}

The field m o m e n t u m i s
4 2 FENEUILLE

i.1.2. Canonical f o r m a l i s m

L e t us d e f i n e

Qjf- = ( а ( £ , й ) - а * ( Й , й ) )

P = Q(k u) =
iTö Ii ' " i k c ( a ( k u ) - a*(kw))

kD
H F i s a H a m i l t o n i a n only if

Э— h = and then N = —^
9P 9t

кш

T h i s is the H a m i l t o n i a n f o r a h a r m o n i c o s c i l l a t o r .

8 . 1 . 3 . H a r m o n i c o s c i l l a t o r and second q u a n t i z a t i o n

L e t u s f i r s t d e f i n e the c r e a t i o n and a n n i h i l a t i o n o p e r a t o r s f o r one


h a r m o n i c o s c i l l a t o r by

ьш=Нр2+"2Ч2}

P = [p,q] = - №

b+ = {2ftu}" 1 / 2 [ u q - i p ] Ь ш = { 2 З Д " 1 / 2 [ioq + ip]

[ b i . b j = -i
BOSONS

h J n > = (n + | ) h u | n >
b b n
£ J > = nln>
It i s quite e a s y to show (using the c o m m u t a t i o n r e l a t i o n ) t h a t

b j n > = n ^ l n - i )

b £ | n > = (n + l ) 1 / 2 | n + l >
IAEA-SMR-12 / 2 1 43

|n> = (n!)" 1 / 2 (b£) n |o>

I
vacuum state
o r ground s t a t e

bJo> = 0

If we c o n s i d e r N independent h a r m o n i c o s c i l l a t o r s ( u j . . . Uj ... w N ), the


corresponding equations read

t b ^ , b + . ] = 6<j.i). [ b t . , b t . ] = 0, 1Ь Ш .,Ь И .] = 0

H = Z Вы, (bt. Ь ш . + i )
j

| П 1 . . . П , . . . n N > = { П 1 ! . . . п л . . . n N ! } " 1 / 2 ( b i p ... ( b t / N j o )

8.1.4. Q u a n t i z a t i o n of a f r e e e l e c t r o m a g n e t i c field

b l _ = { 2 f i w r 1 / 2 { u Q r _ - iP^_}
К UJ KOJ

bf_ = { 2 u/h}+1/2 a | _ . = hk(b|_

P l a n e wave: b e a m of n p a r t i c l e s , e a c h of t h e m having an e n e r g y e q u a l to
hw and a m o m e n t u m hit; t h e s e p a r t i c l e s a r e called p h o t o n s . We have to
s t r e s s that it would have b e e n p o s s i b l e to expand a l l the e l e c t r o m a g n e t i c
q u a n t i t i e s in t e r m s of s p h e r i c a l w a v e s (multipole f i e l d s ) . This r e p r e s e n -
t a t i o n i s well suited to c o n s i d e r the a n g u l a r m o m e n t u m of photons [7] .

8.2. General f o r m u l a s f o r transition probabilities

F o r t h i s p a r a g r a p h , s e e Ref.[9] , C h a p t e r s XVII, XXI.


P a r i s (1964) C h a p t e r s XVII, XXI.

Fundamental results

H = H0 + V

V i s the t i m e - i n d e p e n d e n t p e r t u r b i n g H a m i l t o n i a n and H 0 is the p r i n c i p a l


H a m i l t o n i a n [ e i g e n s t a t e s | a > , | b > ...]-. In a f i r s t - o r d e r a p p r o x i m a t i o n
44 FENEUILLE

W =<b|v|a>zXf(uba,t)

• W , ] 2
i sin- t
f ( u , t ) = t2 Ц 2 -

t - 00; f ( U , t ) - 2 7Г t б (CO )

^ = < b | v | a > 2 X 2ir 6 (u)

The e n e r g y i s c o n s e r v e d d u r i n g t r a n s i t i o n s .

W a . b = < b | v | a > 2 f pb Eb = Ea

pb = level d e n s i t y around the e n e r g y E b .

3.3. O n e - p h o t o n r a d i a t i v e p r o c e s s e s

5.3.1. H a m i l t o n i a n f o r an a t o m in an e l e c t r o m a g n e t i c field

• J i/j

kuj

In a P a u l i a p p r o x i m a t i o n (valid f o r dipole t r a n s i t i o n s and e l e c t r i c q u a d r u -


pole t r a n s i t i o n s )

=%r+ w z • ^ + {1
>•
+
w (Â ,2+
i S • ^
H can be r e w r i t t e n in the following f o r m : H = H 0 + H ^ j + H j + H n + Н ш where

н0 = ^ + — + magnetic t e r m s (spin-orbit interaction)


IJ
J

H = { ( Â ) + {Â ;
I l2b Pi' i j Pi)}
j

кш 3
IAEA-SMR-12 / 2 1 45

) + c
S I Z H ^ • ^ - 4

H III ^ (Aj) 2 = t e r m s involving ^ ^ (b + b + bb + )


2цс'

l e v e l s h i f t (not c o n s i d e r e d h e r e ) .

8.3.2. A b s o r p t i o n , induced and s p o n t a n e o u s e m i s s i o n

H] + H t I a r e t i m e - i n d e p e n d e n t p e r t u r b i n g H a m i l t o n i a n s d e s c r i b i n g t r a n s i -
t i o n s b e t w e e n the s t a t e s of the u n p e r t u r b e d H a m i l t o n i a n H 0 + H R a d . The r a d i a -
tion s p e c t r u m i s a s s u m e d to be continuous; it is then p o s s i b l e to d e f i n e
t r a n s i t i o n p r o b a b i l i t i e s p e r unit t i m e .
In a f i r s t - o r d e r c o n s i d e r a t i o n o n e - p h o t o n t r a n s i t i o n s a r e obtained only
if we c o n s i d e r H j + H n .

- Ef < E f initial state E j + n photons


final state E f + (n-1) photons

Ef - E , = f t u f i Absorption

• E; > Ef initial state E j + n photons


final state E f + (n +1 ) photons

E; - E f fiuh. Induced e m i s s i o n

- E; > Ef initial state Ei


final state E f + 1 photon
E j - E f = fiUlf Spontaneous e m i s s i o n

8.3.3. Spontaneous e m i s s i o n

Initial state Et, |i//i>|o>

Pinal state E f + fiuif, 11//^ | k Jf ш )•

P h o t o n e m i t t e d in the d i r e c t i o n к with the p o l a r i z a t i o n e & l The


t r a n s i t i o n p r o b a b i l i t y p e r unit t i m e and p e r unit s o l i d - a n g l e is given by

2 Vu 2
w;j =£|<f|H I + Hn|i>|
2(2FF)3F, C 3
46 FENEUILLE

T = S T j

Tj = | ( p j . + ift(Sj • { £ x e ® » ! e

W
if |<*f|T(S.i3)K>|2

Usually ( k - r ) « 1 for atomic transitions. M o r e o v e r , j5 and If have opposite


parity.

E l e c t r i c dipole t r a n s i t i o n s

Tj(ED) = (Pj • e) i s an odd o p e r a t o r .

<0f|T(ED)|^> = i ^ p M |0-е|^!>

D =e ^ rj {2jt и = и}
j

M a g n e t i c dipole and e l e c t r i c g u a d r u g o l e t r a n s i t i o n s

T
KMD + EQ> = i l i P j - Ï X I Î - ^ O + fttej-flîXcïïlipj.lXlî.r,)

= { ( ( P j X r p . f é x l ) )+ (e-ÎjXS-pj) + ( ï . ^ e . ? , ) }

T MD = j-g I ( [ J . + 2g . f 1 ' . {k1} (1) ) even operators

27гим({еШ (2) ) possible interferences


IAEA-SMR-12 / 2 1 47

9. E L E C T R I C DIPOLE RADIATIVE TRANSITIONS

9.1. Definitions

We c o n s i d e r a spontaneous t r a n s i t i o n between the two s t a t e s i and f


which have the e n e r g i e s Ef and Ef ( E ; > E f ) . We denote by a the wave v e c t o r ,
cr = |ст| i s the wave n u m b e r , и = ос/2-я = (Ej - E f ) / h is the f r e q u e n c y and e
is the p o l a r i z a t i o n v e c t o r of the single photon e m i t t e d in this t r a n s i t i o n .
If this t r a n s i t i o n is an e l e c t r i c dipole t r a n s i t i o n , the e m i s s i o n p r o b a b i l i t y
of s u c h a photon (per unit t i m e and within the i n f i n i t e s i m a l solid angle df2)
is given by

2
w(i,f)=^|<^|D£W|0f>|

where

L e t the i n i t i a l s t a t e be given by a' J' M' and s i m i l a r l y the final s t a t e by a J M .


Then we obtain

1 J
w(i,f)-=( ) <aj||Da>||a'J.>2±^î
\-M m M'/ ^

This f o r m u l a allows us to obtain the intensity d i s t r i b u t i o n when the a t o m


i n t e r a c t s with a s t a t i c f i e l d . S i m i l a r r e s u l t s hold f o r other m u l t i p o l e s .
U n l e s s the light s o u r c e is placed in a s t r o n g m a g n e t i c f i e l d , we do
not r e s o l v e the individual Z e e m a n components. We r a t h e r c o n s i d e r the
s u m of all components of a given line. If the a t o m s a r e not p o l a r i z e d
(i.e. if all s u b l e v e l s a r e equally populated) we can a v e r a g e over the i n i t i a l
s u b l e v e l s M' and s u m o v e r the f i n a l sublevels M. We also c o n s i d e r the
total p r o b a b i l i t y f o r a photon to be emitted in an a r b i t r a r y d i r e c t i o n with
a r b i t r a r y p o l a r i z a t i o n . P o r t h i s p u r p o s e we have to multiply by 8ir. The
new t r a n s i t i o n p r o b a b i l i t y is the E i n s t e i n c o e f f i c i e n t f o r spontaneous
e m i s s i o n A i f given by

A , <aj||D(1) ||o'J'>2
3 fi (2J'+1)
-M m M'/
M.M'

4 a3 1
Aif =
3 ^ i 7 .

w h e r e S ( a J , a ' J ' ) = < q<j||dW | | a ' J ' > is the line i n t e n s i t y of the t r a n s i t i o n .
In the d e s c r i p t i o n of r a d i a t i o n a b s o r p t i o n we often u s e the following
quantities:
48 FENEUILLE

Bfi = Ajf (Einstein coefficient for absorption)

/ №
ffi = &L A i f ^ ° f —J ( o s c i l l a t o r s t r e n g t h , a d i m e n s i o n l e s s quantity)
gj отг e \v/

L e t u s note that the E i n s t e i n c o e f f i c i e n t s f o r a b s o r p t i o n and induced


e m i s s i o n a r e , r e s p e c t i v e l y , r e l a t e d by:

g j Bfi = g j . Bif (Ej > Ef)


t t
A IE a'J1 aJ

R e g a r d l e s s w h e t h e r we d e s c r i b e a p r o c e s s in t e r m s of t h e E i n s t e i n
c o e f f i c i e n t o r t h e o s c i l l a t o r s t r e n g t h , a l l e x p l i c i t r e f e r e n c e to a t o m i c
s t r u c t u r e o c c u r s in t h e line i n t e n s i t y only (the f r e q u e n c y of the t r a n s i t i o n
i s u s u a l l y known f r o m e x p e r i m e n t ) .
In p r a c t i c e S i s c a l c u l a t e d in two s t e p s . F i r s t the r e d u c e d m a t r i x
e l e m e n t s a r e d e r i v e d f o r s o m e s i m p l e convenient coupling (usually LS).
T h i s m a t r i x i s then t r a n s f o r m e d into the e n e r g y s c h e m e (including s o m e -
t i m e s c o n f i g u r a t i o n i n t e r a c t i o n ) u s i n g the u n i t a r y t r a n s f o r m a t i o n <( a j | r j ) >
b e t w e e n t h e L S s t a t e s | r J M ) > and the e n e r g y e i g e n s t a t e s | a J M ) > . T h e
r e s u l t obtained r e a d s

S M ^ ' J ' ) ^ < o j | r J > < r j | | D ( D ||Г"J'> < Г ' J ' I a-'J' >
ГГ '

O b v i o u s l y , s u m m a t i o n m u s t be done b e f o r e s q u a r i n g ; t h e n i n t e r f e r e n c e o r
cancellation effects may appear.

9.2. The l i n e and m u l t i p l e t f a c t o r s

In LS coupling, the r e d u c e d m a t r i x e l e m e n t s of DW have the f o r m

< aSLjIlD*1' ||a'S'L'J'>

Since d № a c t s on o r b i t a l p a r t s only ( s p i n - i n d e p e n d e n t o p e r a t o r ) we can


write

rJ i j'l
< a S L j | | D t t > | | a ' S ' L ' J ' > = {[JltJ 1 ]} 1 / 2 6(S,S') \ \ (,-l)J + l + L4S
L' S L

X <aSL||DW ||a'S'L'>

The line f a c t o r á ? ( S L J , S'L 1 J ' ) i s defined by

J 1 J'
â t (SLJ, S ' L ' J ' ) = { [ j ] [ j ' ] } 1 / 2 6(S, S') • (-1 )J + 1 + L' + S
L' S L
IAEA-SMR-12 / 2 1 49

^ 2 ( S L J , S ' L ' J ' ) gives the r e l a t i v e i n t e n s i t i e s of the l i n e s of a m u l t i p l e t


in the c a s e of p u r e LS coupling. Since 6(S,S') a p p e a r s in we hence
obtain the s e l e c t i o n r u l e AS = 0. F r o m the p r o p e r t i e s of the 6j s y m b o l
we can d e r i v e a l s o the s e l e c t i o n r u l e s

ALI Š 1 S [L + L'J

A J I g 1 s [J + J ' l

The s u m m a t i o n p r o p e r t i e s of R a c a h ' s c o e f f i c i e n t s p r o v i d e u s with two


u s e f u l s u m r u l e s which r e a d

^Ts(SL'J',SLJ) = j g j | < a S L | | D « ||aSL'>|2


J

S ( S L ' J ' , S L J ) = [S]|< oSL||D ( 1 ) | | a S L ' > | 2


J.J"
We s e e that the r e d u c e d m a t r i x e l e m e n t | aSL | | d № | | a S L ' ^ | y i e l d s the
r e l a t i v e i n t e n s i t i e s of d i f f e r e n t m u l t i p l e t s . R e p e a t e d application of the
t e c h n i q u e s d e s c r i b e d in c h a p t e r s 4, 5, 6, m a k e s it p o s s i b l e to w r i t e t h i s
r e d u c e d m a t r i x e l e m e n t in a f i n a l f o r m , a s the p r o d u c t of a s i n g l e - e l e c t r o n
r e d u c e d m a t r i x e l e m e n t e 2 ^ n í || r W ||п'Л'^> which depends only on the
q u a n t u m n u m b e r s of the jumping e l e c t r o n and on a f a c t o r which we s h a l l
c a l l t h e m u l t i p l e t f a c t o r 9 t ( a SL, o ' S L ' )

< a S L | | D ( 1 ) H a' S' L 1 > = e 2 < n i || r ( 1 ) || n ' i 1 {a SL, a' SL')

where

< nil I rU) | | n ' i ' > = < i | | C U ) | | i ' > < n i | r | n ' i ' > = ( - l ) í _ í > nTí> < n i | r | n ' i ' >

With t h e s e definitions the line i n t e n s i t y with p u r e LS coupling i s given by

S ( a S L J , a ' S ' L ' J ' ) = ât2(SLJ, S L ' J ' ) á? 2 (a SL, a ' S L ' ) б (S, S' ) i > < n i | r | n ' i '> 2

Many a u t h o r s u s e a quantity a 2 defined by

2 = <ni|r|n'i'>2
" (4i2 - 1 )

The m u l t i p l e t f a c t o r d e p e n d s upon the two p a r t i c u l a r c o n f i g u r a t i o n s involved


in the t r a n s i t i o n . In any c a s e , it can be e a s i l y obtained by m e a n s of the
t e c h n i q u e s d e s c r i b e d in c h a p t e r s 4 , 5 , 6 . F o r e x a m p l e , if we c o n s i d e r
t r a n s i t i o n s of the type

iN oSL JM í N - l a Š L i ' S' L ' J ' M'

the m u l t i p l e t f a c t o r is given by:


50 FENEUILLE

iL 1 L"
1
N < ^aSL^^" aSL>j • {[L][L']} 1 / 2
( - i ) l + L + I + r
L je1 L SL

F r o m the f o r m u l a s obtained f o r the m u l t i p l e t f a c t o r s , it i s v e r y e a s y to


o b t a i n s u m r u l e s f o r line i n t e n s i t y . F o r t r a n s i t i o n s of, e . g . the type
- i N j T , we obtain:

^ S ( o S L J , o ' S L ' J ' ) = -Ц1 < n ' 4 ' || r U> || n " í " > 2 '
LT
L e t us r e m a r k t h a t the o s c i l l a t o r s t r e n g t h a l s o s a t i s f i e s s e v e r a l u s e f u l
s u m r u l e s . B e s t known i s the R e i c h e - T h o m a s - K u h n f - s u m r u l e , which
s t a t e s that t h e s u m of a l l o s c i l l a t o r s t r e n g t h s f r o m a given l e v e l n i s e q u a l
to the n u m b e r of e l e c t r o n s , the s u m going o v e r a c o m p l e t e s e t of s t a t e s n ' ,
including l e v e l s below n , above n , and continuum s t a t e s .

9.3. T r a n s i t i o n i n t e g r a l s

A s a l w a y s , the r a d i a l i n t e g r a l s a p p e a r i n g in t r a n s i t i o n p r o b a b i l i t i e s
a r e t h e q u a n t i t i e s which a r e m o s t d i f f i c u l t to o b t a i n . The a p p r o x i m a t i o n s
d e s c r i b e d in c h a p t e r 1 have b e e n u s e d , but the t a b l e s m o s t f r e q u e n t l y used
a r e t h o s e of B a t e s and D a m g a a r d ; t h e i r wave f u n c t i o n s a r e b a s e d on a
C o u l o m b a p p r o x i m a t i o n to the c e n t r a l f i e l d .
L e t us note that n i | r | n ' i 1 > is u s u a l l y m a x i m u m when |n - n' | i s
s m a l l e r t h a n ( Í - V ) and d e c r e a s e s r a p i d l y when | ( n - n ' ) | b e c o m e s g r e a t e r
t h a n 1.
In the h y d r o g e n i c a p p r o x i m a t i o n n í | r | n ' i ' )> b e h a v e s a s l / Z , so that f
b e h a v e s a s l / Z f o r t r a n s i t i o n s An = 0 and i s a c o n s t a n t f o r t r a n s i t i o n s Д п ^ О .

10. RELATIVISTIC E F F E C T S IN ATOMIC S P E C T R A

10.1. D i r a c equation

1 0 . 1 . 1 . D i r a c equation f o r a f r e e p a r t i c l e

E2 = ^ 2 с 4 + р 2 с 2

h 2 {ci Д - Э 2 } = м2 с 4 K l e i n - G o r d o n equation

h 2 с 2 д - h 2 a 2 - ц 2 с 4 = { - i R c ( o . v ) + m a t + /з^с 2 }

{ihc(a • V) +ih3t - jSmc2} = 0

г
c ( a . p ) +/3рс - E = 0

2
a® = , 3 = 1 , = 2S M U , [ a ß , ß ] + = 0
IAEA-SMR-12 / 2 1 51

I 0 0 <J
4X4 matrices
0 -I I a 0

1 0
а
0 1
=
0 -i
=
Il1 0
х= °y
0 1 1 0 i 0 Il 0 -1

Ф=

( E - / и с 2 ) ф 1 -с(ст-р)ф 2 = О

- c ( t j . p )фг + ( Е + Й С 2 ) Ф 2 = О

10.1.2. D i r a c equation f o r a p a r t i c l e i n t e r a c t i n g with a c l a s s i c a l field

E - E + eV р^тг = р + - А

h D = с ( a - n ) + ß ß d 2 - eV

(E -juc2 + ёЧ)фг - с(о-л)ф2 =0

-с(ст - 7 г 1 + (Е +|ис 2 + еУ)ф2 = 0

The n o n - r e l a t i v i s t i c l i m i t f o r p o s i t i v e e n e r g y s t a t e s i s obtained a s f o l l o w s :
c ( a - Ť ř ) « |uc 2 I eV I « ßc ф «ф

(ст-я)2-еу| = Wc^ W = (E - ßc 2 )

(ст-А)(ст-В) = ( Â - S ) + i(S-{ÂXB})

{ИХж} = - i ^ ( V X Â ) = -

+ (3 eV = Pauli
'^ " } Ration
52 FENEUILLE

10.2. E l e c t r o n in a c e n t r a l field

10.2.1. Motion c o n s t a n t s

h 0 = c{a-p)+ßpc2 - eU(r)

fi 1 = (r Xp)

[ h D , ~l] = - i c ( a X p )

(h D , a] = 2ic(3x p)

f =? +
[hD,j1 = 0

In t h i s way, it i s p o s s i b l e to obtain s t a t e s which a r e s i m u l t a n e o u s l y e i g e n -


f u n c t i o n s of h D , j*2, and j z .

10.2.2. G e n e r a l f o r m of s o l u t i o n s

N o n - r e l a t i v i s t i c l i m i t : Фг Фт <t>2~* ®
Without b e i n g i n c o n s i s t e n t , we can e x p e c t t h a t , in g e n e r a l ,

1
ф1 = ^ G ( r ) | | i j m >

where

||4jm> = < H , i m - i |jm> | i m - i > + < i -i, im+l|jm>

( E + e U - M c 2 ) ^ \\t j m > -c(a-p)ф2 = 0

li-e j m > + (E + eU +дс 2 )ф 2 = 0

( a . V ) - | i i j m > = 2(-l) _ r +.
r dr 2r

I i j
X < i | | s | | | > < 7 | | C ( 1 ) ||i> llüjm) [i = 2 j - i ]
1 i 1

2(-l)^ + { + i < ||C ( 1 ) | | i > < | | | s | | } > Г £ 3


f =1

U(je + l ) - i ( j e + l)] = ( - l ) i + M ( 2 j + l ) = 2k
IAEA-SMR-12/4,5 53

The s e c o n d equation i s s a t i s f i e d if we w r i t e

= -i ÍF(r)|ijíjm>

4 - G + - G = \ (E+MC 2 + e U ) F
dr r cn

Now it i s e a s y to show that

|iijm> = { i £ r - i } J | * i j m ;

so that

dF kF 1 ,_ о . „,
-5 — E - ц c z +eU G
dr r cti

Conclusion:

G
r |iijm>
k) =
. F
- i— |iljm>
r

dG 2ao
dr = |(l+€) + ° u} F

dF
= { ( 1 - е ) - SČlí u | G
dr - Î }
e = E/mc2

f ( F 2 + G 2 )dr = 1
о

10.2.3. N o n - r e l a t i v i s t i c l i m i t

A t t r a c t i v e potential: U = — S(r)

P o s i t i v e - e n e r g y s t a t e s ( d i s c r e t e + continuous)

e = 1 + a2e2 + a4 e4 +

G = G0 + a 2 G 2 +

F = AFJ + O 3 F 3 +
54 FENEUILLE

d 2 Gp Je<Jg + l) n ^
(W + eU)G 0 = 0
dr2

p = oaç, № + к
1
2 dr r

Negative-ejiejrj^y s t ä t e s J o n l ^ continuous)

e = - i + a 2 e2 + a 4 e 4 +

G = oG a + o 3 G 3 +

F = F 0 + a 2 Fz

10.2.4. C o u l o m b f i e l d

F o r t h i s s e c t i o n , s e e R e f . [ 1 1 ] , C h a p t e r V.
F o r bound p o s i t i v e e n e r g y s t a t e s we have

Z2 "Accidental" degeneracy
2
2n 2 e d e p e n d s on |/c] only

Z4 in 3

10.2.5. G e n e r a l f o r m of r a d i a l f u n c t i o n s

With a p o t e n t i a l s a t i s f y i n g the g e n e r a l conditions

S(0) = Z S(°o) = I

e a c h l e v e l can again be c h a r a c t e r i z e d by n ( i n t e g e r >0) i (integer < n) and


j (half i n t e g e r , Í ± i ) , but now the o n e - e l e c t r o n e n e r g i e s a r e no l o n g e r s i m p l y
r e l a t e d to n. H o w e v e r , n s t i l l h a s a p r e c i s e m e a n i n g , s i n c e it can be shown
t h a t (a) the n u m b e r of nodes of G (excluding the o r i g i n ) i s n - i - 1 and (b) the
n u m b e r of nodes of F (excluding the o r i g i n ) i s п - | к | . F u r t h e r m o r e we s e e
t h a t , if we e x c e p t the o r i g i n , the nodes of F and G cannot c o i n c i d e . Let us
m e n t i o n t h a t at the o r i g i n F / r and G / r d i v e r g e f o r j = | .

10.2.6. F u n d a m e n t a l m a t r i x e l e m e n t s

F r o m c e n t r a l - f i e l d o n e - e l e c t r o n s t a t e s , it i s p o s s i b l e to s t u d y the
e f f e c t s of v a r i o u s p e r t u r b i n g H a m i l t o n i a n s (Coulomb and B r e i t i n t e r a c t i o n
between electrons, Zeeman effect, hyperfine structure, radiative transitions,
e t c . ) , j u s t a s in the n o n - r e l a t i v i s t i c c a s e . All t h e s e i n t e r a c t i o n s can be
e x p r e s s e d in t e r m s of two t y p e s of o p e r a t o r s , n a m e l y ^

C® and {aC®}^
IAEA-SMR-12/4,5 55

P r o m the r e s u l t s d e r i v e d p r e v i o u s l y , we know t h a t the only p r o b l e m i s to


o b t a i n the c o r r e s p o n d i n g r e d u c e d m a t r i x e l e m e n t s .
F i r s t , it i s e a s y to show that

( n ' i ' j ' | | c ( k ) | | n i j ) = G ' G < i ' j ' ||c<k> | | i j > + F ' F < I ' j ' | | C < k > p j >

(n4"j||{aC< k >}( K > [I rue j ) = i F ' G ^ ' j ' H i a d ' C « } ^ » | | ^ >

- iG'F ||Í0.C1)C<K) }(К) р 3 > •

T h e n , it f o l l o w s i m m e d i a t e l y that

' j' k j 1 / V k Л \
( n ' i ' j 1 II C ( k ) Hnij) = G G ' l - l l ^ M l j l l j ' l W U 1 ] } 1
i i v J у 0 0 0

f j1 k j , / 7 . k 7 )
r+i 1
+ FF'(-l) {fjJIj'Hilli']) \
i Л' J \ о о 0 /

1
i2 2
i1
i' k Л
( n ' i ' j ' ||{aC ( k ) } ( K ) | | n i j > = i F ' G ( - l ) r { 3 [ j ] [ j ' ] [ K ] [ i ' ] [ i ] / 2 F i" i k
0 0 0
Li' j К

i2 ±г 1í
V к Л
• i G ' F ( - l ) { '{3 [j][j'] [К] [Í'] [í] / 2}^ i' I k
Уо о о
j' j к
H o w e v e r , the p r e c e d i n g f o r m u l a s can be w r i t t e n in a f o r m involving only
3j-symbols:

(n'i'j'||c<k> ||nij)= (-l)i + M 3 k 3


) l { l + ( - l ) k + í + í '}
\i 0 -\j

X A(k,í,i'){[j][j']}ž (GG'+FF1)

( n ' i ' j ' | | { a C ( k ) } ( K ) | | n i j ) = -i{[K][j][j']}* i { l + ( - l ) k + { + r+1


}

/ i k к \ /j- к j4
2Ц-1)1 [A (k, i i ) F ' G + A(k, Í i ) F G ' ]
\-l 0 1 / U -1 i

1 k К \ /j' К j \
+ (Л
- 1 )\Г + * [Д(к, i ' , Í ) G ' F - Д (k, í 1 , Í ) F ' G ]
56 FENEUILLE

Д ( а , Ь , с ) t r i a n g u l a r condition s y m b o l . The proof of t h e s e f o r m u l a s can


be c o n s i d e r e d a s an e x e r c i s e . L e t u s r e m a r k , h o w e v e r , that it i s e s s e n t i a l
to u s e the f o l l o w i n g identity:

= 2"* (-l)i + 1
[iH

10.3. F o u l d y - W o u t h u y s e n t r a n s f o r m a t i o n . Non-relativistic limit

F o r t h i s s e c t i o n s e e R e f . [9] . F o r an e l e c t r o n in a c e n t r a l field we have

H 2 _ Ho P4 . ft2 1 dV - ft2 A V
H H + ( f f i ) +
m - n r j

spin-orbit t e r m

10.4. B r e i t i n t e r a c t i o n , B r e i t - P a u l i a p p r o x i m a t i o n

F o r this section see Ref.Il] .

REFERENCES

[1] BETHE, H . A . , SALPETER, E. E . , Q u a n t u m M e c h a n i c s of O n e - a n d T w o - E l e c t r o n A t o m s , Springer


V e r l a g , Berlin ( 1 9 5 7 ) .
[2] C O N D O N , E . U . , SHORTLEY, G. H . , T h e T h e o r y of A t o m i c S p e c t r a , C a m b r i d g e U n i v e r s i t y Press ( 1 9 5 1 ) .
[3] SLATER, J . C . , Q u a n t u m T h e o r y of A t o m i c S t r u c t u r e , M c G r a w - H i l l , N e w York ( 1 9 6 0 ) .
[4] SHORE, B . W . , MENZEL, D . H . , P r i n c i p l e s of A t o m i c S p e c t r a , W i l e y , N e w York ( 1 9 6 8 ) .
[5] EDMONDS, A . R . , A n g u l a r M o m e n t u m i n Q u a n t u m M e c h a n i c s , P r i n c e t o n U n i v e r s i t y Press ( 1 9 6 0 ) .
[6] JUDD, B . R . , O p e r a t o r T e c h n i q u e s in A t o m i c S p e c t r o s c o p y , M c G r a w - H i l l , N e w York ( 1 9 6 3 ) .
[7] BRINK, D . M . , SATCHLER, G . R . , A n g u l a r M o m e n t u m , C l a r e n d o n Press, O x f o r d (1968).
[8] JUDD, B. R . , S e c o n d Q u a n t i z a t i o n a n d A t o m i c S p e c t r o s c o p y , T h e John H o p k i n s Press, B a l t i m o r e ( 1 9 6 7 ) .
[9] MESSIAH, A . , Q u a n t u m M e c h a n i c s , D u n o d , Paris ( 1 9 6 4 ) .
[10] HEITLER, W . , T h e Q u a n t u m T h e o r y of Radiation, O x f o r d U n i v e r s i t y Press ( 1 9 4 4 ) .
[11] ROSE, M . E . , R e l a t i v i s t i c E l e c t r o n T h e o r y . W i l e y , N e w York ( 1 9 6 1 ) .
IAEA-SMR-12/52

THEORY OF ATOMIC STRUCTURES,


TRANSITIONS, AND M O L E C U L A R P O T E N T I A L
CURVES WITH E L E C T R O N CORRELATION
IN GROUND AND E X C I T E D S T A T E S

O. SIN AN OG LU
Sterling Chemistry Laboratory,
Yale University, New Haven, Conn.,
United States of America
and
Kuramsal Kimya Bölümü
Orta Dogu Teknik Evrenkenti,
Ankara, Turkey

Abstract

THEORY OF A T O M I C STRUCTURES, T R A N S I T I O N S , AND MOLECULAR POTENTIAL CURVES WITH


ELECTRON CORRELATION IN GROUND AND EXCITED S T A T E S .
1. Introduction; 2, N e w a t o m i c - s t r u c t u r e t h e o r y with e l e c t r o n c o r r e l a t i o n ; 3 . T h e o r y of t h e N - e l e c t r o n
excited state; 4 . T h e a l l - e x t e r n a l c o r r e l a t i o n E^ and e n e r g y l e v e l s ; 5. T r a n s i t i o n p r o b a b i l i t i e s ;
6. M o l e c u l a r b i n d i n g and p o t e n t i a l e n e r g y c u r v e s ; 7. T h e s e m i - i n t e r n a l c o r r e l a t i o n e f f e c t and m o l e c u l a r
potential energy curves; 8 . T h e c h a r g e w a v e f u n c t i o n and c h a r g e d i s t r i b u t i o n r e l a t e d p r o p e r t i e s of m o l e c u l a r
excited states.

1. INTRODUCTION

M o d e r n a t o m i c and m o l e c u l a r e l e c t r o n i c s t r u c t u r e t h e o r y can be
s u b d i v i d e d i n t o t h r e e p a r t s : (1) o r b i t a l t h e o r y , (2) c o r r e l a t i o n t h e o r y ,
a n d (3) r e l a t i v i s t i c t h e o r y .
T r a d i t i o n a l m e t h o d s , t h e H a r t r e e - F o c k (H. F . ) m e t h o d , h y d r o g e n i c
Z - d e p e n d e n t m e t h o d , the C o n d o n - S h o r t l e y and S l a t e r - R a c a h m e t h o d s , the
m o l e c u l a r o r b i t a l (M. O. ) a n d v a l e n c e bond ( V . B . ) m e t h o d s a r e a l l b a s e d
on t h e o r b i t a l a p p r o a c h .
Y e t , m a n y a t o m i c a n d m o l e c u l a r p r o p e r t i e s a r e not given a d e q u a t e l y ,
n o r at t i m e s even qualitatively c o r r e c t l y by o r b i t a l s . Table I shows this.
M o l e c u l a r binding, v a n - d e r - W a a l s a t t r a c t i o n s , and e l e c t r o n a f f i n i t i e s
r a r e l y e x i s t e v e n if one u s e s t h e b e s t o r b i t a l s , t h e H. F . o n e s . T r a n s i t i o n
p r o b a b i l i t i e s c a n b e i n c o r r e c t b y f a c t o r s l i k e 2 - 3 in C , N, O, . . . , a n d
f a c t o r s l i k e 1 0 - 3 0 in M g , Si, C l , F e , e t c . T h e d i f f i c u l t y in t h e s e p r o p e r t i e s
i s d u e t o " e l e c t r o n c o r r e l a t i o n " , t h e d e v i a t i o n of t h e m o t i o n s of e l e c t r o n s
f r o m t h e i r a v e r a g e o r b i t a l b e h a v i o u r due t o i n s t a n t a n e o u s C o u l o m b r e p u l s i o n s .
T h e a t o m i c and m o l e c u l a r N - b o d y p r o b l e m , t h e m a n y - e l e c t r o n p r o b l e m ,
d i f f e r s in i t s n a t u r e f r o m t h e " m a n y - b o d y p h y s i c s " p r o b l e m s l i k e e l e c t r o n
gas, n u c l e a r m a t t e r , superconductivity, field theory, etc. F o r this
g r e a t d i f f e r e n c e a n d c o m p a r i s o n of v a r i o u s p r o b l e m s a s w e l l a s h i s t o r i c a l
a p p r o a c h e s to e l e c t r o n c o r r e l a t i o n , p l e a s e s e e t h e b o o k b y O. S i n a n o g l u
a n d K . A. B r u e c k n e r , " T h r e e A p p r o a c h e s t o E l e c t r o n C o r r e l a t i o n in
A t o m s " ( Y a l e Univ. P r e s s , 1971). T h e b o o k a l s o g i v e s t h r e e m o d e r n

57
58 SINANOGLU

T A B L E I. O R B I T A L THEORY VERSUS E X P E R I M E N T - I M P O R T A N C E
OF E L E C T R O N C O R R E L A T I O N IN ATOMIC AND M O L E C U L A R
PROPERTIES

Orbital theory Experiment


Property
(Hartree-Fock; MO) (Hartree-Fock + correlation)

E l e c t r o n a f f i n i t y of -0.54 " 1.465


o x y g e n a t o m (eV)

D e of F 2 m o l e c u l e (eV) - 1 . 37 c
1. (
e
U of H e . . . H e P. E. c u r v e van-der-Waals van-der-Waals
repulsion attraction
( m i n i m u m u / к ~ 10 К . )

Excited s t a t e energy
separation-term splitting

Ratio — i n 1s2 2 f ? of 0 + 4 1.47 ' 3.15

Electric dipole transition-


o s c i l l a t o r s t r e n g t h f g ^ of
Is 2 2s? 2p 2 (3 P) Is 2 2s2p 3 (3 D) of N + 0. 236 8 0.101

O s c i l l a t o r s t r e n g t h f E 1 of P +

3p2(3P)-»3p3(3P°) 0. 2 5 6 J

a
R O O T H A A N , C . C . I . , KELLY, P . S . , Phys. Rev. 131, (1963) 1 1 7 7 .
b
BATES, D. R . , MOISEWITSCH, B. L. , P r o c . Phys. S o c . (London) A 6 8 , (1955) 5 4 0 .
c
WAHL, A . C . , J. C h e m . Phys. 4 1 , (1964) 2 6 0 0 . N o t e o p p o s i t e sign t o e x p e r i m e n t a l .
d
I C Z K O W S K I , R. , MARGRAVE, J. , J. C h e m . Phys. 30, ( 1 9 5 9 ) 4 0 3 . (Zero point correction from
GAYDON, A . G . , Dissoc. E n e r g i e s C h a p m a n H a l l L t d . , London ( 1953).
e
KESTNER, N . R . . SINANOGLU, O . , J. C h e m . Phys. 4 5 , ( 1 9 6 6 ) 194.
' Based on MOORE, C . , A t o m i c Energy L e v e l s , NBS, W a s h i n g t o n D. C . ( 1 9 4 9 ) .
a
8 Calculated from the Hartree-Fock wave functions (cf. ).
h HEROUX, L. , Phys. Rev. 153, ( 1 9 6 7 ) 1 5 6 .
' BECK, D . R . , SINANOGLU, O. , Phys. Rev. Lett. 28, (1972) 9 4 5 .
J
SAVAGE, B . D . , LAURENCE, G . M . , Astrophys. J. 146, ( 1 9 6 6 ) 940.

a p p r o a c h e s to e l e c t r o n c o r r e l a t i o n in g r o u n d - s t a t e a t o m s . F o r excited
s t a t e s , t h e t h e o r y of e l e c t r o n c o r r e l a t i o n h a s b e e n d e v e l o p e d r e c e n t l y by
Sinano§lu ( N o n - C l o s e d Shell M a n y - E l e c t r o n A t o m i c S t r u c t u r e T h e o r y
N C M E T / M E T ) [1] and applied and c o m p a r e d with e x p e r i m e n t s by h i m and
his co-workers.
T h e t h i r d p h a s e of e l e c t r o n i c s t r u c t u r e t h e o r y , the r e l a t i v i s t i c one,
b e c o m e s p a r t i c u l a r l y c r u c i a l at a t o m s like tin (Sn) and h i g h e r Z - v a l u e s .
R e l a t i v i s t i c H . F . o r b i t a l s a r e obtained in s e v e r a l l a b o r a t o r i e s , but the
b a s i c t h e o r y i n v o l v e s c o r r e l a t i o n , r e l a t i v i s t i c and r a d i a t i v e e f f e c t s beyond
t h e D i r a c - l i k e o r b i t a l s and is v e r y l i t t l e developed at p r e s e n t .
In t h i s p a p e r we f i r s t outline t h e new e l e c t r o n i c s t r u c t u r e t h e o r y
with e l e c t r o n c o r r e l a t i o n in ground and excited s t a t e s ( N C M E T / M E T ) [1].
IAEA - S M R - 1 2 / 5 2 59

T h e n we a p p l y it to o p t i c a l t r a n s i t i o n p r o b a b i l i t i e s c o m p a r i n g the r e s u l t s
with new e x p e r i m e n t a l a t o m i c m e t h o d s . T h e new t h e o r y b r i n g s t h e
a c c u r a c y [2, 3] to 5-10% c o m p a r e d to f a c t o r s of 2 - 3 0 of the e a r l i e r m e t h o d s .
T h e m o l e c u l a r - p o t e n t i a l - e n e r g y - c u r v e s p r o b l e m i s a l s o one of highly
o p e n - s h e l l s with c r u c i a l c o r r e l a t i o n e f f e c t s l e a v i n g the MO 1 s i n a d e q u a t e [4].
T h e N o n - C l o s e d Shell M a n y - E l e c t r o n T h e o r y (NCMET) now p e r m i t s a
s y s t e m a t i c t r e a t m e n t of t h e s e c o r r e l a t i o n e f f e c t s a l s o . T h u s it h a s b e c o m e
p o s s i b l e with the u s e of N C M E T to obtain p o t e n t i a l e n e r g y c u r v e s and
s u r f a c e s h a v i n g a p p l i c a t i o n s in a t o m and m o l e c u l e c o l l i s i o n p r o b l e m s , in
m o l e c u l a r s p e c t r o s c o p y and in c h e m i c a l k i n e t i c s [5].

2. NEW A T O M I C - S T R U C T U R E T H E O R Y WITH E L E C T R O N
CORRELATION
T h e a t o m i c s t r u c t u r e t h e o r y m a y be t r e a t e d in two p a r t s :
(1) ground s t a t e s , (2) e x c i t e d s t a t e s . M o r e r i g o r o u s l y t h i s d i v i s i o n i s
one into (a) c l o s e d (and q u a s i - c l o s e d s h e l l s , i. e. s i n g l e d e t e r m i n a n t a l
s t a t e s ) and (b) open s h e l l s y s t e m s .
L e t u s c o n s i d e r f i r s t the t h e o r y of the g r o u n d s t a t e s . T h e g e n e r a l
n o n - r e l a t i v i s t i c H a m i l t o n i a n can b e w r i t t e n a s

IN IN

H (i)

w h e r e the t e r m s h? a r e o n e - e l e c t r o n o p e r a t o r s

hN-H-Ц
i
and the t w o - e l e c t r o n o p e r a t o r i s the i n t e r e l e c t r o n i c C o u l o m b r e p u l s i o n

Sij = 7 ~ (3)
ij
T h e H a r t r e e - F o c k f u n c t i o n of such a s y s t e m i s

^RHF = ^ ( 1 , 2 , 3, . . . i, . . N) (4)

with i = i(xi ) a s p i n - o r b i t a l with an a s s o c i a t e d e n e r g y E R H F .


C o m p a r i n g with the e x a c t solution of (1)

HI// = ENRI// ( E n r = non-relativistic energy) (5)

we d e f i n e t h e c o r r e l a t i o n e n e r g y a s

E E + E
NR " RHF CORR (6)
60 SINANOGLU

T h e a t o m i c Í^RHP i m p l i e s the 0(3) © SU(2) s y m m e t r y f o r e a c h s p i n -


o r b i t a l ; i. e. c e n t r a l s y m m e t r y in c o n f i g u r a t i o n s p a c e and s p i n f o r e a c h
spin-orbital. H e r e the designation " R H F " m e a n s " r e s t r i c t e d H a r t r e e -
F o c k " . T h i s i s t h e s t a n d a r d H a r t r e e - F o c k m e t h o d u s e d in e x c i t e d s t a t e s .
O u r p r o b l e m i s to o b t a i n t h e r e s t of t h e e x a c t w a v e f u n c t i o n (wf)
a n d E c o r r f o r t h e g e n e r a l N - e l e c t r o n (N - e") p r o b l e m . We h a v e the N -
fermion Hilbert space . . . ® L 2 . F i r s t we d e f i n e t h e o r t h o g o n a l
c o m p l e m e n t of $ R H F = ф0:

ф = ф0+ x With < ф01 X > = 0 (7)

<ф0|ф0>=1 and = 1+ < x | x > (8)

s o a s to k e e p t h e c o r r e l a t i o n wf o r t h o g o n a l t o the H . F . s e a , a s in E q . (7).
T o h a v e a n e s t i m a t e of c o r r e l a t i o n we h a v e

< 2 ^ « l a n d | « 2 £ $ 1 % (9)
1
ERHF

We h a v e t h e a d v a n t a g e o v e r a n i n f i n i t e s y s t e m l i k e a n e " - g a s t h a t < x | x У
i s finite, but the finite N-e" p r o b l e m h a s other difficulties a s c o m p a r e d to
an infinite s y s t e m .
W e s h a l l u s e t h e t w o t o o l s w e h a v e i n t r o d u c e d f o r t h e f i n i t e N-body-
problem:
(1) T h e m e t h o d of s u c c e s s i v e p a r t i a l o r t h o g o n a l i z a t i o n s M S P O
( s u c c e s s i v e d e c o m p o s i t i o n s of t h e N - p a r t i c l e H i l b e r t s p a c e ) [6] and
(2) T h e s u b v a r i a t i o n a l p r i n c i p l e s (we a l s o c a l l e d it t h e v a r i e d - p o r t i o n s
a p p r o a c h V P A [1] ).
T o u s e M S P O f o r a g r o u n d s t a t e we s t a r t with i£ r h f = Д ( s i n g l e S l a t e r
d e t e r m i n a n t ) . Suppose f o r the m o m e n t we have the exact wave function
фЫ1,х2, . . . xn).
W e m a k e t h e wf s u c c e s s i v e l y o r t h o g o n a l t o N , t h e n t o ( N - l ) s p i n -
o r b i t a l p r o d u c t s down t o one s p i n - o r b i t a l l e f t , b y S c h m i d t o r t h o g o n a l i z a t i o n
p r o c e d u r e s , and f i n a l l y we s u m a l l the n u m b e r s t h u s c o n s t r u c t e d .

s o
X = - |ф 0 > <<í>ok > > =0 <10)

and

(И)

N o t e t h a t x i s in t h e N - e l e c t r o n s p a c e , but b e c a u s e of t h e s p i n - o r b i t a l in
t h e d e n o m i n a t o r it i s m u l t i p l i e d b y an ( N - l ) - e l e c t r o n f u n c t i o n
[1, 2, . . . , h , k , . . . N } and s o (11) d e f i n e s a ( 1 - e " ) - f u n c t i o n ; a l s o n o t e t h a t
f j (x ; ) d e p e n d s on i.
W e d e f i n e x1 a s :

X1 = x - У Л*Ч|1,2 h , k , . . . N > < 1 , 2 , . . , h , k , . . ,N|X >} (12)

i = 1
IAEA - S M R - 1 2 / 5 2 61

We t h e n do t h e s a m e in t h e ( N - 2 ) - e l e c t r o n s p a c e , e t c . We c a l l t h e (N-2)
m e m b e r û | j , t h e (N-3) - o n e t h e t h e ûj'jk , . . . and f i n a l l y s u m t h e m a l l up
and obtain

N N N
{ Û } + {Û + +
ф = Ф0 + Y Ф + X b i 'iik> • • • <Û123...N> ( 1 3
>

i=1 i>j ijk

with e. g.

{u
ij}= W (14)

and we obtain f r o m E q s (10)-(12) a l s o the " o r b i t a l - o r t h o g o n a l i t y " r i g o r o u s l y .

< ф > =0, Kûyfxi, x - í U í x j ) ) =0, etc. (15)


x
i

with £ = 1, 2, . . . N. T h e s e c o n d p a r e n t e s e s contain a f u n c t i o n of Xj b e c a u s e
we only i n t e g r a t e with r e s p e c t to x j , and s o on. T h i s i s r e l a t e d to the F o c k -
Dirac density p = £ | - O 0 | .
T a k e и^ к е , f o r e x a m p l e . It can be put a s a s u m of a l l p o s s i b l e p r o d u c t s
of p r e v i o u s û ' s without r e p e a t e d s u b s c r i p t s .

f
û'ijki = fj 4 e ) + tfk û
ij ) + u
ijk ) + ( û
û û
kf) + - - . + úijkř (16)

T h e l a s t t e r m i s a q u a t e r n a r y " c o l l i s i o n " of t h e type J | a g a i n s t b i n a r y


c o l l i s i o n s like о о', e t c .
Not only i s (16) a f i n i t e c l o s e d e x p r e s s i o n but it a l s o i n t r o d u c e s a
c l o s e d e x p r e s s i o n f o r the e n e r g y , u s i n g E q s (13-16) in

E — - — j — = E (17)
/

T h e next s t e p is t o v a r y a l l c o m p o n e n t s

{ó^} = {ófj, áújj ÔÛm_ _N} (18)

o b t a i n i n g a f i n i t e n u m b e r of coupled E u l e r e q u a t i o n s that a r e e q u i v a l e n t
to S c h r ö d i n g e r 1 s equation. B u t t h e detailed e n e r g y now gives i n s i g h t into
t h e c o n s t i t u e n t s of ? and E and we can p r o c e e d to g u e s s o r d e d u c e the
i m p o r t a n t p a r t s and only v a r y t h o s e .
We c h o o s e a s i g n i f i c a n t p o r t i o n of the Ë and v a r y it. We have an
E u l e r ( n o n - h o m o g e n e o u s ) e q u a t i o n whose solution m a y e x i s t . If not, it
c o m e s f r o m a w r o n g c h o i c e of the i m p o r t a n t p o r t i o n of Ë and it i s
r e c o g n i z e d b e c a u s e if the s o l u t i o n e x i s t s we get s t a t i o n a r y p o r t i o n s of Ë .

6 ('important part') =0 (19)


62 SINAN OG LU

W e s h a l l p r o c e e d t o show t h a t t h e ûjj a r e t h e m o s t r e l e v a n t t e r m s . So
f r o m t h e E u l e r e q u a t i o n s we get t h e ûjj ' s . H o w e v e r , we h a v e l o s t the
u p p e r bound p r o p e r t y

E ф (important part) (20)

B u t we can u s e t h e ûjj o b t a i n e d and o b t a i n f r o m t h e f u l l Ë of E q . (17):

E = (Imp. ) + R' (21)

and a m e a s u r e of a d e q u a c y of t h e c h o i c e i s t h e s m a l l n e s s of R ' . One can


e v e n o b t a i n the l o w e r b o u n d s f r o m t h i s m e t h o d . W e can a l s o p r o c e e d in
t h e s a m e w a y f u r t h e r and o b t a i n h i g h e r a p p r o x i m a t i o n s [7].
Lately MSPO h a s been developed f o r the density m a t r i x o p e r a t o r

D = |^>0| (22)

a l s o with D = D r h f + D x b y 0. Sinanoglu and T . Shibuya (J. M a t h . P h y s .


1_0, 1032).
F r o m t h e M S P O and the s u b v a r i a t i o n a l a p p r o a c h d i s c u s s e d a b o v e we
c a n d e r i v e m a n y a p p r o x i m a t i o n s and t h e o r i e s , but f o r a t o m s t h e - m o s t
a p p r o p r i a t e one e m e r g e s f r o m p h y s i c a l c o n s i d e r a t i o n s . We c a l l it the
" M a n y - e l e c t r o n t h e o r y of a t o m s and m o l e c u l e s f o r g r o u n d s t a t e s " ( M E T ) [ l , 7].
In c l o s e d - s h e l l s y s t e m s , we showed t h a t ( 1 - е " ) - f u n c t i o n s a r e v e r y
s m a l l [7]

fi « 0 (23)

f o r i n s t a n c e f o r H e , t h e f c o n t r i b u t e r o u g h l y 0.001 eV to the e n e r g y w h i l e
t h e t o t a l c o r r e l a t i o n e n e r g y i s 1.1 eV. Why a r e t h e û j ^ , û£j-ki f o r t r u e
3, 4 - b o d y c o l l i s i o n s s m a l l ? We a r e d e a l i n g with H . F . e " ' s . T h e s e h a v e
i n d i v i d u a l and d i s t i n c t o r b i t a l m o t i o n s . T h e y i n t e r a c t t h r o u g h a v e r a g e d
H . F . potentials

Si (xj )

The difference to the instantaneous Coulomb repulsions is


N
mii =
Hex-HHF- X I 77- - š ; ( j ) - š : ( i ) + J ^ (24)
i>j ü
T h e m j j i s t h e " f l u c t u a t i o n p o t e n t i a l " [1] given by the d i f f e r e n c e b e t w e e n
t h e C o u l o m b p o t e n t i a l (long r a n g e , i n f i n i t e f o r v a n i s h i n g r t j ) and t h e H . F .
p o t e n t i a l ( f i n i t e a t r ^ -» 0, b u t a l s o l o n g r a n g e ) w h i c h t a k e s the l o n g r a n g e
p a r t q u i t e w e l l i n t o a c c o u n t . So m ^ i s of q u i t e s h o r t r a n g e ( h a s even a
m i n i m u m in it s o m e t i m e s ) . I t s r a n g e i s s m a l l e r t h a n a F e r m i h o l e
a C O R R < a F . S o f o r t h r e e e^ t h e w o r s t p o s s i b i l i t y i s , a t m o s t , two s p i n s t h e s a m e .
IAEA - S M R - 1 2 / 5 2 63

äcORR

and {ûjj} and t h e i r p r o d u c t s d o m i n a t e


N

^MET = W + ^ ÎÛij> + i Û
û X Û
k«> + {U X U X U } +
(25)
> <j

with i , j =£{k,1}.
The variational MET energy [1,7] is

E S E = Erhf + ; ^ + R- (26)

with ë _ 2< j ^ ( i j ) I gjj I ûjj > + < ûjj )ej + ej + mjj ] u.j >
Û
+ < ij IÛy >

where

е-i 11
1 - е- (27)

E q u a t i o n (27) i s called a " H e - l i k e e q u a t i o n " , b e c a u s e i t l o o k s j u s t like


the H e - a t o m e q u a t i o n . F o r a ( m a n y - e " ) - s y s t e m we have two e x t r a e f f e c t s .
F i r s t , t h e " H . F . s e a " m o d i f i e s the ûjj through change of t h e o r b i t a l and the
total H.F. potential. The second effect comes f r o m the " o r b i t a l orthogonality",
<^Uy \l )xi = 0, of Eq.(15) b e c a u s e the e" cannot go to occupied Orbitals,
T h i s i s the " e x c l u s i o n e f f e c t " and c a n even l e a d to " e x c l u s i o n binding" in
molecules.
F o r the He a t o m t h e c o m p l e t e c o r r e l a t i o n e^ h a s a s an u p p e r bound

(28)

only in t h e ground s t a t e but it i s m o r e t r o u b l e s o m e f o r excited s t a t e s .


C o m p a r e d to t h e s e H e - s t a t e s , the p a i r s of the ( N - e " ) - s y s t e m a r e s i m p l e r
to t r e a t . H e r e E q . (28) a p p l i e s to a l l the p a i r s of the a t o m ! T h i s i s
p o s s i b l e b e c a u s e of E q . (15).
T h e q u e s t i o n i s w h e t h e r t h e r e e x i s t s a p r o h i b i t i v e l y l a r g e n u m b e r of
p a i r s . A c t u a l l y the s y m m e t r y r e d u c e s the n u m b e r of d i s t i n c t p a i r s , f o r
i n s t a n c e e (2px2) = e (2py2). So", i n s t e a d of having p a i r s of the o r d e r of
N ( N - l ) / 2 , we h a v e ~ N . T h i s p r o b l e m is a l m o s t a s s i m p l e a s the H . F .
m e t h o d . It i s m u c h e a s i e r t h a n the o r d i n a r y slowly c o n v e r g e n t t o t a l С. I.
(configuration interaction).
64 SINAN OG LU

In a p p l y i n g the M E T e q u a t i o n s one m u s t r e c a l l that E £ E H F + £ ?..


i J
even though E q . (28) h o l d s f o r e a c h (ij). T o get an u p p e r bound to E , one
n e e d s the e x t r a m a t r i x e l e m e n t s like

<û123|m13|Û32l> =

(and t h e r e a r e r e p e a t e d s u b s c r i p t s s o you a r e including h i g h e r c o r r e l a t i o n


t e r m s ) which a r e in the R' of

и
E S E
RHF + + R' (26)'

i>j

To e s t i m a t e R' is h a r d w o r k . I n d i r e c t l y you can show that R 1 is


e x p e c t e d to b e s m a l l . (The exactly soluble a t o m m o d e l of M . M o s h i n s k y [8]
h a s b e e n u s e d r e c e n t l y to a n a l y s e such e f f e c t s [9]. M a n y r e c e n t c a l c u l a t i o n s
u s i n g M E T a l s o show R' to be s m a l l a s p r e d i c t e d b y the t h e o r y . )
E a c h ejj b e h a v e s d i f f e r e n t l y , so old r u l e s like

(1) large correlation


pre-MET rules-of-
(2) e small correlation t u m b which M E T
showed to be i n c o r r e c t
(3) e e,,. - 1 eV

do not apply.
New r u l e s p r e d i c t e d by t h e new t h e o r y which t u r n e d out to be c o r r e c t a r e :

(1) All a r e n e e d e d , in f a c t e , and

(2) T h e r e a r e two t y p e s of the individual p a i r c o r r e l a t i o n s :


T h e r e a r e " H e - l i k e p a i r s " ; we c a l l t h e s e e^ , " d y n a m i c a l p a i r s " .
T h e y depend on s h o r t - r a n g e l o c a l e f f e c t s which e x p l a i n s why C . I . d o e s not
w o r k and it i s b e t t e r to u s e the H y l l e r a s - t y p e c o r r e l a t i o n f o r t h e m

ûjj ( r 1 2 o r r> , r<)

Our " e x c l u s i o n e f f e c t " i s s m a l l on such p a i r s and s o i s the " H . F . s e a "


p o t e n t i a l change e f f e c t . If you have such a p a i r you can t r a n s f e r i t s
€jj - v a l u e quite w e l l to d i f f e r e n t ions, a t o m s o r m o l e c u l e s . T h a t i s to s a y
dynamical pairs are transferable.
But in e x c i t e d s t a t e s and ground s t a t e s that a r e not r e a l l y c l o s e d s h e l l s
t h e r e a r e a l s o n o n - t r a n s f e r a b l e p a i r s . In t h i s c a s e we s p e a k of " n o n -
dynamical pairs". F o r e x a m p l e the (2s 2 ) p a i r in n e u t r a l neon and i t s i o n s
differs greatly.
IAEA - S M R - 1 2 / 5 2 65

In neon lü?2£?2p 6 , e(2s 2 ) N e œ °> but in t h e ion Ne + 6 , l s 2 2 s 2 , e(2s 2 ) N e + 6


« - 3 . 5 eV. T h i s c o m e s f r o m the " e x c l u s i o n e f f e c t " . F o r t u n a t e l y n o n -
t r a n s f e r a b l e p a i r s a r e s i m p l e to c a l c u l a t e .
T h e r e a r e t h r e e a p p r o a c h e s f o r closed s h e l l s : M E T , the d i a g r a m m a t i c
p e r t u r b a t i o n t e c h n i q u e [10] and t h e n o n - u n i f o r m e l e c t r o n g a s t r e a t m e n t [11]
w h i c h , h o w e v e r , d i v e r g e s . M E T p e r m i t s p h y s i c a l insight into the c o r r e -
l a t i o n m e t h o d s it i n t r o d u c e s . T h e d i a g r a m m e t h o d d o e s not p r e d i c t t h e
e f f e c t s a s M E T , but i s a t e c h n i q u e .
F o r g e n e r a l e x c i t e d s t a t e s we h a v e at p r e s e n t only one m e t h o d , the
n o n - c l o s e d s h e l l M E T , the NC M E T [1]. T h e d i a g r a m m a t i c t e c h n i q u e d o e s
not apply to s u c h s y s t e m s .

3. T H E O R Y OF T H E N - E L E C T R O N E X C I T E D STATE

Above we a n a l y s e d the ( N - e " ) - g r o u n d - s t a t e p r o b l e m u s i n g two g e n e r a l


t o o l s we d e v i s e d f o r the p u r p o s e .
(a) MPSO: S e p a r a t i n g the L 2 ® L 2 ® . . . <2> L 2 H i l b e r t s p a c e we pick
up a f i n i t e p a r t of the infinite H i l b e r t s p a c e . We s t a r t with t h e H . F . s e t
of occupied s p i n - o r b i t a l s (s. o. ' s ) .
It i s a s if f o r e a c h s. o. you find an i m a g e outside t h e H . F . s e a , then
f o r e l e c t r o n p a i r s , t r i p l e t s , e t c . , until you h a v e c o v e r e d t h e whole s e t a s
shown in the f i g u r e

© f.
N

but t h i s i s only a f o r m a l solution; then we n e e d a m e t h o d f o r a p p r o x i m a t i o n s


and c a l c u l a t i o n s , so we h a v e :
(b) the " s u b v a r i a t i o n a l p r i n c i p l e " : P i c k i n g out the m o s t r e l e v a n t
p o s i t i o n of the E , c h e c k i n g if it l e a d s to s t a t i o n a r y s o l u t i o n s and then getting
an u p p e r bound u s i n g the f u l l v a r i a t i o n a l e x p r e s s i o n .
U s i n g t h e s e t o o l s and p h y s i c a l n o t i o n s , we obtained E q . (2 5). F r o m
t h i s we d e r i v e d o u r decoupled p a i r c o r r e l a t i o n s in the e n e r g y

(29)

i>j
with
N

(30)
i>j
t h i s w a s a new p r e d i c t i o n of t h e t h e o r y by the a u t h o r (1959). F o r the
e " - g a s t h e o r y which m a n y w o r k e r s (Slater and o t h e r s ) t r i e d to apply to
a t o m s , E q . (30) i s not t r u e .
66 SINANOGLU

Without R 1 we h a v e no u p p e r bound to E . H o w e v e r , f o r each " H e - l i k e


equation" we h a v e an u p p e r bound to i t s p a i r e n e r g y

сц (Йц) (31)

E q u a t i o n s (29-31) a r e not u s e d in n u c l e a r t h e o r y . In n u c l e a r t h e o r i e s a l l
û ' s depend on a l l o t h e r û ' s . (cf. E . U . Condon, Rev. Mod. P h y s .
(1968) 872).
We h a v e two t y p e s of е ц , d y n a m i c a l ( t r a n s f e r a b l e p a i r s ) and a l s o n o n -
d y n a m i c a l . E x a m p l e s of the f i r s t type a r e I s 2 and 2p 2 ; of the s e c o n d type
2 s 2 , which i s n o n - t r a n s f e r a b l e but e a s i e r to c a l c u l a t e .

G e n e r a l N - e l e c t r o n n o n - c l o s e d s h e l l s (excited s t a t e s )

T h e c l o s e d - s h e l l t h e o r y w a s i n t r o d u c e d by the a u t h o r and developed


b e t w e e n 1959 and 1964 [7] in o u r l a b o r a t o r y ; i t s a p p l i c a t i o n s a r e studied
and continued in s e v e r a l o t h e r l a b o r a t o r i e s . T h e n o n - c l o s e d s h e l l M E T ,
N C M E T [1] w a s obtained and applied b e t w e e n 1964 and 1970 by t h e a u t h o r
and h i s c o - w o r k e r s . It led to an a t o m i c - s t r u c t u r e t h e o r y [1-3] capable of
a c c u r a t e p r e d i c t i o n s of m a n y p r o p e r t i e s l i k e t r a n s i t i o n p r o b a b i l i t i e s ,
h y p e r f i n e s t r u c t u r e , e t c . ; it i s in good a g r e e m e n t with new e x p e r i m e n t s
c a r r i e d out in 1968 and l a t e r .
We c a n now u s e the n o n - c l o s e d - s h e l l t h e o r y even f o r ground s t a t e s ,
b e c a u s e it g i v e s m o r e i n f o r m a t i o n .
C o n s i d e r f o r i n s t a n c e c a r b o n I.

0RHF (ground s t a t e of C) = ( l s 2 2 s 2 2 p o 2 p " ) c a r b o n 3


P

T h e Roothaan H . F . m e t h o d (1960) is u s e d . In g e n e r a l

J с л
RHF = к к (32)

K=1
with the CR d e t e r m i n e d by s y m m e t r y . F o r n e u t r a l c a r b o n , f o r the
ls 9 '2s 2 2p 2 1 S s t a t e we h a v e к = 3

фт1, = ^ [ 1 s 2 2 s 2 (2p2 + 2py + 2p 2 )]

we need t h e s e t h r e e e q u i v a l e n t d e t e r m i n a n t s to get the 1 S s t a t e . T h e


" H . F . s e a " , the RHF s p i n - o r b i t a l s a r e {k} = {k e { l , 2, . . . M}}
Let u s c o n f i n e o u r s e l v e s to f i r s t - r o w a t o m s and i o n s , L i , B e , В , C ,
O, F , Ne, B e + , B e + 4 , B + , B + + so we h a v e l s n 2 s m 2 p k c o n f i g u r a t i o n s with
t h e r e s t r i c t i o n s t h a t n + m + k = N. We s h a l l take the s e t of M Roothaan
H . F . s p i n - o r b i t a l s a s the H. F . " s e a " .
With t h i s s e t we can c o v e r s e v e r a l h u n d r e d s t a t e s . T h e n u m b e r of
N - e l e c t r o n a r r a n g e m e n t s in M s p i n - o r b i t a l s i s

/м\ M! =
ш (33)
VN/ N! (М-N)! ~
IAEA - S M R - 1 2 / 5 2 67

B u t we h a v e only a l i m i t e d n u m b e r of d e t e r m i n a n t s ( k « m ) in Ф ш р
owing to s y m m e t r y .
We a l w a y s s t a r t f r o m a given H . F . s e a ; now we a r e d e a l i n g with
v a l e n c e c o n f i g u r a t i o n s giving o u r s p e c t r o s c o p i c s t a t e s .
We s e p a r a t e x CORR r i g o r o u s l y into t h r e e p a r t s

ф= + x I N T + XF + ХЦ (34)
RHF

and a l l f o u r t e r m s in x a r e m u t u a l l y o r t h o g o n a l

<XlI*m/=0 L ^ M L , M s { I N T , F , U, RHF}

=
XINT internal correlation
XF = s e m i - i n t e r n a l c o r r e l a t i o n including o r b i t a l p o l a r i z a t i o n s
хи = all external correlation
We h a v e a p a r t i a l l y f i l l e d " H . F . s e a "

~ ^RHF

H . F . " s e a " i n c l u d e s e v e r y t h i n g t h a t c o m e s f r o m the f i n i t e set of the


M s p i n - o r b i t a l s of the H . F . s e t . T h e p r o b a b i l i t y of f i n d i n g the s y s t e m
in Д к i s

~Pk = |C K f s 1 (35)

( e q u a l to 1 only if t h e r e is a s i n g l e det). T h e t o t a l w a v e f u n c t i o n can be


displayed as

X X X
^RHF CNT F u

T h e " i n t e r n a l c o r r e l a t i o n " i s a l l d e t e r m i n a n t s with H . F . s e a ( v i r t u a l


t r a n s i t i o n s to u n o c c u p i e d p a r t s of s e a ) .
T h e m u l t i - c o n f i g u r a t i o n SCF (MCSCF) i s a c o m b i n a t i o n i n c l u d i n g s o m e
p a r t s of <PRHF + XINT . but it g i v e s a n e g l i g i b l e i m p r o v e m e n t in e n e r g y f o r
a t o m s . M o r e g e n e r a l l y we h a v e

+
4>RHF XlNT
^GRHF
(37)
•Л + < % , т ! x i n t >
68 SINAN OG LU

b e c a u s e O R H F I^RHF ^ = r e n o r m a l i z e if w e w i s h to r e l a t e t o t h e 4>GRHF
( g e n e r a l r e s t r i c t e d H . F . d MCSCF) a s the s t a r t i n g point which is m o r e
u s e f u l in d i s s o c i a t i n g - m o l e c u l e p r o b l e m s .
T h e Xp, s e m i - i n t e r n a l p a r t , t a k e s a p a i r with one e" going out, t h e
o t h e r i n s i d e t h e s e a . B u t now t h e f u n c t i o n ( " o u t s i d e " ) , w h e r e the j - t h s p i n -
o r b i t a l e l e c t r o n g o e s t o , d e p e n d s on w h e r e t h e i - t h e l e c t r o n w e n t t o : so

i -> Л and j -> f i j | { ( X j )

a n d f i s o r t h o g o n a l to s e a o r b i t a l s

<fij { |k> =0, k e {1,2 M}

T h e s e m i - i n t e r n a l c o r r e l a t i o n e f f e c t w a s m i s s e d p r e v i o u s l y in a t o m i c
t h e o r y u n t i l it w a s d i s c o v e r e d b y the p r e s e n t t h e o r y in t h e a u t h o r ' s w o r k .
W h e n f i r s t c a l c u l a t e d b y t h e a u t h o r and B . Skutnik, it t u r n e d out t o b e a n
i m p o r t a n t e f f e c t c o m p a r a b l e in m a g n i t u d e t o t h e o t h e r two c o r r e l a t i o n
e f f e c t s we h a v e s e p a r a t e d .
F o r a l l - e x t e r n a l c o r r e l a t i o n s the p a i r t e r m s again a r e dominant just
a s in t h e c l o s e d s h e l l ( M E T ) t h e o r y .

<тдц|к> = 0 orbital orthogonal ke{l,2,...M}

A s W i g n e r noted, e x c i t e d - s t a t e c o r r e l a t i o n s looked v e r y c o m p l i c a t e d —
t h e r e s e e m e d to be no s y s t e m a t i c s . B u t now we k n o w t h i s i n d i v i d u a l i s t i c
b e h a v i o u r c o m e s f r o m x I N T a n d XF w h i c h we can c a l c u l a t e and a r e l e f t
w i t h only c l o s e d - s h e l l - t y p e х ц with t r a n s f e r a b l e p a i r s . A l l t h r e e t e r m s
a r e e q u a l l y i m p o r t a n t in e n e r g y .
In Xp a n o t h e r t e r m e x i s t s which we c a l l " o r b i t a l - p o l a r i z a t i o n " a n d
w h i c h w a s n e g l i g i b l e f o r c l o s e d s h e l l s , b u t h e r e it i s r e l a t i v e l y i m p o r t a n t .
It i s r e l a t e d t o f i j t b y s y m m e t r y s o it m u s t b e i n c l u d e d in Xf.
The exact e n e r g y is

E = ERHF + EINT + E F + ЕЦ (38)

but we m u s t r e s o r t to t h e s u b v a r i a t i o n a l p r i n c i p l e a g a i n to get t h e n o n -
c l o s e d s h e l l e n e r g y . We f i n d s t a t i o n a r y s o l u t i o n s (you do not n e c e s s a r i l y
h a v e an u p p e r b o u n d now) f o r e a c h c o r r e l a t i o n p a r t w i t h t h e v a r i a t i o n a l
energy

E E E r N C ( 3 9
E = ERHF + INT + F + u + )

w h e r e a g a i n R N C i s the r e m a i n d e r ( a s in t h e c l o s e d s h e l l c a s e ) b u t it i n c l u d e s
a l s o s o m e c o u p l i n g t e r m s b e t w e e n t h e e f f e c t s . F o r r o u g h l y the s a m e
r e a s o n s a s in c l o s e d s h e l l s , it should b e s m a l l , b u t we h a v e no d i r e c t
n u m e r i c a l e s t i m a t e , o n l y i n d i r e c t e v i d e n c e (cf. s e c t i o n 4).
IAEA - S M R - 1 2 / 5 2 69

W e c a l c u l a t e f i r s t t h e t h r e e t e r m s , Е и i s t h e s a m e a s in c l o s e d - s h e l l s .
How t o c a l c u l a t e E I N T and E F ? One c a n v a r y E F t o o b t a i n an i n t e g r o -
d i f f e r e n t i a l E u l e r e q u a t i o n f o r t h e fjj ^. S i l v e r s t o n e t r i e d t o s o l v e t h e s e
E u l e r equations n u m e r i c a l l y f o r s m a l l a t o m s but we shall p r o c e e d d i f f e r e n t l y .
We take the " c h a r g e - d e n s i t y wave function" which we introduce a s

= = < W + *INT + (40)

T h e \ > h a s n o s t r o n g e f f e c t on t h e c h a r g e d i s t r i b u t i o n s a n d r e l a t e d p r o p e r t i e s .
F o r e x a m p l e , f o r the t r a n s i t i o n probabilities it i s sufficient to u s e
F o r the e n e r g y we need Е ц a l s o . We have the H . F . - s e a Orbitals (including
t h o s e in t h e x I N T p a r t )

l s
a 2Pzß
M H.F. spin-orbitals

p l u s " s e m i - i n t e r n a l O r b i t a l s " f y к- T h e s e m i - i n t e r n a l O r b i t a l s could c o m e


f r o m the i n t e g r o - d i f f e r e n t i a l e q u a t i o n s m e n t i o n e d a b o v e , but we r e m e m b e r
t h a t <^RHF h a s t h e SU(2) 0 0(3) s y m m e t r i e s , but not t h e f ; . t , s o w e e x p a n d
them as

fi^fSi) = ^ fL(r) YLM(Q)ai (41)


L

T h i s e x p a n s i o n l o o k s only a s if it w e r e i n f i n i t e b u t it i s not b e c a u s e if
фрщр h a s a c e r t a i n s y m m e t r y ( f o r e x a m p l e , XS), xF h a s a l s o a S s y m m e t r y .
So in j ď (12 . . . Í. f i ( . . N) and t h e e x p a n s i o n of f.. { u s i n g v e c t o r c o u p l i n g ,
g i v e s only a f i n i t e n u m b e r of t e r m s in the e x p a n s i o n . O n l y L = 0, 1, 2, 3
f o r the K L s e a . Then we h a v e f s ( r ) , fp(r), fd(r) and f f ( r ) and that is all.
T h e r e would b e a s e t of s u c h r a d i a l f u n c t i o n s f o r e a c h i j however there
a r e not m a n y p o s s i b l e c o m b i n a t i o n s . So u s u a l l y only one s e t e x i s t s in t h e
K L - s h e l l s b e c a u s e of s y m m e t r y .
W e u s e a c o m b i n a t i o n of S l a t e r o r b i t a l e and t h e v a r i a t i o n a l m e t h o d f o r
e a c h f ( r ) , i . e . a n e x p a n s i o n in S T O ' s . C o r r e l a t i o n i s a s e c o n d - o r d e r
e f f e c t and h e n c e not v e r y s e n s i t i v e to the " s e a - o r b i t a l s " . F o r i n s t a n c e ,
t a k e a s i n g l e 3*í S. Т . O. b u t with a v a r i a t i o n a l e x p o n e n t (which w i l l c o m e
out v e r y d i f f e r e n t f r o m t h e r e a l 3 i exponent)

f(r) - 3*i

W e c a n now e v e n p a s s o v e r to t h e M - s h e l l u s i n g t h e l a r g e s t c o m p u t e r s .
P r o g r a m s d e v e l o p e d f i r s t b y O. Sinanoglu and I. Ö k s ü z , h a v e now b e e n
e x t e n d e d t o h e a v i e r a t o m s b e y o n d s o d i u m by O. Sinanoglu and D. B e c k .
S t a r t i n g f r o m t h e H . F . s e a a n d i n f o r m a t i o n of s t a t e , n u m b e r of e l e c t r o n s ,
e t c . , the f u l l y a u t o m a t i c p r o g r a m s c o m p u t e t h e "xF t e r m s b y v e c t o r c o u p l i n g .
F i r s t it g e t s a l l t h e i n t e r n a l a n d s e m i - i n t e r n a l d e t e r m i n a n t s . It u s e s t h e
Condon-Shortly m e t h o d s , spin p r o p e r t i e s , diagonalizes the large m a t r i x
and c o m p u t e s t h e c o e f f i c i e n t s , t h e n i t e r a t e s (only a b o u t 3 i t e r a t i o n s n e e d e d ) .
FLUORINE 111 152 2S 2P4 QUARTET p 07/13/72
COEFFICIENT
BET HF >A С ISA 1SB 2SA 2Р-А 2P0A 2P0B ?Р»А r.sooooooo
COEFpI СIENT CONTRIBUTIONS
«.U. E.V.
DFT г «* ISA 1SU 2S6 2P-A 2P0A гР»А ЗРПА ) .02041446 -7.63356174Е "04 -г. ,07707363Е- 02
DFT 3»A ISA J.SH 2P-A 2P-H 2I'0A ÍP->A ЗП+А ) V.01963041 "1'22«9204?E "03 -3 .33297906Е-•02
DFT 4 cA ISA ISB 2P.A 2P0A 2P.A гр«в 3D-» ) • .01963041 -1.22492042Е -03 -3,,332'79о6Е. 02
DFT Ç.A ISA jSH 2SA 2SB 2P0 A гР-А 3D-A ) « .0SB»Bie0 •8«13475435^ "03 -2.• 21344 714 Е-01
UFT 6 EA ISA IS!) 2SA 2P-U 2P 0 A ?Р*А 3P0A ) .010*4621 -1.56467937Е -04 • 4,, 257455 0 ОЕ-• 03
DET 7s A ISA 1SH 2SA 2P-H 2РПА гР*А 4F0A ) .01387797 -1.3015082бЕ "04 -3..54l37274E- 03
DET fl»A ISA ISB 2SA 2P0A PP.A гр-в 4ř-2A ) .00708017 -4.33U36067E -04 -1.Л8045758Е. 02
DET 9e A ISA 1S4 2SA 2SU A гр.А 35« ) 9 .03463341 -1.JB23543BE "03 -3. 7Í13530«E- 02
DFT 10aA ISA ISH 2SA 2S3 2P-A 2Р*А 3 DO А ) .00775990 -1.0M633Ç1E -02 -2,1951262в5Е- П1
DFT 11 3=A ISA ISH 2SA ?P-A 2P-B ÍP»A ?Р +А ) • .00508411 •7.2673S093E -05 •1.97742875Е. 03
DFT 1? A ISA IS» 2SA 2P-A Rl'-M гР»А 4F»A ) .0 06^3270 •3.470бВв70Е "04 •9.•«4366065Е- (13
DET 13 =A ISA 1SH 2SA 2P-A 2P+A гр»в Зр-А ) .00508411 •7.2673Ь093Е -05 •1.97742P75É- 03
DFT 14»A ISA iSH 2SA 2P-A 2P*A ЕЫ 4F-A ) • ,0»бЗЗ?70 •3.47068В70Е "04 -9,.44366065Е- 0 3
DET lb=A ISA IS4 ZSA 2Sb ? Г-А £Р 0 А ЗП»А ) » .05868180 -8,134754356 -03 -2.21344714Е-П1
DET 16=A ISA J.SH 2SA 2P-A p p - n ÎPOA 4F»2A ) • .0»7UBni7 -4.338360Й7Е -04 -1. IB045758E- 0 2
DFT 17 = A ISA ISH 2SA 2P-A 2K0A с P* H ЗРО А ) .U10 V4621 •1.56467937Е "04 -4 ,,25745500Е- 03
DET 1P = A ISA ISH 2SA ?.P-A ?P0A ЕР*В 4F 0 А ) .003«7797 -1. 301508261: -04 -3,,54137274Е..03
DFT 19=A ISA isa 2P-A 2P0B гр-А ?ЗА ) .00099959 •1.4J. 2В7427Е -06 •3' •844396986- 05
DFT 20=A ISA 1SÍI 2P-A 2Р0Л
Р 2Р* А 3|)П4
2P0B ) * ,оггбб725 -1.63322722Е - 0 3 •4 ,,44397200Е- 02
DET 2 l = A ISA ISH 2SA 2 0А 2l'0« ?Р* А ЗР-А ) .015?4?96 -4. Ц693765Е "04 -1. 1?0?0885Е- 02 8.
P
DFT 22*A ISA 15П 2SA 2 0A ZPOti ГР*А 4F-A ) . 00633270 -3.47068870E'-04 •9. 4 4 366Р65Е-03 E
DET 23aA ISA I S il 2SA гг'» ГР0Н ЕР»А ЗРОА ) . 00 0*8736 -1.02395618Е "06 -2. 78616019Е- 05
DET 24»A ISA ISB 2SA 2P-A 2''OH ŘP+Л 4F0A ) • .00775594 -5.20603304Е "04 -1.•41654910Е- о г
DFT 2Г = А ISA 1SIJ 2S« 2P-A 2P0A 2Р-А 3|>0В ) » .0+2^9424 .2.91798618Е -03 .7. 93977037Е- 0 2
DET 26eA ISA IS'1 2SÍ 2Р-Л 21'OA ;Р«А 4Г0В ) W ., 00000000 1.2270397.76-31 3. 33874577Е- 30
DET 27«A ISA isa 2SA 2P'A 2P0A ?РОВ 3|>»А ) • .01554296 •4.Ц693765Е'"04 -1. 12020Вв5Е- 0 2
DET 2E sA ISA 1SÍ) 2SA 2P-A 2P0A ZP0IÎ 4Г»А ) » .006^3270 •3.47068870Е'•04 •9. 44366065Е- 03
DET 29«A ISA ISH 2se 2P-A 2''0 A ГР*А 4Г0А ) .00000000 0. 0.

EHF(A.U,î a -9.69143342F+01
ETOTALU-U,) » -9.6951917(IE*01
DIFFERENCE!»,U,) > .4.05B35725E-0?
EXPONENTS 3S « г . о з г п о о о CONTRIBUTIONS -1.3«374725E-03
3P • 1•6020000 -*.9È40JI6'3E.03
3D в 2.6750 000 .3.119Н«13УЕ.02
IF з 4.2260000 ,5.03бВ52*1Е.03

REMORMALIZATION FACTOR > .99146072


FIG. 1. Direct computer output for the charge wave function 4<c of the n o n - c l o s e d - s h e l l - m a n y - e l e c t r o n
theory [ 1] of Sinanoglu for the Is2 2s2p4 4 P of fluorine III. T h e orbitals labelled as 3s, 3p, 3d, and 4f refer
to the s e m i - i n t e r n a l orbitals f s , f , f d , and f f described in the text.
IAEA -SMR-12/52 71

F i g u r e 1 s h o w s an e x a m p l e of a d i r e c t c o m p u t e r output ¥ c , the " c h a r g e


wave f u n c t i o n " (i. e. " c h a r g e - d i s t r i b u t i o n w. f. ") of an a t o m i c s t a t e . O u r
a u t o m a t i c p r o g r a m s h a v e p r o d u c e d s e v e r a l h u n d r e d such wave f u n c t i o n s
f o r m o s t s t a t e s of i n t e r e s t in a t o m i c t h e o r y . We t h u s h a v e now an a t l a s
of a t o m i c s t r u c t u r e s with f u l l c o r r e l a t i o n , which y i e l d the a c c u r a t e a t o m i c
properties. T h e new s i t u a t i o n m a y b e c o n t r a s t e d with the p r e v i o u s
l i t e r a t u r e w h e r e h a r d l y one such wave f u n c t i o n e x i s t e d .
C o m p u t e r t i m e i s r o u g h l y 30 s e c o n d s p e r s t a t e on the CDC 6600
c o m p u t e r f o r s e c o n d - r o w a t o m s . We h a v e now s t i l l two p r o b l e m s : how
and how w e l l c a n we c a l c u l a t e t r a n s i t i o n p r o b a b i l i t i e s , and how c a n we
obtain Ец which i s s t i l l a l a r g e p o r t i o n of t h e c o r r e l a t i o n e n e r g y .

4. T H E A L L - E X T E R N A L C O R R E L A T I O N Е ц AND E N E R G Y L E V E L S

In the l a s t s e c t i o n we s u m m a r i z e d the t h e o r y f o r n o n - c l o s e d s h e l l
s t a t e s in the v e r s i o n a p p l i c a b l e to a t o m s and s t a b l e m o l e c u l e s . We h a v e
s e e n two s t a r t i n g p o i n t s , one of t h e m b e i n g the r e s t r i c t e d H a r t r e e - F o c k
m e t h o d (RHF):

к <m

ФRHF = У Ск Д к (42)
Ksi
In t h i s c a s e the c o e f f i c i e n t s a r e a l l d e t e r m i n e d by 0(3) X SU(2) r
s y m m e t r y a l o n e . In the o t h e r c a s e of the g e n e r a l r e s t r i c t e d H a r t r e e -
F o c k (GRHF) m e t h o d we h a v e a g a i n a l i n e a r c o m b i n a t i o n
m
c л
Фскнг = X k к C43)
к
but h e r e the c o e f f i c i e n t s a r e not d e t e r m i n e d by 0(3) s y m m e t r y a l o n e , they
a r e d e t e r m i n e d in p r i n c i p l e by s o m e h i g h e r g r o u p s [12, 13] o r j u s t by
c a l c u l a t i o n . At t h e m o m e n t t h e s e c o e f f i c i e n t s a r e obtained only via m a t r i x
d i a g o n a l i z a t i o n by c o m p u t e r s .
In a t o m s t h i s s t a r t i n g point i s not r e a l l y n e c e s s a r y , b e c a u s e t h i s i s
quite a c c u r a t e l y given by

I A $RHF + * INT
GRHF
" s/l
V I + 4< У Ix—7
INT ' INT
<44>

but with m o l e c u l e s which a r e d i s s o c i a t i n g we cannot do t h i s .


F o r a t o m s , a s we s a i d , we s t a r t with ф к н р . T h e n the exact wave
function is

¥ = + X + X + w i t h
" W INT F V < Ф > = 1 + <x|x> (45)

w h e r e x F i s s e m i - i n t e r n a l and o r b i t a l p o l a r i z a t i o n and x is all external.


72 SINANOGLU

The energy is also

E = E r h f + E[NT+f + Ец (46)

We can c a l c u l a t e the f i r s t two t e r m s u s i n g the H . F . and our " s e m i -


i n t e r n a l o r b i t a l s " and then get Е ц l a t e r .
We can c a l c u l a t e E I N T and E F s e p a r a t e l y o r t o g e t h e r . T h e d i f f e r e n c e
i s not e s s e n t i a l and we let the c o m p u t e r c a l c u l a t e it in one r u n .
It r e m a i n s to obtain the Е ц p a r t , w h e r e we have a c l o s e d - s h e l l - l i k e
s i t u a t i o n , m a i n l y p a i r c o r r e l a t i o n s c a u s e d by s h o r t e r - r a n g e f l u c t u a t i o n
p o t e n t i a l s . ( T h i s i s not t r u e f o r Е ш т o r E p w h e r e the h i g h e r e l e c t r o n
t e r m s are important. )
F o r c l o s e d - s h e l l s we had

Л a n d E e ( 4 7 )
^RHF = 1 U = X ii

i >j

F o r t h e c a s e of n o n - c l o s e d s h e l l s

r
RHF
С
к л к ; Eu = X Pi
i +
)_. Pij;kJ2

ij;ki
(48)
ijke

We h a v e t h e H a r t r e e - F o c k s e t c o n s i s t i n g of

{k} = { ( I s 2 s 2 p ) X ( a , ß ) } dim M s N (49)

with s y m m e t r y 0 ( 3 ) X SU(2) o , and all p^ c o e f f i c i e n t s a r e d e t e r m i n e d by


symmetry.
T h e p;j a r e

T h e sum i s only o v e r such К which contain i, j s p i n - o r b i t a l s .


T h i s i s the p r o b a b i l i t y f o r the occupation of the i, j s p i n - o r b i t a l s in
'PRHF •
Py. k j i s a new t e r m in the n o n - c l o s e d s h e l l b e c a u s e t h e r e a r e now
" c r o s s pairs" or off-diagonal pairs.
In the c l o s e d - s h e l l c a s e , when we m i n i m i z e the 2e~ - p a r t u p p e r bound
е.. s (51)
и ч
w h e r e e,, i s given by

e
ij = < ^ 1 2 ( 4 ) ! ~ l û u >
ij
IAEA - S M R - 1 2 / 5 2 73

и - i s t h e f u n c t i o n w h i c h m a k e s e^ a m i n i m u m . S i m i l a r l y , we h a v e

e
ij;ki = < - * У ч > I ZT7 I û k f i > (52>

we r e m e m b e r

j*12(ij) = {i(Xi) j(3j)}


JT

N o t e t h a t w e c a n t a k e g 1 2 i n s t e a d of ш ц = g 1 2 - §i(2) - S 2 ( l ) + J i 2 , b e c a u s e
J 1 2 f a l l s out u p o n i n t e g r a t i o n and a l s o S 1 (2) b e c a u s e of o r b i t a l o r t h o g o n a l i t y .
T h e Pij. k £ a r e e s s e n t i a l b e c a u s e of s y m m e t r y . If you d r o p t h e m , t h e
e q u a t i o n b e c o m e s i n c o n s i s t e n t , you l o s e t h e i n v a r i a n c e p r o p e r t i e s w h e n
you c h a n g e c o - o r d i n a t e s

C
Pij-Mt = I KCL; (i.j)6AK. (k,i)EAL (53)
К ^L

F o r c l o s e d - s h e l l s we h a v e o n l y one d e t e r m i n a n t A j , P j = 1 p k ? ! 2 = 0;
s o pjj g i v e s a f a c t o r of 1 a n d ру. к 4 i s z e r o , i s a l m o s t the s a m e , e. g.
f o r B e , B e + , B e 2 + , i. e. it i s t r a n s f e r a b l e . B u t the P ; j . k i p a r t c a n m a k e
a difference.
T o s e e h o w we can e v a l u a t e t h e c r o s s p a i r s , l e t u s c o n s i d e r c a r b o n
ls22s2 (2p2+2p2+2p2).
S u p p o s e you t a k e now a l l the p a i r s

T h e i n d i v i d u a l o r b i t a l s b e l o n g to 0(3) X SU(2) but the function


^ 1 2 ( 2 р ^ 2p® ) t r a n s f o r m s a s [0(3) X SU(2) 0 ] X [0(3)"x SU(2) Ö ], b u t , of c o u r s e ,
t h e r e p r e s e n t a t i o n i s r e d u c i b l e . B u t we c a n t r a n s f o r m t o the i r r e d u c i b l e
r e p r e s e n t a t i o n of 0(3) X S U ( 2 ) 0 . So we c a n s a y t h a t

= reducible pairs

2
If we h a v e 2p in s e v e r a l r e d u c i b l e p a i r s , w e c a n m a k e a u n i t a r y
t r a n s f o r m a t i o n to obtain the following i r r e d u c i b l e p a i r s :

(2p2) -> 1
2
(2p ) -> 5 15 w a v e f u n c t i o n s (54)
(2p 2 ) 3 P -> 9

T h e a d v a n t a g e i s , of c o u r s e , i n ' t h e e x p r e s s i o n of t h e e n e r g y

E
u => ei
74 SINANOGLU

w h e r e I r u n s o v e r a l l i r r e d u c i b l e p a i r s , e. g.

e
i = e 2pî 1 s =<ф(2р 2 , 1 s)| I Û2p2 i s > (55)
12

b e c a u s e the û ' s t r a n s f o r m the s a m e way a s the i, j.


The c r o s s t e r m s a r e

e
i.I lr-|GI> =0 ' (56)
1.2

b e c a u s e they b e l o n g to d i f f e r e n t i r r e d u c i b l e r e p r e s e n t a t i o n s and r-^ i s


s p h e r i c a l l y s y m m e t r i c , s o it g i v e s z e r o .
Only one " c r o s s e d p a i r " r e m a i n s in the K L - s h e l l s , n a m e l y
2
^ s ) « ^(гр2)

T h u s one cannot obtain a l l the Ру к{ by s y m m e t r y u n l e s s a l a r g e r g r o u p is


found, but t h i s s t i l l i s an open p r o b l e m . So

^ =I e
i +
I ßa
'
£l1
' (57)
i i?i>

F o r m o s t s t a t e s the second t e r m s do not even a p p e a r , even when they


e x i s t you e i t h e r e s t i m a t e t h e m o r c o n s i d e r t h e m s m a l l . So the p r o b l e m
i s to c a l c u l a t e

I 0 . ei
l
The cross pair

<cp(2s 2 1 S)| —
r
|û(2p 2 1 S)>
12

w a s e s t i m a t e d by s e v e r a l m e t h o d s [14] f o r Ne to t e s t h y b r i d i z a t i o n of the
type u s e d in CH 4 . C h e m i s t s suppose the t e t r a h e d r a l i n t e r - o r b i t a l c o r r e l a t i o n s
t o be s m a l l , but t h i s h a s t u r n e d out to b e w r o n g e v e r y t i m e a c a l c u l a t i o n
h a s b e e n m a d e . So a l l the p a i r c o r r e l a t i o n s a r e n e e d e d a s p r e d i c t e d in o u r
t h e o r y . T h e c h e m i s t s ' " s e p a r a t e d - p a i r " a s s u m p t i o n b a s e d on e l e c t r o n - p a i r
b o n d s only, i s i n c o r r e c t .
F o r a l l s t a t e s in L s h e l l of the type l s 2 2 s n 2 p m , i. e. B , C, N, O, etc.
and t h e i r i o n s , we h a v e E RHF + E I N T + E F and E. e x p , i s a l s o a v a i l a b l e ( f r o m
M o o r e ' s t a b l e s m a k i n g r e l a t i v i s t i c c o r r e c t i o n s ) . So one can get Е и
(experimental)

E u ( e x p ) - > У ß { e, efP(Z) (58)


l
IAEA - S M R - 1 2 / 5 2 75

T h e /3] a r e d e t e r m i n e d by g r o u p t h e o r y , so one d e t e r m i n e s e®xP and u s e s


this to r e c a l c u l a t e t h e s a m e s t a t e s and a l s o o t h e r s that w e r e not u s e d
(cf. the s e r i e s in P h y s . R e v . s t a r t i n g in 1969) (cf. Sinanoglu and O k s ü z ,
P h y s . Rev. L e t t . 21_, (1968) 597);

magnitude E ö ~ 3 - 5 eV
deviation ě 0.02 eV

T h e r e s u l t s f o r i r r e d u c i b l e p a i r c o r r e l a t i o n s in a t o m s a r e shown in
T a b l e II. It can b e s e e n that they a r e i n s e n s i t i v e to c h a n g e s in Z.
A p r e d i c t i o n of o u r t h e o r y i s that

w h e r e we n e g l e c t R ' , i. e. we c o n s i d e r decoupled p a i r c o r r e l a t i o n s (only


f o r Е и ) . We s u p p o s e a d d i t i v i t y and t r a n s f e r a b i l i t y of e a c h e. T h e f a c t
that f r o m the t a b l e in " A t o m i c P h y s i c s " [ l ] we can get good p r e d i c t i o n s
and that Е ц i s obtained with a d e v i a t i o n TO.02 eV m a y b e c o n s i d e r e d a s an
i n d i r e c t proof of t h i s .
We w i l l r e v e r s e the p r o c e d u r e now to give a m e t h o d f o r t h e c a l c u l a t i o n s
of v a r i o u s a t o m i c p r o p e r t i e s .
We f i r s t d i s t i n g u i s h b e t w e e n two b r o a d c l a s s e s of p r o p e r t i e s . (This
i s not a r i g o r o u s d i v i s i o n , but a quite p r a c t i c a l one.)

allowed t r a n s i t i o n s
forbidden transitions
spin d e n s i t y
- = " c h a r g e - l i k e " p r o p e r t i e s (gj) (59a)
absolute charge density
hyperfine constants
multipole moments

and

energetics
EA
IP = " e n e r g y - l i k e " p r o p e r t i e s (g 12 ) (59b)
i n n e r IP
excitation energy

E n e r g y - l i k e p r o p e r t i e s depend on c o r r e l a t i o n m u c h m o r e than c h a r g e -
like p r o p e r t i e s which a r e given b y the o v e r a l l c h a r g e d i s t r i b u t i o n .
We s t a r t with the p r e d i c t i o n that

Ш = Ш (60)
CD "

t h i s i s a l l one n e e d s f o r c h a r g e - l i k e p r o p e r t i e s ; f o r e n e r g e t i c s , h o w e v e r ,
one should u s e the c o m p l e t e f u n c t i o n .
We a l w a y s t e s t the p r e d i c t i o n s by m a k i n g a c a l c u l a t i o n f o r a new
s t a t e (or s t a t e s not u s e d in t h e t a b l e in " A t o m i c P h y s i c s " (1969).
T A B L E II. I R R E D U C I B L E A L L - E X T E R N A L P A I R C O R R E L A T I O N E N E R G I E S O B T A I N E D
F R O M L E A S T - S Q U A R E S ANALYSIS O F G R O U N D - C O N F I G U R A T I O N A L L - E X T E R N A L
ENERGIES ONLY

e (2s-*-2p) 21
e(ls2) 6(1S2-2S) e(ls2-2p) e(2s2) <=(2p2;3p) «(2 P VD) e(2p ; S)
c(2s2p;3p) e(2s2p;Xp)

В 1.221 0.104 0.102 0.060 0.421 - - -

0.131 0.449

с 1.240 0.090 0.102 0.102 0.407 0.282 0.591 1.107


0.121 1 Ů.H0

N 1.256 0.071 0.102 0.147 0.420 0.244 0.589 1.165


0.118 1 0.485
0 1.261 0.082 0.102 0.190 0.431 0.219 0.556 1.111
0.104 1 0.551

F 1.266 0.079 С. 102 0.230 0.446 0.201 0.541 1.106


0.100 1 0.592
Ne 1.268 0.085 0.102 0.275 0.448 0.192 0.563 1.133
0.100 1 0.596
Na 1.274 0.083 0.102 0.318 0.471 0.168 0.594 1.149
0.100 1 0.642

e ( l s ? - » 2 s ) = [ 3 6(ls2s; 3 S) + e ( l s 2 s ; ' S ) 3 / 2 a n d t í l s ^ ž p ) = [ 3 e ( l s 2 p ; 3 P) + e ( l s 2 p ; ' p ) ] / 2 . For Boron t h r o u g h o x y g e n s e p a r a t i o n


of e(2s 2 -» 2p) i n t o e(2s2p; 3 P) a n d e(2s2p; !p) is o b t a i n e d b y a s s u m i n g the s a m e £(2s2p; 3 P ) / e ( 2 s 2 p ; >P) r a t i o as o b t a i n e d f r o m
analysis of all ground + e x c i t e d c o n f i g u r a t i o n s . In F , N , a n d N a e(2s2p; зр) a r e a s s u m e d t o r e m a i n - 0 . 1 e V . [ e ( 2 s 2 ) a l l - e x t ]
values a r e f r o m V. M c K o y a n d O . S i n a n o g l u , J. C h e m . Phys. 4 1 , (1964) 2 6 8 9 ; e ( l s 2 - » 2p) is f i x e d at the o x y g e n v a l u e by
H. P. K e l l y , Phys. Rev. 144, ( 1966) 39. s i n c e t h e s e s m a l l q u a n t i t i e s would b e t o o s e n s i t i v e in a l e a s t - s q u a r e s f i t .
IAEA - S M R - 1 2 / 5 2 77

T A B L E III. I N T E R N A L ( E I N T ) . S E M I - I N T E R N A L ( P L U S T H E S M A L L O R B I T A L
P O L A R I Z A T I O N S = E f ) AND T H E " E X P E R I M E N T A L " A L L - E X T E R N A L
C O R R E L A T I O N E N E R G I E S IN SOME S T A T E S AND IONS O F N I T R O G E N AND
OXYGEN

2 2 2 2 2 3 2 2
Is 2s 2p Is 2s 2p Is 2s2p
CONFIGURATION
STATE 3 4 2 2 4
P *D 2
S 2
P
P b> S D P

E
int -0.58 -0.56 -2.15 0.00 0.00 -0.95 0.00 0.00 0.00 0.00
Z = 7 Ef -1.14 -1.15 -0.07 -1.28 -1.31 -0.59 -0.14 -1.13 -0.18 -1.60
Eu("exp") -2.83 -3.18 -3.74 -3.84 -4.35 -4.76 -1.97 -2.40 -3.22 -2.54

E -0.68 -0.67 -2.57 0.00 0.00 -1.17 0.00 0.00 0.00 0.00
int
Z = 8 Ef -1.20 -1.23 -0.05 -1.40 -1.45 -0.64 -0.15 -1.14 -0.14 -1.64

Eu("exp") -2.88 -3.27 -3.80 -3.85 -4.35 -4.76 -2.13 -2.52 -3.28 -2.68

E x a m p l e s of o r d e r s of m a g n i t u d e s f o r d i f f e r e n t t e r m s , e. g. f o r

Z = 7; N = 7 ; ls22s22p3<^ : 2
D
4 4
S

a r e given in T a b l e III.
In g e n e r a l the t h r e e t e r m s a r e b a s i c a l l y c o m p a r a b l e .
L e t u s now a n a l y s e s e v e r a l c a l c u l a t i o n s of t e r m - s p l i t t i n g r a t i o s .
F i r s t u s i n g F a n d G i n t e g r a l s (without c o r r e l a t i o n ) a s in C o n d o n - S h o r t l e y ' s
or Slater's books for

'S
2 2 J
Z =6 lsř 2s 2p D

o n e f i n d s the r a t i o R = S D / D P = 1.5. M a k i n g a s e p a r a t e H . F . c a l c u l a t i o n
f o r e a c h t e r m , t h e r a t i o c h a n g e s b y 1 o r 2%, u s i n g the u s u a l C . I. o r
M C S C F one a l s o g e t s 1 - 2 % . C o m p a r i n g w i t h e x p e r i m e n t s , w e n o t e t h a t
t h e C o n d o n - S h o r t l e y - H a r t r e e - F o c k - M C S C F m e t h o d s w o r k f o r low c o n f i g u -
r a t i o n s but f a i l f o r h i g h e r c o n f i g u r a t i o n s . C o n s i d e r , e. g.
78 SINANOGLU

Z =6 I s 2 2s2p R =
F and G m e t h o d g i v e s 1.5
B a c h e r - G o u d s m i t method gives 4.34
Layser Z-dependent theory 1.45 (61)

Experim ental 2.3


Our theory 2.75

E r r o r s in e l e c t r o n a f f i n i t y a r e a l s o of the o r d e r of 10-15% while H . F .


y i e l d s a w r o n g sign.
U s i n g the l a r g e new p r o g r a m by O. Sinanoglu and D. B e c k we can go
to 3 r d - r o w a t o m s (i. e. Mg, Al, Si, . . . ) and a l s o r e c a l c u l a t e 2 n d - r o w
a t o m s m o r e a c c u r a t e l y and we can study h i g h e r e x c i t a t i o n s .

5. TRANSITION P R O B A B I L I T I E S

So f a r we c o v e r e d the t h e o r y of g r o u n d s t a t e s and then we s u m m a r i z e d


the t h e o r y of e x c i t e d s t a t e s . We c a l c u l a t e d the d i f f e r e n t c o r r e l a t i o n
c o n t r i b u t i o n s to open s h e l l s y s t e m s . We c o n s t r u c t e d the " c h a r g e -
d i s t r i b u t i o n wave f u n c t i o n "

+ X
^c - ^CD" ^RHF INT+ F

F u r t h e r we showed that t h e a l l - e x t e r n a l c o r r e l a t i o n in e n e r g y could b e


c a l c u l a t e d in the s a m e way a s f o r the c a s e of closed s h e l l s y s t e m s .
We s h a l l d i s c u s s now s e v e r a l t o p i c s :
(1) T h e t r a n s i t i o n p r o b a b i l i t i e s . We c o n s i d e r the new t h e o r y and new
e x p e r i m e n t s . We s h a l l d i s c u s s two k i n d s of t r a n s i t i o n p r o b a b i l i t i e s f o r
which the e x p e r i m e n t a l and t h e o r e t i c a l s i t u a t i o n is quite d i f f e r e n t :
(a) Allowed t r a n s i t i o n p r o b a b i l i t i e s
(b) F o r b i d d e n t r a n s i t i o n p r o b a b i l i t i e s
T h e s e t o p i c s a r e i n t e r e s t i n g f o r s e v e r a l r e a s o n s . T h e y have a p p l i c a t i o n s
in p l a s m a p h y s i c s , in a t m o s p h e r i c p h y s i c s and in a s t r o p h y s i c s . T h e y a l s o
give c o n f i d e n c e upon s u c c e s s f u l t e s t s of the t h e o r y of a t o m s , in s i m i l a r
molecular calculations.
Then we s h a l l c o n s i d e r
(2) S t a b l e - m o l e c u l e s binding e n e r g i e s .
So l e t u s s t a r t with the t r a n s i t i o n p r o b a b i l i t i e s .
We s h a l l not c o n s i d e r now c o l l i s i o n a l t r a n s i t i o n s t h a t m o d i f y t h e
l i f e t i m e s т . We u s e the s p o n t a n e o u s e m i s s i o n f o r m u l a :

(62)
Tm =
2 A,
n

.where e = ДЕ i s the e n e r g y d i f f e r e n c e , ûi i s the d e g e n e r a c y of the i n i t i a l


s t a t e and c ' i s v e l o c i t y of light (in a . u . 137), while S i s t h e line s t r e n g t h .
IAEA - S M R - 1 2 / 5 2 79

An a l t e r n a t i v e i s to u s e t h e o s c i l l a t o r s t r e n g t h

f=f ^ S
d Uj

S(yLS ^ y'L'S') (63)

F o r t h e l e v e l s of the l i g h t e r a t o m s one u s e s L S - c o u p l i n g and t h e j - j


s e p a r a t i o n i s not too l a r g e , s o one i s i n t e r e s t e d in m u l t i p l e t o s c i l l a t o r
strengths.
T h e u s u a l c a l c u l a t i o n s a r e b a s e d on the o n e - e l e c t r o n m o d e l w h i c h t u r n s
out i n a d e q u a t e , b e it R a c a h ' s m e t h o d or C o n d o n - S h o r t l e y 1 s. One h a s to
c a l c u l a t e t h e w h o l e N - e l e c t r o n m a t r i x e l e m e n t e v e n in t h e c e n t r a l f i e l d ,
i. e. t h e R H F a p p r o x i m a t i o n :

S(YLS Y'L'S') = ^ |< Y L S M l M J R I T ' L ' S ' M ; ivy > | 2 (64)

M l ,M s ,M' l , Mg

W e s t a r t with d i p o l e t r a n s i t i o n s E l . We c a n u s e e a c h of t h r e e o p e r a t o r s
to get t h e s e allowed t r a n s i t i o n s :

(i) 1 d i p o l e length г Й ï? ; f r = b e Sr
i=l
Л
(ii) velocity operator v =y Vj; fy = ь ^ s v (65)
i —1

(iii) acceleration f a = b -4- S,


» e

with
S r = |<i|?|f > | ? S v = | < i | v | f >| 2 , Sa = | < i | w | f >|*

and

v = -V -+ У
1=1

but one d o e s not n e e d t o c a l c u l a t e m a t r i x e l e m e n t s of ( 2 - e " ) - o p e r a t o r s


b e c a u s e t h e y c a n c e l out, owing to t h e f a c t t h a t t h e f o r c e a c t i n g on i - t h e"

1
T o e l i m i n a t e t h e d e p e n d e n c e on e , w e c a n a l s o c a l c u l a t e f = Vf r
80 SINAN OG LU

b e c a u s e of t h e j - t h one i s c a n c e l l e d by the f o r c e of i - t h e" a c t i n g on


j - t h e~. In f a c t we have

Vi У Z_
i V =
/ , r? r2
i=l i=l

s o the p o r t i o n n e a r the o r i g i n i s dominant in t h i s 3rd c a s e .


F o r the H - a t o m all t h r e e o p e r a t o r s give the s a m e r e s u l t . F o r the He
a t o m they a r e r e a s o n a b l y c l o s e .
T h e NBS t a b l e s r e p o r t m o s t l y H a r t r e e - F o c k c a l c u l a t i o n s with r e s u l t s
(f r and f v ) which a r e often w r o n g by about a f a c t o r of 2 c o m p a r e d to the
t r u e v a l u e s . T h e f a with with H . F . u s u a l l y d i f f e r s by a f a c t o r of 500. In
t h e NBS (3 v o l u m e s ) T a b l e s (1969) the r e s u l t s a r e often an a v e r a g e of
v a r i o u s e x p e r i m e n t a l v a l u e s and H . F . , o r m a y b e C . I . (a couple of c o n -
f i g u r a t i o n s a t m o s t by and l a r g e ) . But l a t e l y the new e x p e r i m e n t a l
t e c h n i q u e s and M E T c a l c u l a t i o n s a r e changing t h i s s i t u a t i o n .
Now we h a v e f o r i n i t i a l and f i n a l s t a t e s (a = i o r f)

+
CD " 'PRHF MNT +F

b u t we h a v e a l a r g e n u m b e r of d e t e r m i n a n t s in b r a and k e t f o r the t r a n s i t i o n
p r o b a b i l i t y m a t r i x e l e m e n t without o r t h o g o n a l i t y p r o p e r t i e s to help u s .
F o r i n s t a n c e we could h a v e an i n i t i a l s t a t e l s 2 2 s m 2 p n a s H . F . " s e a " and
the f s f p f d f f a s the a d d i t i o n a l s e m i - i n t e r n a l o r b i t a l e , going to l s 2 ' 2 s m ' 2p n '
with new o r b i t a l s that a r e n o n - o r t h o g o n a l to the e a r l i e r o n e s . H o w e v e r ,
a new l a r g e p r o g r a m h a s b e e n developed b y P . W e s t h a u s and O. Sinanoglu [2],
which i n v o l v e s i n i t i a l t r a n s f o r m a t i o n s of the n o n - o r t h o g o n a l o r b i t a l s and
d e a l s with t h i s p r o b l e m e f f e c t i v e l y .
P r e v i o u s l y only c a l c u l a t i o n s c o m p a r a b l e in m a g n i t u d e w e r e c a r r i e d
out b y W e i s s [15], f o r c a r b o n , u s i n g about 20 c o n f i g u r a t i o n s in С. I. , but
with the u s u a l d e f e c t s of the С. I. m e t h o d , so it w a s not s u f f i c i e n t l y
a c c u r a t e o r g e n e r a l . (The u s u a l С. I. k e e p s adding c o n f i g u r a t i o n s , but it
i s not c l e a r which to c h o o s e ; it i s slowly c o n v e r g e n t and m a y take into
a c c o u n t u n i m p o r t a n t o n e s and o m i t s i g n i f i c a n t o n e s , like the x s e m i - i n t e r n a l .
MET eliminates these defects.)
In the С - I I t r a n s i t i o n which we show h e r e a s an e x a m p l e ,

С II 2p 2 P ° -> 2p 2 2 D
j. RHF f RHF -NBS „new (66)
! 1
*r V exp

0.263 0.262 0.27 0.114

Without the new e x p e r i m e n t a l r e s u l t s one would r e a c h the c o n c l u s i o n that


one had v e r y good R H F r e s u l t s as f r , f v and " e v e n " f N B S c o i n c i d e . But
f"®p showed t h e v a l u e s to b e i n c o r r e c t . T h e a r g u m e n t t h a t RHF g i v e s the
s a m e r e s u l t s f o r d i f f e r e n t o p e r a t o r s , i s a l s o not t r u e g e n e r a l l y as we s e e
in a n o t h e r e x a m p l e ,
IAEA - S M R - 1 2 / 5 2 81

N III 2p 2 P° -> 2p 2 2 S

fRHF fRHF fNBS fej[p (67)

0.056 0.035 0.11 ?

Now let u s c o n s i d e r the new t h e o r e t i c a l (MET) c a l c u l a t i o n s of


Sinanoglu and W e s t h a u s :

f new jRHF fNBS jMET


о л 9 9
С II 2р Р -» 2р D 0 114 0 263 _ 0 1 2 5

N II 2р 2 3 Р -» 2р 3 3 D° { 0109 °-236 0 Л 7 0 Л 0
°
(68)

L e t u s now look at the e x p e r i m e n t s :


T h e t r a d i t i o n a l m e t h o d s w e r e of the e m i s s i o n o r a b s o r p t i o n t y p e s .
In o r d e r to d e t e r m i n e i n t e n s i t i e s f r o m e m i s s i o n one n e e d s the n u m b e r
of a t o m s v e r y a c c u r a t e l y ; a l s o f o r a b s o r p t i o n , and t h i s m a k e s the o l d e r
m e t h o d s u n r e l i a b l e , no b e t t e r than b y a f a c t o r of two. H o w e v e r , s i n c e
about 1965 new m e t h o d s h a v e c o m e about:
(1) B e a m - f o i l s p e c t r o s c o p y (BFS)
(2) P h a s e s h i f t m e t h o d
B a s h k i n (1965) developed B F S L16] . You a c c e l e r a t e ions (even with a
t a n d e m l i n e a r a c c e l e r a t o r , f o r example) and then n e u t r a l i z e t h e m o r s e l e c t
them, etc.

->x

atom beam
1 - 5 MeV

foil

In p a s s i n g t h r o u g h the thin f o i l , the a t o m s a r e e x c i t e d . How do they


r e t u r n to the ground s t a t e ? B y r a d i a t i n g a p e n c i l of light of d e c r e a s i n g
d e n s i t y along the b e a m a x i s .
T h e o b s e r v e d line i n t e n s i t y i s a function of d i s t a n c e and the l i f e t i m e т
i s obtained f r o m the r e l a t i o n

I(x) = I(XQ) E - x / " (69)

w h e r e I(x) i s the i n t e n s i t y of light along t h e b e a m at x and v is the b e a m


velocity.
82 SINANOGLU

If t h e p a r t i c u l a r p r o c e s s i s w e l l - k n o w n , e. g. t h a t t h e l i g h t i s known
t o b e due t o a s i n g l e t r a n s i t i o n i -> f, one a l s o h a s :

t =-£- (70)
if

and one o b t a i n s A w i t h a n a c c u r a c y of 3-10%. B u t one can h a v e a c a s c a d e


and h a v e a s u p e r p o s i t i o n of e v e n t s . So it i s c r u c i a l to h a v e a good i n t e r -
p r e t a t i o n . And h e r e the t h e o r y c o m e s in; in new t h e o r y we c a n r e a c h
a c c u r a c i e s of 3 - 1 0 % , s o w e c a n d i s t i n g u i s h b e t w e e n e x p e r i m e n t a l r e s u l t s
b a s e d on d i f f e r e n t i n t e r p r e t a t i o n s .
F o r e n e r g i e s a b o v e 5.5 M e V , one n e e d s a t a n d e m V a n - d e - G r a a f f
a c c e l e r a t o r o r a h e a v y - i o n l i n e a r a c c e l e r a t o r . O n e c a n get unknown l e v e l s
in h e a v y a t o m s , o r i o n s n e v e r o b s e r v e d in l a b o r a t o r y b e f o r e . In a s t r o -
p h y s i c s , 20% of t h e o b s e r v e d s o l a r u . v . l i n e s h a v e not b e e n i d e n t i f i e d a s
l i t t l e i s known a b o u t h e a v y i o n s . So t h i s i s a v e r y f r u i t f u l f i e l d .
B e y o n d the A r a t o m r e l a t i v i s t i c e f f e c t s b e c o m e i m p o r t a n t . We m u s t
m o d i f y the t h e o r y to have a reasonable approximation to r e l a t i v i s t i c theory

N, N

h
=Z i 4 <71>
i =1 i >j
quasi-relativistic Dirac Breit

The exact solution f o r HB , will again be

p
r e l RHF T
S T + x ' e l + Xff 1
XINT (72)

R e l a t i v i s t i c c o r r e c t i o n s c a n b e c o m p a r a b l e to c o r r e l a t i o n c o r r e c t i o n s
f o r a t o m s with Z S 10. So t h e e n e r g y m u s t b e s u b d i v i d e d a s :

E = E + E
rel r e l HF r e l CORR

F o r l i g h t e r a t o m s we c u s t o m a r i l y a s s u m e

E E
r e l . correlation ~ correlation (74)

and

E = E + E E
R H F C0RR+ rel (+ E
radiative corrections) ( 7 5
)

T h e r e a r e i m p o r t a n t r a d i a t i v e e f f e c t s w h i c h w e do not r e a l l y know
h o w t o h a n d l e y e t . T h e r e l a t i v i s t i c a r e a m a y b e the t h i r d p h a s e in the
a t o m i c - s t r u c t u r e t h e o r y . (The f i r s t p h a s e was the H a r t r e e - F o c k one,
t h e s e c o n d p h a s e t h e n o n - r e l a t i v i s t i c c o r r e l a t i o n , b o t h of w h i c h a r e now
q u i t e w e l l w o r k e d out. )
N o w w e p a s s o v e r to f o r b i d d e n t r a n s i t i o n s w h i c h h a v e a l o n g l i f e t i m e
s o t h a t a t o m s in a b e a m w o u l d h a v e t o t r a v e l a t l e a s t 108 t i m e s l o n g e r
b e f o r e r a d i a t i n g . In t h i s c a s e t h e b e a m - f o i l m e t h o d i s not u s a b l e .
IAEA - S M R - 1 2 / 5 2 83

New e x p e r i m e n t s f o r f o r b i d d e n l i f e t i m e s c a p a b l e of b e t t e r than f a c t o r -
o f - t w o a c c u r a c y w e r e a c c o m p l i s h e d only v e r y r e c e n t l y .
F o r b i d d e n t r a n s i t i o n s a r e i m p o r t a n t in a s t r o p h y s i c s and a t m o s p h e r i c
p h y s i c s . So one h a s to r e l y on t h e o r e t i c a l v a l u e s a s f e w e x p e r i m e n t s a r e
p o s s i b l e so f a r .
F o r b i d d e n t r a n s i t i o n s [17] (e. g. [ О I]). T h e r e i s a line (E2) a t
X = 5577 A; t h i s i s the f a m o u s oxygen g r e e n line a s o b s e r v e d in the a u r o r a .
T h i s t r a n s i t i o n i s f o r b i d d e n by the s e l e c t i o n r u l e s b e c a u s e they belong to
the s a m e c o n f i g u r a t i o n so t h a t E l i s not p o s s i b l e . It i s c a u s e d p r i m a r i l y
b y E 2 , the e l e c t r i c q u a d r u p o l e t r a n s i t i o n . O t h e r l i n e s a r e c a u s e d by
m a g n e t i c dipole (Ml) (or M l and E2) t r a n s i t i o n s so we would h a v e to c o n -
s i d e r s p i n - o r b i t coupling, e t c . f o r t h o s e l i n e s .
A c t u a l l y , H . F . - c a l c u l a t i o n s of q u a d r u p o l e t r a n s i t i o n s h a v e a s m a l l e r
e r r o r b e c a u s e of the n a t u r e of t h e o p e r a t o r . T h e d i f f e r e n c e with c o r r e l a t e d
f u n c t i o n s i s 20-30%. In o u r N C M E T , the new a t o m i c - s t r u c t u r e - t h e o r y
c a l c u l a t i o n s h a v e y i e l d e d the only a c c u r a t e r e s u l t s a v a i l a b l e in t h i s f i e l d .
T h e r e s u l t s a g r e e v e r y well with two r e c e n t e x p e r i m e n t s . A s to t h e s e
r e s u l t s we r e f e r to the r e a d e r our r e c e n t p a p e r s [18].
T h e study of the a u r o r a , w h e r e s o l a r - e m i s s i o n e l e c t r o n s e x c i t e oxygen
which r e r a d i a t e s at night, y i e l d s i n f o r m a t i o n on the e l e c t r o n d i s t r i b u t i o n
in the u p p e r a t m o s p h e r e .
Some s t u d i e s of s o l a r f o r b i d d e n and allowed t r a n s i t i o n s to t e s t
a b u n d a n c e s h a v e led to c e r t a i n d i s c r e p a n c i e s . With P . W e s t h a u s and
C. N i c o l a i d e s O. Sinanoglu h a v e m a d e c a l c u l a t i o n s with t h e new a c c u r a t e
M E T - v a l u e s of f o r b i d d e n - t r a n s i t i o n p r o b a b i l i t i e s m o d i f y i n g s o m e abundance
v a l u e s in t h e sun.

6. M O L E C U L A R BINDING AND P O T E N T I A L E N E R G Y CURVES

O r b i t a l t h e o r i e s p r e d i c t no f o r m a t i o n of F 2 f r o m two f l u o r i n e a t o m s
and no v a n - d e r - W a a l s a t t r a c t i o n s even b e t w e e n He a t o m s . T h u s , c a l c u l a t i o n s
of m o l e c u l a r e x c i t e d s t a t e g e o m e t r i e s , l i f e - t i m e s , e x c i t a t i o n e n e r g i e s ,
p o t e n t i a l e n e r g y c u r v e s on s u r f a c e s f o r ground and e x c i t e d s t a t e s , including
the m i n i m a , i . e . d i s s o c i a t i o n (De) o r a t o m i z a t i o n e n e r g i e s ( - Д Е а ) , a l l
require a non-closed-shell many-electron theory.
T h e binding e n e r g y Л Е а of, say,

A + В + С -> (ABC); Л Е а (76)

r i g o r o u s l y c o n s i s t s of a " H a r t r e e - F o c k (MO) b i n d i n g " , AE RHF and a


"correlation binding", ДЕСШК,

Д Е а = ДЕ„нг + AE CORR (7 7)

where for each species, e . g . (ABC)

E
" -ERHF + ECORR (78)
84 SINAN OG LU

with t h e e x a c t e l e c t r o n i c , a d i a b a t i c w a v e f u n c t i o n

=
^ ^RHF"1" x
CORR (79)

X = 0
^ ^RHF I CORR^

T o give an i d e a of the r e l a t i v e m a g n i t u d e s of t h e two k i n d s of c o n -


t r i b u t i o n t o m o l e c u l a r b i n d i n g , we c o m p i l e d in T a b l e s IV and V,
Д Е с о к к / Л Е а (exp), t h e b i n d i n g r a t i o , f o r a wide v a r i e t y of m o l e c u l e s . T h e
A E c o r r v a l u e s h a v e b e e n obtained u s i n g o u r c o r r e l a t i o n t h e o r y (ground
s t a t e v e r s i o n , M E T [7]) and a r e c e n t m e t h o d d e v e l o p e d b y P a m u k and
Sinaňoglu [19] which u s e s a s input the s i m p l e L C A O MO c o e f f i c i e n t s and
a t o m i c d a t a . We s e e t h a t in the g r o u n d s t a t e s t h e c o r r e l a t i o n b i n d i n g i s
t y p i c a l l y 30-40%, b u t i n c r e a s i n g to 200% (two h u n d r e d p e r cent!) in
d i a t o m i c m o l e c u l e s l i k e F 2 . T h e e f f e c t should b e even l a r g e r f o r e x c i t e d
states.
P o t e n t i a l - e n e r g y - c u r v e c a l c u l a t i o n s h a v e b e e n a t t e m p t e d in the
l i t e r a t u r e f o r s o m e t i m e . F i r s t , t h e H a r t r e e - F o c k MO m e t h o d w a s u s e d .
It i s , h o w e v e r , w e l l - k n o w n now t h a t t h e m e t h o d y i e l d s p o o r b i n d i n g and
i m p r o p e r d i s s o c i a t i o n . T h e l a t t e r i s due to t h e o v e r l o o k e d n e c e s s i t y of
t r e a t i n g even the g r o u n d s t a t e s of m o l e c u l e s a s n o n - c l o s e d s h e l l s y s t e m s
(see below). The difficulty has been o v e r c o m e by mixing a few configurations
f r o m t h e v a l e n c e s h e l l (in H 2 , log + lcr^). Thus the n e x t c a l c u l a t i o n
m e t h o d e m p l o y e d in t h e p a s t t e n y e a r s in t h e l i t e r a t u r e h a s b e e n to do
H a r t r e e - F o c k c a l c u l a t i o n s with t h e f i r s t f e w v a l e n c e - s h e l l c o n f i g u r a t i o n s

T A B L E IV. BINDING E N E R G I E S (ATOMS -> M O L E C U L E S ) O F S M A L L


P O L Y A T O M I C M O L E C U L E S - RATIO OF C O R R E L A T I O N BINDING T O
H A R T R E E - F O C K MO BINDING - P R E D I C T E D BINDING B A S E D ON
C O R R E L A T I O N T H E O R Y C O M P A R E D WITH E X P E R I M E N T (eV)
b
В. E.H. F. B E
- 'CORRB В. E. .. ,
predicted
Molecule B Е B. E.C
(H.F. МО) - - С ORR В Е (MET-EPCE-F 2 O) exp
- - exp

HCN 8. 89 4.48 33. vk 13. 6 13. 54

H20 6.77 2. 73 27. Vh 9. 6 10. 08

C02 11. 39 5.36 31. №h 16.8 16. 86

N20 3.97 6.57 56.0% 10. 5 11.73

C2N2 13.01 8.29 38. \°k 21.4 21.75

CH4 13.87 4. 34 23. 9fy 18.2 18. 18

C 2 H4 17.63 6.86 28. Vjo 24.5 24. 37

FCC H 11. 91 5.45 < 30 4


- %ED. 17.9 -

a
From various sources; references in (b).
b
O. Sinanoglu and H. Ö. Pamuk, Ref. [ 19].
c
Based on G. Herzberg, "Infrared and Raman Spectra", Van Nostrand, N . Y . (1945).
IAEA - S M R - 1 2 / 5 2 85

T A B L E V. BINDING E N E R G I E S (В. E . ; eV) (ATOMIZATION ENERGIES)


OF SIZABLE P O L Y A T O M I C S - CONTRIBUTION OF C O R R E L A T I O N T O
BINDING AND P R E D I C T I O N OF В. Е . WITH T H E T H E O R Y M E T - E P C E - F 2 c r

B E,
' C0RR
Molecule R F a
B.E.b
• CORR exp B. E. <*>' predicted
exp

Pyrrole 0. 6182 1. 7 7 6 34.8% 1.78

Pyridine 0.7233 2. 0 5 35.2% 2 . 09

Pyrazine 0.6911 1.9 36. 4% 2 . 00

Benzene 0.7530 2.24 33. 5% 2. 17

Naphthalene 1.193 3.47 34. 3<Уо 3.44

a
O. S i n a n o g l u and H. Ö. P a m u k , Ref. [ 1 9 ] .
b F r o m v a r i o u s s o u r c e s i n d i c a t e d in Ref. [ 1 9 ] .

t o g e t h e r ( m u l t i - c o n f i g u r a t i o n a l MO SCF = M C S C F , OVC, etc. ). But t h i s


t o o p r o v e s i n a d e q u a t e to obtain m o s t of the binding and the P . E . curve.
T h e following s c h e m e i l l u s t r a t e s t h i s f o r the F 2 m o l e c u l e w h e r e the b e s t
e f f o r t s by Wahl and D a s [20] and o t h e r s yielded about 30% of the D e . One
d i f f i c u l t y i s to d e c i d e how to c h o o s e the new c o n f i g u r a t i o n s .

De f o r m o l e c u l e , by d i f f e r e n t m e t h o d s

a
F2 D e (exp. ) = 1.68 eV
D e (M О SCF ; H . F . ) = -1.37 e V b
D e (MCSCF; OVC) ~ 0.6 eV°
D e (including the n o n - c l o s e d » 1.5 eV d
s h e l l new N C M E T c o r r e l a t i o n
effects, p a r t i c u l a r l y the s e m i -
internal correlation)

A s y s t e m a t i c a n s w e r i s p r o v i d e d by the r i g o r o u s N C M E T which, a s
we showed a b o v e , g i v e s t h e c o r r e l a t i o n e f f e c t s

*ЕХАСТ= ^RHF4" X
INT + + X
U

with a l l p a r t s m u t u a l l y o r t h o g o n a l .
F i g u r e 2 d e m o n s t r a t e s t h e s e e f f e c t s . T h e s e p a r t s of ¥ a r e f u l l y
s p e c i f i e d , once the i n i t i a l d o m i n a n t o r b i t a l s in the s i m p l e MO o r VB
p i c t u r e a r e s p e c i f i e d to c o n s t i t u t e the finite H a r t r e e - F o c k set o r " s e a " .

* I C Z K O W S K I , R. , MARGRAVE, J. , c f . (d) of T a b l e I .
WAHL. A . C . , J. C h e m . Phys. 4 1 , ( 1 9 6 4 ) 2 6 0 0 .
Ref. [ 2 0 ] i n t e x t ,
c f . R e f s [ 2 1 , 22] a n d [ 2 4 ] i n t e x t .
86 SINANOGLU

(Mj-Uij)
occ'd unocc'd
H.F. H.F.
NO'S MO's
J V
"CHARGE WAVE F U N C T I O N OF N C M E T " = Ф с = « R H F • X | N T • XSEM,_INT (CLOSED-SHELL-LIKE
CORRELATIONS NEEDED
(YIELDS LIFETIMES, HFS-CONSTANTS, DIPOLE MOMENTS, ETC.)
M A I N L Y FOR E N E R G Y
PROPERTIES )

FIG. 2. N e w c o r r e l a t i o n e f f e c t s in m o l e c u l e s g i v e n b y t h e N C M E T t h e o r y . ipexact- «RHF + X


C0RR;

>
<®RHf!xC0RR = о e^p-non-closed-shell Hartree-Fock M O wf "H.F. sea" = {ki} = { l o g , lo|, lo",... lir|}.

In m o l e c u l e s c o n s i s t i n g of H, B , C, N, O, and F , the

' H . F . s e t " ={ki} = -j и { l s a , 2s a , 2 p J (80)


all

i. e. the K, L spin o r b i t a l s of e a c h c o n s t i t u e n t a t o m . Or, equivalently,

H . F . s e t = {k;} = {1 Og, l o u , 2 o g , . . . 1тг§} (81)

occupied o r u n o c c u p i e d К and v a l e n c e s h e l l M O ' s (given in E q . (81) f o r


linear molecules).
In t h e n o n - c l o s e d s h e l l <ŘRHF and XINT- i n t e r n a l c o r r e l a t i o n , we have
a l l d e t e r m i n a n t s (dets), Д к , m a d e up of only t h e s e H . F . spin o r b i t a l s ,
M in n u m b e r . T h e t o t a l n u m b e r of p o s s i b l e d e t s a r e then f o r an

N-electron state.

О
0RHF + X
INT - У (82)

k= 1
T h e p r e v i o u s M C S C F (OVC, etc. ) included s o m e d e t s f r o m E q . (82).
T h e new e f f e c t found f i r s t f o r a t o m s , in N C M E T [1], is x F = s e m i -
i n t e r n a l c o r r e l a t i o n s (Fig. 2). H e r e e l e c t r o n s m a d e v i r t u a l t r a n s i t i o n s ,
s o m e within the H. F . s e t , but s o m e to new " s e m i - i n t e r n a l o r b i t a l s " , f,
beyond the f o r m e r . T h a t i s ,

k j k j -> k j fjj.

with

< f | k m > = 0 for all 1 s km s M


IAEA - S M R - 1 2 / 5 2 87

M o s t of t h e s e m i - i n t e r n a l M O ' s (dictated by s y m m e t r y ) a r e of the


o, it, 6, ф t y p e s , e. g. in l i n e a r m o l e c u l e s (made of A O ' s t h a t a r e of r o u g h l y
n = 3 r a d i a l b e h a v i o u r ) . In a single s e c o n d - r o w a t o m like С o r O, the
s e m i - i n t e r n a l Orbitals w e r e a s we s a w , 3*s, 3*p, 3*d and at m o s t
4 * f - l i k e l l ] . T h e d i s s o c i a t i o n b e h a v i o u r of t h e s e new t y p e s of M O ' s i n d i c a t e
t h e i r r e l a t i v e i m p o r t a n c e in m o l e c u l e f o r m a t i o n .
T h e l a s t e f f e c t in the e x a c t -p i s t h e " a l l - e x t e r n a l c o r r e l a t i o n " wave
f u n c t i o n х и . In the c o n f i g u r a t i o n - i n t e r a c t i o n (CI)-language it c o n s i s t s of
a l l d e t s , none of which include a n y v i r t u a l H . F . M O ' s o r A O ' s to which
t r a n s i t i o n s f r o m ф к н р h a v e taken p l a c e . Note that in the c l o s e d - s h e l l l i m i t
of a s y s t e m

^rhf ^ A 0 (single det)

\F -» 0
so that

^closed shell = Д 0 + Xu (83)

T h u s х и a r e c l o s e d - s h e l l - l i k e c o r r e l a t i o n s , t r e a t e d a s such by the c l o s e d -
s h e l l c o r r e l a t i o n t h e o r y , M E T [7], which showed the d o m i n a n c e of M O -
p a i r c o r r e l a t i o n s ûy and ey . T h e s e N ( N - l ) / 2 decoupled М О - p a i r c o r r e -
l a t i o n s , Cjj, f o r N - e l e c t r o n s i n g l e - d e t s t a t e s r e - i n t r o d u c e d in 1959-1962
with the g r o u n d s t a t e c o r r e l a t i o n t h e o r y , M E T [7] h a v e now b e e n studied
by m a n y a u t h o r s , notably K u t z e l n i g g , D a v i d s o n , C i z e k , P a l d u s , S c h a e f e r ,
K e s t n e r , King, Stanton, S t e i n e r , L a b z o w s k i , B r o w n , Roby, and o t h e r s ,
a s w e l l a s in the continuing w o r k of our own l a b o r a t o r y , f o r m a n y s m a l l
m o l e c u l e s , n o n - e m p i r i c a l l y a s w e l l a s s e m i - e m p i r i c a l l y . T h e e^- c o n -
s t i t u t e a quite a d e q u a t e way of a c c o u n t i n g f o r m o s t of the a l l - e x t e r n a l
c o r r e l a t i o n e n e r g y . How they o c c u r in n o n - c l o s e d s h e l l s t a t e s i s given
by N C M E T [1].

7. T H E S E M I - I N T E R N A L C O R R E L A T I O N E F F E C T AND M O L E C U L A R
POTENTIAL ENERGY CURVES

A s m e n t i o n e d above, the ( H . F . ) M O ' s did not yield p r o p e r P . E .


c u r v e s f o r m o l e c u l e s . T h e i n c l u s i o n of s o m e v a l e n c e c o n f i g u r a t i o n s ,
though i m p r o v i n g m a t t e r s c o n s i d e r a b l y , s t i l l did not a c c o u n t f o r m u c h of
the binding and e x c i t e d - s t a t e p r o p e r t i e s . H o w e v e r , a f t e r the s e m i - i n t e r n a l
e f f e c t w a s t h e o r e t i c a l l y found and shown to yield q u a n t i t a t i v e a t o m i c
p r o p e r t i e s , it w a s s u g g e s t e d t h a t it should be i n c l u d e d in m o l e c u l a r c a l -
c u l a t i o n s [21]. Indeed, upon i t s i n c l u s i o n , even p a r t i a l l y , f o r the f i r s t
t i m e an a d e q u a t e F 2 D e could be obtained [22]. It a l s o yielded o t h e r
m o l e c u l a r P . E . c u r v e s f o r s o m e ground and e x c i t e d d i a t o m i c s [23]. T h e
wave f u n c t i o n c a l c u l a t e d and i n c l u d i n g the c o r r e c t q u a l i t a t i v e f e a t u r e s of
P . E . s u r f a c e s , i s what we c a l l e d f o r s h o r t t h e " c h a r g e wave f u n c t i o n "
'ř c of N C M E T [24],

^c - $RHF+ XiNT+ Xf (84)


SINANOGLU

R (Ä)
1
FIG. 3. P o t e n t i a l e n e r g y c u r v e of I + BeO. T h e lower c u r v e is based on t h e N C M E T t h e o r y of
O. S i n a n o g l u (Refs [ 1, 21, 2 4 ] in t e x t ) as c a l c u l a t e d by H. F. S c h a e f e r , J. C h e m . Phys. 55, ( 1 9 7 1 ) 176.

T w o e x a m p l e s of P . E . c u r v e s a r e c o m p a r e d with e x p e r i m e n t in F i g s 3
a n d 4 w h e r e the t h e o r e t i c a l o n e s a r e o b t a i n e d with N C M E T . T o g e t m o r e
q u a n t i t a t i v e r e s u l t s , t h e a l l - e x t e r n a l c o r r e l a t i o n e n e r g y Д Е и can b e
o b t a i n e d b y t h e n e w l y d e v e l o p e d s e m i - e m p i r i c a l m e t h o d [19] and a d d e d
to the c h a r g e wave function r e s u l t

Л Е Л Е Л Е
(Р.Е.) = с + и <85)

One m a y a l s o n o t e t h e l i m i t of t h i s e q u a t i o n f o r a t r u e c l o s e d - s h e l l
s y s t e m in w h i c h , h o w e v e r and t h e r e f o r e , one c a n h a v e no c h e m i c a l binding:
t h e He - - H e , A r - - A r , e t c . n o n - b i n d i n g v a n - d e r - W a a l s c u r v e s . H e r e
( a s in E q . (83)),

ДЕ С -> A E r h f ( s i n g l e - d e t H . F . ' s ) (86)


IAEA - S M R - 1 2 / 5 2 89

2.0

FIG. 4 . P o t e n t i a l c u r v e of X 3 I ~ of 0 2 . T h e m i d d l e c u r v e is b a s e d on t h e c h a r g e w a v e f u n c t i o n of t h e N C M E T
t h e o r y by O. S i n a n o g l u (Refs [ 1, 21, 2 4 ] in t e x t ) as i m p l e m e n t e d for 0 2 by H. F. S c h a e f e r , J. C h e m . Phys.
54 ( 1 9 7 1 ) 2 2 0 7 .

and
Л Е A E Л Е
(Р.Е.) • RHF+ и <87>

He - - He,
Ar -- Ar,
etc. v a n - d e r - W a a l s i n t e r a c t i o n s

F u r t h e r m o r e , it w a s found s o m e t i m e ago that [25]

AE RHF (R) « v a n - d e r - W a a l s r e p u l s i o n s
9 A E r (R)
( v d W - r e p u l s i o n f o r c e Frep = - ^ ^ (88)

f o r a l l i n t e r n u c l e a r d i s t a n c e s , R. We h a v e in the l i m i t of l a r g e R,
AEjjfR) ^ v a n - d e r - W a a l s a t t r a c t i o n s

ЭДЕИ (R)
(89)
3R

lim AERHF-> 0

and

lim ДЕ П -> —
U
R- » R6
90 SINANOGLU

H o w e v e r , the M E T [7] and N C M E T [1], yield t h e s e v a n - d e r - W a a l s f o r c e s


f o r a l l R without a s s u m p t i o n s of n o - o v e r l a p , e t c . The a p p l i c a t i o n s of the
M E T t h e o r y [7] to v a n - d e r - W a a l s f o r c e s h a v e b e e n t r e a t e d in d e t a i l in the
r e c e n t book by M a r g e n a u and K e s t n e r [26].'
We s e e f r o m E q . (12) that, f o r a p o l y a t o m i c s y s t e m with c h e m i c a l
f o r c e s ( n o n - c l o s e d s h e l l a t o m s ) , c h e m i c a l binding e f f e c t s a r e in ДЕ С ,
while ДЕц i s a g e n e r a l i z a t i o n of the v a n - d e r - W a a l s f o r c e concept even to .
the a t o m s of an individual m o l e c u l e .
T h e l o n g - r a n g e and s h o r t - r a n g e p a r t s of i n t e r m o l e c u l a r f o r c e s u s u a l l y
w e r e c a l c u l a t e d in the old l i t e r a t u r e a s s e p a r a t e p r o b l e m s ; but the p r o b l e m
h a d r e m a i n e d of how to join s m o o t h l y t h e s e two p a r t s in the i n t e r m e d i a t e
r e g i o n of the i n t e r m o l e c u l a r potential. T h i s w a s an o u t s t a n d i n g p r o b l e m
r e f e r r e d to in m o s t t e x t b o o k s , f o r which no solution had e x i s t e d . Now
with the above r i g o r o u s n o n - c l o s e d s h e l l m a n y - e l e c t r o n f o r m u l a t i o n , the
a n s w e r t o t h e P . E . c u r v e t r e a t e d in i t s e n t i r e t y f r o m R = 0 to R -» °o i s
p r o v i d e d . We showed above that both s h o r t - r a n g e and l o n g - r a n g e f o r c e s
r e s u l t f r o m t h e s a m e r i g o r o u s t h e o r y which a l s o c o m b i n e s the c h e m i c a l
f o r c e s (ДЕ С ) with t h e v a n - d e r - W a a l s a t t r a c t i o n s ( Д Е и ) .

8. THE CHARGE WAVE FUNCTION AND CHARGE DISTRIBUTION


R E L A T E D P R O P E R T I E S OF M O L E C U L A R E X C I T E D STATES

The p o r t i o n f c of t h e e x a c t wave f u n c t i o n У we called the c h a r g e wave


f u n c t i o n b e c a u s e it i s the p a r t t h a t a f f e c t s the e l e c t r o n i c c h a r g e d i s t r i b u t i o n
s i g n i f i c a n t l y , w h i l e , a s we d e m o n s t r a t e d f o r a t o m s , t h e a l l - e x t e r n a l х и
h a s l i t t l e e f f e c t e x c e p t on e n e r g y [1, 7, 24]. A s a r e s u l t , p r o p e r t i e s of
m o l e c u l a r s t a t e s r e l a t e d to c h a r g e d i s t r i b u t i o n , such a s t h e s t a t i c (dipole,
q u a d r u p o l e , . . . ) m o m e n t s , spin d e n s i t i e s , h y p e r f i n e c o n s t a n t s , including
t h e n u c l e a r q u a d r u p o l e coupling c o n s t a n t , a s well a s the s i m i l a r t r a n s i t i o n
m o m e n t s giving r i s e to e l e c t r i c dipole and q u a d r u p o l e t r a n s i t i o n p r o b a b i l i t i e s ,
a r e given by the c h a r g e wave f u n c t i o n s ¥ c . Although such p r o p e r t i e s h a v e
now b e e n e x h a u s t i v e l y studied and obtained f o r m a n y a t o m s [ l ] , a n a l o g o u s
(and j u s t a s f e a s i b l e ) a u t o m a t e d c o m p u t a t i o n s on m o l e c u l e s have j u s t begun.

REFERENCES

[1] SINANOGLU, 0 . , A t o m i c Physics V o l l , P l e n u m Press, N e w York ( 1 9 6 9 ) 131, and r e f e r e n c e s t o his e a r l i e r


papers c o n t a i n e d t h e r e i n .
[2] WESTHAUS, P . , SINANOGLU, O. , Phys. Rev. 183 (1969) 5 6 .
[3] SINANOGLU, O . , BECK, D. R . , T h e o r . C h i m . A c t a 34 ( 1 9 7 4 ) 183; Phys. Rev. L e t t . 28 (1972) 9 4 5 .
[4] SINANOGLU, O. , J. M o l . S t r u c t . , (Proc. Int. C o n f . on M o l e c u l a r S p e c t r o s c o p y , S p e c i a l Issue)
W r o c l a w , P o l a n d , 19A ( 1 9 7 2 ) 81.
[5] SINANOGLU, O . , C o m m e n t s A t . M o l . Phys. I l l (1971) 53.
[6] SINANOGLU, O . , Rev. M o d . Phys. 3 5 (1963) 5 1 7 .
[7] SINANOGLU, O . , A d v . C h e m . Phys. VI (1964) 3 1 5 .
18] MOSHINSKY, M. , NOVARO, O . , CALLES, A . , J. Phys. (Paris) 3 1 C 4 ( 1970) 125.
[9] CALLES, A . , MOSHINSKY, M . , NOVARO, 0 . , SINANOGLU, O . , Phys. L e t t . 40A ( 1972) 79.
[10] KELLY, H . P . , Phys. Rev. Д 6 B896 (1964); 144 (1966) 39.
[11] MA, S . K . , BRUECKNER, K. A. , Phys. Rev. 2 6 5 (1968) 18.
[12] CHACON, E. , MOSHINSKY, M. , NOVARO, O. , WULFMAN, C . , Phys. Rev. A 3 ( 1 9 7 1 ) 166.
[13] ALPER, J . S . , SINANOGLU, O. , Phys. Rev. 177 ( 1 9 6 9 ) 77.
[14] SINANOGLU, O. , S K U T N I K , В . , C h e m . Phys. L e t t . 1 ( 1 9 6 8 ) 6 9 9 .
IAEA - S M R - 1 2 / 5 2 91

[15] WEISS, A . W , , Phys. Rev. 162 ( 1 9 6 7 ) 71.


[16] BASHKIN, S . , B e a m - F o i l S p e c t r o s c o p y , G o r d o n and B r e a c h , N e w York ( 1 9 6 8 ) .
[17] SINANOGLU. O. , C o m m e n t s A t . M o l . Phys. j l (1970) 7 9 .
[18] a) SINANOGLU, O . , N u c l . I n s t m r n . M e t h o d s , Proc. T h i r d I n t . BFS C o n f . 110 (1973) 193.
b ) SINANOGLU, O . , C o m m e n t s A t . M o l . Phys. 2 N o . 3 ( 1 9 7 0 ) 7 9 ;
NICOLAIDES, C . A . , SINANOGLU, O . , WESTHAUS, P . , Phys. Rev. A 4 ( 1 9 7 1 ) 1400.
[19] SINANOGLU, O . , PAMUK, H. Ö . , T h e o r . C h i m . A c t a 27 ( 1 9 7 2 ) 2 8 9 ; J. A m . C h e m . S o c . 9 5 ( 1973) 5 4 3 5 .
[20] WAHL, A . C . , DAS, G . , J. C h e m . Phys. £ 7 (1967) 2 9 3 4 .
[21] SINANOGLU, O . , C o m m e n t s A t . M o l . Phys. I l l (1971) 5 3 and e a r l i e r r e m a r k s .
[22] DAS, G . , WAHL, A . C . , Phys. Rev. L e t t . 2 4 (1970) 4 4 0 ; WAHL, A . C . , GILBERT, T . C . ,
SINANOGLU, O. e t al. , I n t . J. Q u . C h e m . Ills (1969) 4 7 9 .
[23] SCHAEFER, H . , J. C h e m . Phys. _55 ( 1 9 7 1 ) 176.
[24] BECK, D . , NICOLAIDES, C . , LUKEN, W . , SINANOÖLU, O . , I n t . J. Q u a n t . C h e m . _VIs( 1972) 1,
[25] KESTNER, N . R . , SINANOGLU, O . , J. C h e m . Phys. 4 5 ( 1 9 6 6 ) 194.
[26] MARGEN A U , H . , KESTNER, N . R . , T h e o r y of I n t e i m o l e c u l a r F o r c e s , 2nd Edn, P e r g a m o n Press,
London ( 1 9 7 1 ) .
IAEA-SMR-12/4, 5

O B S E R V E D S T R U C T U R E O F ATOMIC S P E C T R A

B. EDLÉN
Institute of Physics,
University of Lund,
Lund, Sweden

Abstract

OBSERVED STRUCTURE OF ATOMIC SPECTRA .


1. T h e c e n t r a l - f i e l d m o d e l of t h e a t o m ; 1 . 1 . Nucleus plus o n e e l e c t r o n ; 1.2. Closed shells plus o n e
e l e c t r o n (Rydberg series, i s o - e l e c t r o n i c sequences); 1 . 3 . Closed shells plus two electrons; 2. Series limits
and i o n i z a t i o n energies; 2 . 1 . T h e Ritz formula; 2 . 2 . T h e p o l a r i z a t i o n f o r m u l a ; 2 . 3 . I o n i z a t i o n energies
as functions of Z and N; 3 . Level intervals in i s o - e l e c t r o n i c sequences; 3 . 1 . " E l e c t r o s t a t i c " intervals;
3 . 2 . S p i n - o r b i t intervals; 3 . 3 . W a v e numbers of transitions; 4 . Survey of e l e c t r o n configurations and t e r m
systems; 4 . 1 . Ground configurations in t h e first half of the p e r i o d i c system (structure of 2 - to 1 0 - e l e c t r o n
systems, 1 1 - to 1 8 - e l e c t r o n systems, N = 1 9 - 2 8 , 3dk configurations); 4 . 2 . Ground configurations for N==47
4 . 3 . Brief survey of l i t e r a t u r e .

1. THE C E N T R A L - F I E L D MODEL OF THE ATOM

To d e s c r i b e t h e s y s t e m c o r e p l u s e l e c t r o n (n, t ) w e u s e t h e f o l l o w i n g
d e f i n i t i o n s : Z = n u c l e a r c h a r g e ; N = t o t a l n u m b e r of e l e c t r o n s ; Z - N = s t a g e
of i o n i z a t i o n ; Z - (N - 1) = Ç, t h e n e t c h a r g e of t h e c o r e = s p e c t r u m " n u m b e r "

f H, He + , L i 2 + , . . . Л
VH I, He II, L i III, . . . У

1.1. N u c l e u s p l u s one e l e c t r o n

T h e b i n d i n g e n e r g y i s g i v e n by

T =RZ2/n2; n = 1, 2, 3, . . . (1)

1. 2. C l o s e d s h e l l s p l u s one e l e c t r o n

D e g e n e r a c y in I i s r e m o v e d by p e n e t r a t i o n and i s q u a l i t a t i v e l y e x p l a i n e d
by e l l i p t i c o r b i t s . T h e b i n d i n g e n e r g y in t h e l i m i t of n e g l i g i b l e p e n e t r a t i o n i s

T = R Г 2 /п 2 (2)

D e p a r t u r e s f r o m (2) a r e e x p r e s s i b l e in two w a y s :

(a) T =RÇ2/(n-6)2 (3)

w h e r e n - ó = n* i s t h e e f f e c t i v e q u a n t u m n u m b e r and б i s t h e q u a n t u m d e f e c t ;
it d e p e n d s on SL but i s a p p r o x i m a t e l y i n d e p e n d e n t of n; h e n c e t h e g e n e r a l
f o r m u l a for a Rydberg s e r i e s is obtained.

93
94 EDLEN

FIG. 1 . I s o e l e c t r o n i c r e l a t i o n s for Li I a n d Na I l i k e s p e c t r a . A g a i n s t Z a r e p l o t t e d ( f r o m t o p to b o t t o m ) :
t h e " r e d u c e d " t e r m v a l u e t = T / R Ç 2 = ( n * ) " 2 ; V T / R = £ / n * = (£ + p ) / n , i l l u s t r a t i n g M o s e l e y ' s l a w ; t h e p e n e t r a t i o n
p = nVT7Ř"-S; from Ref.[11].
IAEA-SMR-12/4, 5 95

T A B L E I. C O M P L E T E F O R M U L A S FOR pf AND p g IN T H E P A I R -
C O U P L I N G A P P R O X I M A T I O N ( f r o m Ref. [ I l l )
Limit Designation
Config. Relative energy
J L К I

li G (4i) 5,4 +k p + 5F 2

li G <3i) 4,3
1 - f e p - 5 F 2 ± У ( Й р - 5 Е , ) 2 + Т5рг
i F (3i )' 4,3
pf .
li D (2i) 3,2
} -4Cp-fF2±y(ICp-iF/+180F2
i F (2i)' 3,2

li D (li) 2,1 + kp+12F2

r li H (5Í) 6,5 + Í C p + 28F 2

li H (4i) 5,4
i -iSp-¥F 2 W(Í5p-¥F2) + 2 1 5 6 F2
ii G (4Í)' 5,4
pg -
li F (3i) 4,3
j -ií p - 1 1 F Z ± 7 ( | i ; p - l l F 2 ) 2 + 4 2 3 5 F*
i G (3i)' 4,3

li F (2i) 3,2 + Í C p + 55F2

T A B L E II. F O R M U L A S F O R p 6 f , p 5 g , d 9 f , AND d 9 g IN P U R E P A I R
C O U P L I N G ( f r o m R e f . [11])
Parent Pair Pair
Relative energy Relative energy
level symbol symbol

Configuration p5f Configuration p5g

(3i)' + CP (4ÍV
r P
(2i)' H p (3i)" H p
i
(4i) - k p - 5F 2 (5i) " i c p - 28F 2

! (34) -kp+10F2 (4i) -Í£p+49F2


РзА
(2i) -kp+ 3F 2 (3i) -i£p+22F2

-
(li) - k p - 12F 2 (2i) -iCp-55F2

9
Configuration d f Configuration d 9 g
+
(4i)' +fcd- 7F 2 (5i)- f£d-39;F 2
(3i)' + 14F 2 (4i)' + fCd+68|F2

(2i)' +fcd +
4*F 2 (3i)> + f£d+30|F2
+
- (li)' |Cd-16jF2 (2i) ' +
fcd- "f2

(5i) - Cd" "F, (6i) - Cd- 56F 2


(4i) + 12
- Cd F2 (5i) - Cd + 5 3 i F 2

2
(3i) - Cd+ 12F
2 (4i) - £ d + 66|FZ
d5/2
(2i) - Cd+ rFz (3i) - Cd+23|F2
13
(li) - Cd" iF2 (2i) - Cd " « !
(i) - С d ~ 2 4 F2 di) - Sd " 1 1 0 F í
96 EDLEN

(b)

T = R(Ç+p)2/n® (4)

w h e r e Ç + p i s t h e e f f e c t i v e c h a r g e and p i s t h e p e n e t r a t i o n ; p d e p e n d s o n n
a n d JL but i s a p p r o x i m a t e l y i n d e p e n d e n t of Ç; it i s s u i t e d f o r i s o e l e c t r o n i c
comparison.
Ç+p = Z - s , s is called the s c r e e n i n g p a r a m e t e r .
F i g u r e 1 s h o w s t h e Z - d e p e n d e n c e of T / R and t h a t

(1) T / R Ç 2 = (n*)" 2 t e n d s t o w a r d t h e h y d r o g e n i c v a l u e .
(2) N/T/R= (Ç + p ) / n i s l i n e a r in Z ( M o s e l e y ' s law).
(3) n ^ T / R - Ç = p i s a p p r o a c h i n g a c o n s t a n t v a l u e .

1. 3. C l o s e d s h e l l s p l u s two e l e c t r o n s

T o t h e c e n t r a l - f i e l d - e n e r g y i s a d d e d t h e m u t u a l i n t e r a c t i o n e n e r g y of
t h e two e l e c t r o n s : t h e C o u l o m b e n e r g y , e x p r e s s e d by S l a t e r ' s F k , -
e x c h a n g e e n e r g y , e x p r e s s e d by S l a t e r ' s G k , and t h e m a g n e t i c i n t e r a c t i o n
e n e r g y of t h e o r b i t a l (SL) and s p i n (s) a n g u l a r m o m e n t a of e a c h e l e c t r o n ,
e x p r e s s e d by the p a r a m e t e r Ç n i .
The four angular m o m e n t a s b i 2 , s 2 , c o u p l e to t h e t o t a l a n g u l a r
m o m e n t u m J . C o u p l i n g i s p e r f o r m e d in s t e p s a r r a n g e d to give m e a n i n g f u l
i n t e r m e d i a t e r e s u l t a n t s . F o u r c a s e s of c o u p l i n g a r e p o s s i b l e :
(1) L S : (jř^í2)(sis2) LS - J ( e l e c t r o s t a t i c coupling)
(2) j j : ( í 1 s 1 ) ( í 2 s 2 ) - j g 2 - J ( m a g n e t i c coupling)
(3) jK: ( i l S l ) i 2 s2 - (j!Í2)s2 - K s 2 - J I „ „ C0UDling
Р&1Г C0U
(4) LK: ( M 2 ) Sl s 2 - (L Sl ) s 2 - KS2 - J J Pllng
H\SL<1 a r e c o u p l e d by C o u l o m b f o r c e s ,
SjS 2 a r e c o u p l e d by e x c h a n g e f o r c e s ,
m a g n e t i c c o u p l i n g of ( i j i 2 ), ( s ^ ) , ( í ^ ) , ( í 2 Sj) i s n e g l i g i b l e . D a t a and
r e l a t i o n s c o n c e r n i n g p a i r - c o u p l i n g a r e c o m p i l e d in T a b l e s I and II.

M
'P 'P, +/
+a„ 1n
/
/
/
/

S
/ electro- spin- magnetic
P / static orbit field
\
\
\\
\
\
4

-èr
3
P<
\ 3p

I con fig. 2 terms h levels 12 states

FIG.2. T h e o r e t i c a l p i c t u r e of a n s p - c o n f i g u r a t i o n in d i f f e r e n t a p p r o x i m a t i o n s ; f r o m R e f . [ 1 1 ] .
IAEA-SMR-12/4, 5 97

JJ

v —
FIG.3. G r a p h i c r e p r e s e n t a t i o n of t h e l e v e l s t r u c t u r e for t h e c o n f i g u r a t i o n s sp a n d sp 5 in i n t e r m e d i a t e c o u p l i n g ;
from Ref.[ll].
785 r~

aos 0.Ю DJS


Fz/t, Ш0/Т13
F I G . 4 . Structure of pf In i n t e r m e d i a t e coupling in t h e p a i r - c o u p l i n g FIG. 5. Structure of 2 p 5 nf in N e I showing pure pair c o u p l i n g ( s e e
a p p r o x i m a t i o n a c c o r d i n g to the formulas in T a b l e I ( a f t e r K . B . Eriksson, T a b l e II), t h e straight lines represent the t h e o r e t i c a l structure, from Ref.f 11],
Ref.[11]).
IAEA-SMR-12/4, 5 99

T h e L S - c o u p l i n g of s p , LS-*jj f o r sp a n d s p 5 , a s w e l l a s L K - c o u p l i n g
f o r 2p nf in N II and j K - c o u p l i n g f o r 2 p 5 nf in N e I a r e i l l u s t r a t e d in F i g s 2 - 5 .
F o r f u r t h e r i n f o r m a t i o n , we m a y r e f e r to t h e a r t i c l e " A t o m i c S p e c t r a "
in H a n d b . d e r P h y s i k , Vol. XXVII, S p r i n g e r - V e r l a g , B e r l i n (1964), and a l s o
" C o u p l i n g c o n s i d e r a t i o n s in t w o - e l e c t r o n s p e c t r a " by R. D. C o w a n and
K. L . A n d r e w , p u b l i s h e d in J . Opt. Soc. A m . _55 (1965), a s w e l l a s R e f . [2].

2. S E R I E S L I M I T S AND IONIZATION E N E R G I E S

2.1. The Ritz f o r m u l a

Let us f i r s t give the definitions:

E n - level e n e r g y counted u p w a r d s f r o m the ground level;


E
i i m = e n e r g y of s e r i e s l i m i t on t h e s a m e s c a l e ;

T n = E U m - E n = i o n i z a t i o n e n e r g y of t h e l e v e l E n , and t n = T n / R Ç 2 = ( n - 6 ) " 2

When w r i t i n g

Tn = R Ç 2 / ( n - 6 ) 2 (5)

we find 6 t o b e n e a r l y l i n e a r in T :

6n = a + b t n (6)
T a b l e III and F i g . 6 d e m o n s t r a t e t h i s r e l a t i o n s h i p (the R i t z f o r m u l a )
f o r a t e r m s e r i e s in Al III. T h e s l o p e (sign of b) i s p o s i t i v e f o r t h e
" p e n e t r a t i n g o r b i t s " n s and np, n e g a t i v e f o r t h e " n o n - p e n e t r a t i n g "

T A B L E III. AI III, R I T Z F O R M U L A S ( f r o m I S B E R G , B. , A r k . F y s . 35
(1968) 561)
n s 2 S i / 2 : = 0.8948072 + 0 . 1 1 6 6 4 7 t + 0.062977 t 2 ;
n p 2 P i / 2 : = 0.5897972 +0.186943 t + 0.18388 t 2 +0.11721 t 3 ;
np2P3/2: = 0.5881677 +0.188183 t+0.17540 t2 +0.14607 t 3 ;
nd2D: = 0.0736909 - 0 . 1 7 8 4 2 4 t - 0.23931 t 2 .
T
obs"Tcalc . cm"1
n
2 2 2
Si/Z Pф *P3/2 D
3 (0) (0) (0) (0)
4 (0) (0) (0) (0)
5 (0) (0) (0) (0)
6 0.04 (0) (0) 0.00
7 -0.04 -0.08 -0.05 -0.02
8 -0.09
100 EDLEN

FIG. 6 . Ritz d i a g r a m of t h e t e r m s e r i e s in AI III ( a f t e r В. I s b e r g , A r k . Fys. 3 5 ( 1 9 6 8 ) 5 6 1 ) .

nd, nf, e t c . To account f o r d e v i a t i o n s f r o m l i n e a r i t y t h e R i t z f o r m u l a


m a y be e x p a n d e d :

б n = a + bt n +ctl+.
n .. v(7)
'

The s e r i e s l i m i t is d e t e r m i n e d by v a r y i n g t h e v a l u e of E l i m until t h e Ritz


l i n e s p r o p e r l y a p p r o a c h l i n e a r i t y with i n c r e a s i n g n.
F o r a t o m i c s y s t e m s with m o r e t h a n one e l e c t r o n o u t s i d e c l o s e d s h e l l s
t h e R i t z l i n e s a r e o f t e n d i s t o r t e d by p e r t u r b i n g t e r m s , T 0 , which do not
belong to the s e r i e s but h a v e t h e s a m e p r o p e r t i e s (parity, J and o t h e r valid
IAEA-SMR-12/4, 5 101

q u a n t u m n u m b e r s ) a s t h e s e r i e s t e r m s Tn . The d e v i a t i o n s can be t a k e n
into account by adding to t h e Ritz e x p r e s s i o n a t e r m a / ( T n - T 0 ) with the sign
c o r r e s p o n d i n g to r e p u l s i o n b e t w e e n T 0 and T n . The e f f e c t i s due to m a t r i x
c o m p o n e n t s c o n n e c t i n g d i f f e r e n t c o n f i g u r a t i o n s . Such c o n f i g u r a t i o n i n t e r -
a c t i o n s a r e v e r y c o m m o n . F i g u r e s 7, 8 and 9 show s o m e e x a m p l e s .

2. 2. The p o l a r i z a t i o n f o r m u l a

The R i t z d i a g r a m f o r AI III s h o w s f o r nf, ng and nh a s t r i k i n g r e g u l a r i t y


in t h e Í - d e p e n d e n c e of 6. F o r t h e s e s t r i c t l y n o n - p e n e t r a t i n g o r b i t s t h e
i n c r e a s e in binding e n e r g y o v e r the h y d r o g e n i c v a l u e T H i s due a l m o s t
e n t i r e l y to a p o l a r i z a t i o n of t h e c o r e in the f i e l d of t h e o u t e r e l e c t r o n :

Л
Р = Т
" Т
н ="dR<r"4> (8)
102 EDLEN

FIG. 8 . P e r t u r b e d series in Si III ( a f t e r Y . T o r e s s o n , A r k . Fys. 18 (1960) 4 1 2 ) . (a) P e r t u r b a t i o n of t h e


s e r i e s 3 s n f 3 F 4 a n d !F 3 by t h e l e v e l s 3 p 3 d 3 F 4 a n d ' F 3 . (b) P e r t u r b a t i o n in t h e series 3 s n d . The perturbing
t e r m 3p2 ID 2 is s i t u a t e d a t T = 141.9 k K .

H e r e • \ r " 4 / i s an a v e r a g e v a l u e of r ~ 4 ; r i s the r a d i u s of t h e e l e c t r o n ' s


o r b i t in u n i t s of a 0 , and o-j is t h e dipole p o l a r i z a b i l i t y of t h e a t o m i c c o r e
F o r an o u t e r e l e c t r o n with the q u a n t u m n u m b e r s n and i t h e
theory gives

/ -4 \ _ «4 3 n 2 - 1 ( 1 + 1)
' 2n5(s>-D-eu+lm + D(i +1)

A c c o r d i n g to E q s (8) and (9) a single p a r a m e t e r , o?d , would d e t e r m i n e T f o r


any o r b i t n i with SL s u f f i c i e n t l y l a r g e . To extend t h e validity r a n g e of the
f o r m u l a we m a y include q u a d r u p o l e p o l a r i z a t i o n :

Др = a d R < r - 4 > + * q R < r - 6 > (10)


IAEA-SMR-12/4, 5 103

•к

FIG.9. P e r t u r b e d series in C a I ( a f t e r G . Risberg, A r k . Fys. 37 (1968) 2 4 4 ) / (a) n - n * versus l e v e l v a l u e


for t h e 4sns s e r i e s , (b) n - n * versus l e v e l v a l u e for t h e 4snp 3 P 2 a n d i P j s e r i e s .
104 EDLEN

T A B L E IV. AI III, T H E POLARIZATION FORMULA; C A L C U L A T E D AND


OBSERVED VALUES O F Д р FOR T H E H Y D R O G E N - L I K E TERMS ( f r o m
IS BERG, В . , A r k . F y s . 35 (1968) 560)
Д р = 20.510 P ( n , l ) [1 + 12.710 q(n, 1)].

Term Ap(calc) Ap (obs) A p (obs)-


TH,cm"i T
c a l c • с™"1
symbol cm-1 cm"i Ap (calc)

4f 61726.709 105.90 105.90 (0) 61832.61

5f 2 F 39 505.142 64.29 64.29 (0) 39 5 6 9 . 4 3

6f 2 F 27 4 3 4 . 1 2 2 40.43 40.43 0.00 27 4 7 4 . 5 5


2
7f F 20 1 5 5 . 6 6 9 26.70 26.79 0.09 20 1 8 2 . 3 7

8f 2 F 15431.673 18.43 18.56 0.13 15450.10

9f 2 F 12 1 9 2 . 9 1 8 13.21 13.48 0.27 12 2 0 6 . 1 3


2
5g G 39 504.903 12.21 12.21 (0) 39 5 1 7 . 1 1

6g2G 27 4 3 3 . 9 8 3 8.00 8.15 0.. 15 27 4 4 1 . 9 8

7g2G 20 155.582 5.40 5.60 0.20 20 1 6 0 . 9 8


2
8g G 15431.615 3.77 3.87 0.10 15 4 3 5 . 3 9

9g2G 12 1 9 2 . 8 7 7 2.72 2.66 -0.06 12 1 9 5 . 6 0


2
6h H 27 4 3 3 . 8 9 5 2.40 2.10 -0.29 27436.29

7h2H 20 1 5 5 . 5 2 6 1.68 1.72 0.05 20 1 5 7 . 2 0

8h2H 15 4 3 1 . 5 7 7 1.20 1.20 0.01 15 4 3 2 . 7 7


2
9h H 12 1 9 2 . 8 5 1 0.87 0.70 -0.П 12 1 9 3 . 7 3

71 e I 20155.487 0.63 20 1 5 6 . 1 2

8i 2 I 15431.551 0.46 15 4 3 2 . 0 2
2
9i I 12 1 9 2 . 8 3 3 0.35 12 1 9 3 . 1 8

8k 2 K 15431.532 0.20 15431.73


2
9k K 12 1 9 2 . 8 1 9 0.15 12 1 9 2 . 9 7
2
9i L 12 1 9 2 . 8 0 9 0.07 12 1 9 2 . 8 8

w h e r e o-q is in u n i t s of a§ and < ^ r - 6 ) i s given by an e x p r e s s i o n in n and S.


a n a l o g o u s to (9). If (10) is w r i t t e n a s

Ap/P(n,J>)=A + Bq(n,i) (11)

P and q being t a b u l a t e d f u n c t i o n s of n and I , and o b s e r v e d v a l u e s of Д р / Р


a r e plotted a g a i n s t q, they should f a l l on a s t r a i g h t line f r o m which t h e
p a r a m e t e r s A ( c o r r e s p o n d i n g to a<j ) and В ( c o r r e s p o n d i n g to o q ) a r e
d i r e c t l y obtained (see also T a b l e IV). F i g u r e 10 s h o w s this plot f o r AI III,
and F i g . 11 f o r В III, С IV, N V.
IAEA-SMR-12/4, 5 105

FIG. 10. G r a p h i c i l l u s t r a t i o n of t h e p o l a r i z a t i o n f o r m u l a a p p l i e d t o AI III. I n d i c a t e d error l i m i t s c o r r e s p o n d


to i 0 . 1 5 c m " ' in Д р ( a f t e r B . I s b e r g , A r k . Fys. 3 5 (1968) 5 6 0 ) .

2. 3. Ionization e n e r g i e s a s f u n c t i o n s of Z and N

By u s e of the Ritz and the p o l a r i z a t i o n f o r m u l a s a c c u r a t e v a l u e s f o r


i o n i z a t i o n e n e r g i e s h a v e b e e n d e r i v e d f o r m a n y a t o m s and ions. F o r o n e -
and t w o - e l e c t r o n s y s t e m s (H- and H e - l i k e ) t h e o r e t i c a l c a l c u l a t i o n s s u r p a s s
o r c o m p e t e in a c c u r a c y with e x p e r i m e n t a l v a l u e s . In t h e s e c o n d p e r i o d
(N = 3 - 10) e x p e r i m e n t a l ionization e n e r g i e s a r e now s u f f i c i e n t l y a c c u r a t e
and c o m p l e t e to p e r m i t an i n t e r e s t i n g study of t h e i r d e p e n d e n c e on Z at
c o n s t a n t N ( i s o - e l e c t r o n i c s e q u e n c e ) and on N at c o n s t a n t We adopt
the f o r m :

T = Rn'2 [ ? 2 + a Ç + b + c ( Ç + d ) - 1 ] + A r (12)

w h e r e a i s t a k e n f r o m t h e o r y , b, с and d a r e a d j u s t e d to fit o b s e r v a t i o n s ,
and Л r r e p r e s e n t s the r e l a t i v i s t i c c o n t r i b u t i o n . In T a b l e s V and VI the
r e s u l t s a r e c o m p i l e d f o r N = 3 ( l s 2 2 s ) and N = 4 ( I s 2 2 s 2 ) ; s e e a l s o F i g . 12.
F o r t h e s y s t e m s l s 2 2 s 2 2 p k (k= 1 - 6 ) t h e i o n i z a t i o n p o t e n t i a l s T c w e r e
t a k e n a s the e n e r g y d i f f e r e n c e b e t w e e n c e n t r e s of g r a v i t y of ground
c o n f i g u r a t i o n s of c o n s e c u t i v e i o n s . Then all p a r a m e t e r s b e c o m e s m o o t h
106 EDLEN

0 0.10 0.20 0.30 q(nl)

FIG. 11. Д р / P í n S ) as a f u n c t i o n of q ( n í ) for В III, С IV a n d N V. T h e lines for С IV a n d N V a r e based o n


t h e o r e t i c a l v a l u e s of A a n d o b s e r v e d v a l u e s of Ap(3d) ( a f t e r A . Ö l m e , A r k . Fys. 4 0 (1969) 4 3 ) .

T A B L E V. IONIZATION ENERGY O F I s 2 2s ( f r o m R e f . [12])

T(obs), c m " 1 V RM/4 6(calc)b T(calc) c

He" 0 27 4 3 0 . 5 7 -0.02481 -680

Li I 43 4 8 7 . 1 3.2 27 4 3 2 . 1 6 -0.23242 43 4 8 7 . 1

ВеП 146 8 8 2 . 9 ± 0.3 21.8 27 4 3 2 . 6 6 -0.28161 146 8 8 2 . 9

В in 305931.1± 0.6 79.3 27 4 3 2 . 9 4 -0.30363 305 930.7

С IV 520 1 7 8 . 4 ± 1.5 209.8 27 4 3 3 . 0 7 -0.31612 520 1 7 9 . 6

N V 7 8 9 537 ± 3 458.6 27 4 3 3 . 2 5 -0.32416 789 5 3 8 . 6

О VI 1 114008 ilO 882.1 27 4 3 3 . 3 9 -0.32978 1 1 1 4 008

F VII 1547.2 27 4 3 3 . 5 3 -0.33392 1 4 9 3 629

N e VIII 2532.1 27 4 3 3 . 5 8 -0.33710 1 9 2 8 462

a 4
Дг = 0.4565(5+0.63) cm-i, w h e r e 0 . 4 5 6 5 = -|rRc(2 •
b
6 = -0.361344+0.20899ÍC +0.621)-!.
c
T=(RM/4)fe2 + 0 . 8 1 7 5 6 £ + 0 ) + A r i w h e r e 0 . 81756 = 4 - 8 A e t w i t h Д С 1 f r o m t h e o r y .
IAEA-SMR-12/4, 5 107

T A B L E VI. IONIZATION E N E R G Y O F l s 2 2 s 2 ( f r o m R e f . [12])


a
С T(obs),cm_1 6(calc)b T(calc)c

Li" 0 0.18755 5 145

Bel 1 75 1 9 2 . l è 0 . 1 10.7 0.03233 75192.1

В II 2 202 8 8 7 . 4 è 0 . 8 47.9 - 0.02248 202 8 8 7 . 4

С III 3 3 86 2 4 1 . 0 ± 2 142.0 -0.05051 386241.5

N IV 4 6 2 4 866 ±3 333.8 -0.06753 624 8 6 4 . 6

O V 5 918657 ±4 674.5 - 0.07896 918 6 5 8 . 5

F VI 6 1226.8 - 0.08716 1 267 622

N e VII 7 2063.9 - 0.09334 1 6 7 1 792

a
Д г =0.4565(C + 1 . 2 0 ) « c m - i , where 0.4565 = - | r R a 2 .
b
6 = - 0 . 1 3 7 1 6 8 + 0 . 3 5 4 5 9 f e + 1. 092) - l .
c
T=(RM/4)fe2 + 1.70825c+6) + Д г , where 1.70825 = 6 - 8Де! withÄCj from theory.

f u n c t i o n s of k, and Д г i s s i g n i f i c a n t l y r e d u c e d and m a y b e p r o v i s i o n a l l y
n e g l e c t e d . T h e d e p e n d e n c e of T c on к and on Ç i s shown in F i g . 13 and
T a b l e VII.
We w i s h t o c o m p a r e t h e e m p i r i c a l r e l a t i o n s with r e s u l t s of s e c o n d -
o r d e r p e r t u r b a t i o n c a l c u l a t i o n s e x p r e s s e d in t h e f o r m

E(N) = E q (N)Z 2 + E 1 ( N ) Z +E2(N) (13)

w h e r e E(N) i s t h e t o t a l e n e r g y of t h e N - e l e c t r o n s y s t e m . If we put

A E j ( N ) = Ej(N) - E j ( N - 1) (14)

and i n t r o d u c e t h e v a l u e f o r E 0 ( N ) , we get f r o m (13) t h e i o n i z a t i o n p o t e n t i a l s


(in H a r t r e e u n i t s ) :

- AE(N) = (2n 2 )" 1 [(Z 2 - 2 n 2 A E 1 ( N ) Z - 2n 2 AE 2 (N)] (15)

C o m p a r i s o n of E q . (15) with t h e e m p i r i c a l e x p r e s s i o n (12) a f t e r r e p l a c e -


m e n t of Ç by Z - (N - 1) g i v e s :

a=2(N-l)-2n2AE1(N) (16)

- A E 2 ( N ) = ( N - 1) A E j Í N ) - [(N - l) 2 - b ] (2П 2 )" 1 (17)

H e r e n= 2. By a d o p t i n g t h e known t h e o r e t i c a l v a l u e f o r Д Е : and i n t r o d u c i n g
t h e e m p i r i c a l l y d e r i v e d b in E q . (17) we o b t a i n an e x p e r i m e n t a l v a l u e of Д Е 2 .
S i n c e t h e H a r t r e e - F o c k v a l u e s A E 2 F a r e e x a c t l y known we can e x p r e s s t h e
r e s u l t s in t e r m s of t h e c o r r e l a t i o n e n e r g y

AE",r = A E 2 - A E f (18)

The c o m p a r i s o n of e x p e r i m e n t a l and t h e o r e t i c a l v a l u e s f o r ДЕ 2 0 Г Г
in F i g . 14 r e v e a l s t h e p r e s e n t u n c e r t a i n t y in t h e t h e o r y .
1 0 8 EDLEN

FIG. 12. T h e quantities ó = ( T - A r ) r f / R M + a Ç ) p l o t t e d a g a i n s t С = Z - (N - 1); f r o m R e f . [ 1 2 ] .

3. L E V E L INTERVALS IN I S O - E L E C T R O N I C SEQUENCES

3. 1. "Electrostatic" intervals

F r o m the f a c t t h a t t h e p e n e t r a t i o n p a r a m e t e r p in the e x p r e s s i o n f o r
binding e n e r g i e s

T = R(Ç + p ) 2 / n 2

r e m a i n s r o u g h l y c o n s t a n t when Ç v a r i e s , it f o l l o w s t h a t i n t e r v a l s b e t w e e n
l e v e l s with e q u a l n a r e a p p r o x i m a t e l y l i n e a r in Z (or Ç) and t h o s e
IAEA-SMR-12/4, 5 109

1 2 3 4 5 6
40

39

38

i 37

36

35

34
СИ N11 ОП F II Nell Nail

FIG. 13. T h e d e p e n d e n c e on к of t h e i o n i z a t i o n p o t e n t i a l s T a n d T c of 2s2 2 p k f o r £ = 2 ; f r o m R e f . [ 1 2 ] .

c o r r e s p o n d i n g to d i f f e r e n t n a r e q u a d r a t i c in Z (or f ) . T h u s , by dividing
t h e i n t e r v a l s by a l i n e a r f u n c t i o n , Ç + a, one o b t a i n s in t h e f i r s t c a s e an
a p p r o x i m a t e l y c o n s t a n t value and in t h e s e c o n d c a s e a l i n e a r function.
T h i s is t h e s i m p l e b a s i s f o r t h e i s o - e l e c t r o n i c c o m p a r i s o n of e l e c t r o s t a t i c
energy intervals.
It f o l l o w s a l s o t h a t binding e n e r g i e s tend t o w a r d t h e i r h y d r o g e n i c v a l u e s
s i n c e , with i n c r e a s i n g t h e quotient (Ç + p)/Ç a p p r o a c h e s unity.
The c h a n g e s with Ç in t h e r e l a t i v e p o s i t i o n s of c o n f i g u r a t i o n s having
d i f f e r e n t c o m b i n a t i o n s of n - v a l u e s a r e well i l l u s t r a t e d in the Ca I s e q u e n c e
a s shown in F i g . 15. The l o w - l y i n g c o n f i g u r a t i o n s a r e in t u r n (4s4s), (4s3d)
and (3d3d). All l i n e s r e p r e s e n t i n g a given c o m b i n a t i o n of (n, n) a r e p a r a l l e l .
Such a g r o u p is b e s t s t u d i e d by t a k i n g one of the l e v e l s of t h e g r o u p as
r e f e r e n c e l e v e l , a s shown in F i g . 16 f o r 3 d 2 . Note i r r e g u l a r i t i e s in t h e
beginning of t h e s e q u e n c e , due to c o n f i g u r a t i o n i n t e r a c t i o n when t e r m s
f r o m different configurations r e v e r s e their relative positions as Ç changes.
The d i a g r a m in F i g . 17 f o r the t e r m s of 2s3£ and 2p3ü in t h e Be I s e q u e n c e
s h o w s a s i m i l a r b e h a v i o u r , f i r s t s o m e i r r e g u l a r i t i e s and then a p e r f e c t l y
s m o o t h a s y m p t o t i c Ç - d e p e n d e n c e . T h i s i s a v e r y i m p o r t a n t aid in t h e
p r a c t i c a l a n a l y s i s of s p e c t r a , e s p e c i a l l y f o r high i o n i z a t i o n s t a g e s .

3. 2. Spin-orbit intervals

In t h e h y d r o g e n i c e x p r e s s i o n f o r t h e s p i n - o r b i t e n e r g y p a r a m e t e r
D 2 Z„ 4
_ Rtt
-
nai(í +1)

we r e p l a c e Z by a " s c r e e n e d " c h a r g e , Z - s, and f i n d t h a t s p i n - o r b i t i n t e r v a l s


should v a r y a s (Z - s) 4 with s a p p r o x i m a t e l y c o n s t a n t . A f i n e e x a m p l e i s t h e
110 EDLEN

T A B L E VII. IONIZATION ENERGIES T c (cm" 1 ) F O R CONFIGURATION


C E N T R E S O F I s 2 2 s 2 2 p k ( f r o m Ref. [ 12])

Spectrum Tc(obs) 6(calc)a Tc(calc)b T-T c

2s 2 2 p

ВI 66 918 -0.41474 66 918 10

С II 196 622 -0.54087 196 622 42

N III 3 8 2 588 -0.61618 3 8 2 588 116

О IV 6 2 4 125 -0.66624 6 2 4 115 257

F V -0.70192 920 904 496


г
2s* 2р

С I 86004 -0.33472 86 0 0 4 4 816

N II 231529 -0.49983 231529 7 222

0 III 433 583 - 0.60440 4 3 3 583 9 504

F IV -0.67656 691394 11736

Ne V -0.72936 1004604 13 938

2sz 2p3

N I 106 2 9 8 -0,20765 106 2 9 8 10 928

0 II (267 467) -0.41519 267 467 15787

F III 485491 - 0.55030 485491 2 0 287

N e IV -0.64527 759484 ( 2 4 506)

Na V -0,71567 1 0 8 9 020 2 8 603


z
2s 2p4

О I 127 797 -0,03423 127 797 - 17 960

F II 3 0 4 525 -0.28486 3 0 4 525 -22466

N e III (538416) - 0.45184 538416 ( - 2 6 797)

Na IV -0.57105 828486 -31109

Mg V -0.66043 1174242 -35155

2S2 2p5

F I 150 4 4 3 0.18285 150 4 4 3 - 9918

N e II 342 649 -0.11200 3 4 2 649 - 12 260

Na III (592297) -0.31302 5 9 2 297 - 14 584

M g IV -0.45885 8 9 8 327 - 16 895

Al V - 0.56948 1 2 6 0 191 - 19249


2
2s 2p6

Ne I 174190 0.44138 174190 - 260

Na II 381850 0.10278 3 8 1 850 -455

M g III 647 152 -0.13471 647 152 -743

A l IV -0.31050 969 014 - 1 148

Si V -0.44587 1 3 4 6 854 -1698


IAEA-SMR-12/4, 5 111

N O T E S T O TABLE VII

a
Ó = T c / 2 7 4 3 4 ~ ( £ 2 + a £ ) , w h e r e a = 2(N - 1) - 8 Д £ 1 , w i t h f r o m t h e o r y and 2 7 4 3 4 = R / 4 .
k T c ( c a l c ) from t h e following formulas with 3 adjusted parameters:
2s 2p : T c / 2 7 4 3 4 = £ 2 + 1 . 8 5 3 9 8 t - 0 . 9 1 4 7 2 + 1 . 4 8 1 9 4 ( ç + 1. 9 6 4 Г 1
2

2s22p2: T c / 2 7 434 = £2 + 2 . 4 6 9 6 6 £ - 1 . 0 7 0 1 3 + 2 . 5 4 0 1 ( Ç + 2 . 4 5 4 ) " 1


2s 2 2 p 3 : T c / 2 7 4 3 4 = £2 + 3 . 0 8 2 3 3 ? - 1 . 1 8 9 5 3 + 3 . 6 6 3 4 (C+2.731)-1
2 s 2 2 p 4 ; T c / 2 7 4 3 4 = £ 2 + 3 . 69257C - 1 . 2 8 5 3 8 + 4 . 9946 (Ç+2.992)"1
2s 2 2p5 ; T c / 2 7 4 3 4 = £ 2 + 4 . 3 0 0 9 7 C - 1 . 3 7 5 4 2 + 6 . 6 7 7 2 fe+3.285)"1
2 s2 2p 6 : T c / 2 7 4 3 4 = £ 2 + 4 . 9 0 8 0 4 Ç - 1 . 4 8 7 9 5 + 9 . 0640 (£ + 3 . 6 9 8 ) " *

™ (N ^ <N <N (NI <N


l/> V> U) 1 Л 1 Л 1 Л 1 Л 1 Л
C N t N ^ ( N f v j C M f N C M

FIG. 14. C o m p a r i s o n of t h e o r e t i c a l a n d e x p e r i m e n t a l values of Д Е 2 ° Г Г = Л Е 2 - Д Е Р ' ' . Curve A calculated


by K n i g h t ( 1 9 6 9 ) ; C u r v e В d e r i v e d o b s e r v a t i o n s by using from s e m i - e m p i r i c a l f o r m u l a s g i v e n by Edlen in R e f . [12];
C u r v e С c a l c u l a t e d by S a f r o n o v a a n d I v a n o v a ( 1 9 6 9 ) .
112 EDLEN

FIG. 15. S u r v e y d i a g r a m of t h e m a i n c o n f i g u r a t i o n s i n C a I - l i k e s p e c t r a . S e r i e s l i m i t s a r e i n d i c a t e d by
dashed lines; from Ref.[11].

FIG. 16. L e v e l s of 3d^ in C a I - l i k e s p e c t r a . T h e ' S l e v e l , w h i c h falls h i g h a b o v e t h e rest of t h e c o n f i g u r a t i o n ,


has b e e n o m i t t e d ; f r o m R e f . [ 1 1 ] .
IAEA-SMR-12/4, 5 113

г-ptà 'P
i-p 3 i ' F

2s3tL 'D

L-грзр 'D

lS3p 'P
-Ь грзр 'P

FIG. 17. I s o e l e c t r o n i c c o m p a r i s o n of t h e t e r m s of 2 s 3 i a n d 2 p 3 i in Be I - l i k e s p e c t r a . Д Е - E - 2s3d 1 D o r


E - 2s3d 3 D; AL = 0 f o r 2 s 3 i and ÄL = 2p2p - 2s 2 S for 2 p 3 i ; f r o m R e f . [ l l ] .
114 EDLEN

(Z-S)"1
0.18 0.16 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.0

FIG. 18. G r a p h i e r e p r e s e n t a t i o n of t h e s p i n - o r b i t i n t e r v a l 2 s 2 2 p S ( 2 P 1 / 2 - 2 р з / г ' - T h e v a l u e s m a r k e d by c i r c l e s


a r e o b t a i n e d f r o m f o r b i d d e n t r a n s i t i o n s o b s e r v e d in t h e solar c o r o n a , t h o s e m a r k e d by crosses a r e f r o m
-
laboratory observations. T h e s i z e of t h e i n t e r v a l i n c r e a s e s f r o m 4 0 4 c m ' i n F I t o 30 0 4 5 c m " ' i n C a XII;
f r o m Ref. [ 1 4 ] .

g r o u n d - t e r m i n t e r v a l , 2 P i / 2 " 2 Р з / г in t h e F I s e q u e n c e s h o w n in F i g . 18.
H e r e the s c r e e n i n g p a r a m e t e r s is plotted against ( Z - s ) " 1 , producing a
straight line.
T h e i n t e r v a l s in t h e g r o u n d c o n f i g u r a t i o n s 2 s 2 2 p k (k = 1 - 5 ) and 3 s 2 3 p k
a r e of s p e c i a l a s t r o p h y s i c a l i n t e r e s t a s h o l d i n g t h e c l u e t o t h e " f o r b i d d e n "
l i n e s in t h e g a s e o u s n e b u l a e and the s o l a r c o r o n a . A c c o r d i n g l y , t h e i r
Z - d e p e n d e n c e h a s b e e n m u c h s t u d i e d . F i g u r e 19 s h o w s two of t h e
i n t e r v a l s of 2 s 2 2p 4 in t h e О I s e q u e n c e , X D 2 - 3 P X and 3 Р г - 3 P 2 , r e p r e s e n t e d
by s t r a i g h t l i n e s o b t a i n e d by u s i n g a s u i t a b l e t r a n s f o r m a t i o n .

3.3. W a v e n u m b e r s of t r a n s i t i o n s

T h e t r a n s i t i o n s s e p a r a t e w i t h i n c r e a s i n g Ç into two d i s t i n c t g r o u p s
c o r r e s p o n d i n g t o A n = 0 (wave n u m b e r b e i n g a l i n e a r f u n c t i o n of £) and
A n / 0 (wave n u m b e r b e i n g a q u a d r a t i c f u n c t i o n of f ) . T h i s i s i l l u s t r a t e d
by t h e d i a g r a m in F i g . 20 f o r t h e Na I s e q u e n c e .
It i s i n t e r e s t i n g t o n o t e t h a t t h e v a l u e s of t h e t r a n s i t i o n p r o b a b i l i t i e s
t e n d to z e r o with i n c r e a s i n g Ç f o r A n = 0 and t o n o n - z e r o h y d r o g e n i c v a l u e s
f o r An / 0.
IAEA-SMR-12/4, 5 115

у,/у
1.0 0.9 0.8 0.7 0.6 0.5 0.3 0.2 0.1 0

( 2 , - 3 . 2 5 у ' ( 2 - 3.25)

FIG. 19. G r a p h i c r e p r e s e n t a t i o n of i n t e r v a l s in t h e g r o u n d c o n f i g u r a t i o n s 2s 2 2p 4 in t h e О I i s o e l e c t r o n i c
sequence. T h e lines labelled a n d F2 r e p r e s e n t t h e i n t e r v a l s C P j - 3 Р г ) a n d № г - з р ^ , respectively. The
design of t h e d i a g r a m is e x p l a i n e d i n R e f . [ 1 5 ] ,

4. SURVEY O F E L E C T R O N CONFIGURATIONS AND T E R M SYSTEMS

4. 1. G r o u n d c o n f i g u r a t i o n s in t h e f i r s t half of t h e p e r i o d i c s y s t e m

The g r o u n d c o n f i g u r a t i o n s of s u c c e s s i v e s t a g e s of ionization a r e
r e s p o n s i b l e f o r the l o w - l y i n g t e r m s a s well a s f o r t h e s e r i e s l i m i t s , and
t h u s d e t e r m i n e the m a i n f e a t u r e s of t h e s y s t e m s of e n e r g y l e v e l s . T a b l e VIII
shows t h e s e ground c o n f i g u r a t i o n s o r d e r e d a c c o r d i n g to t h e t o t a l n u m b e r
of e l e c t r o n s N f o r the f i r s t half of t h e p e r i o d i c s y s t e m . C l o s e d s h e l l s
a r e o m i t t e d when p a s s i n g f r o m one p e r i o d to t h e next. In t h e l a s t r o w of
e a c h p e r i o d we have given only t h e f i r s t e l e m e n t of e a c h i s o e l e c t r o n i c
s e q u e n c e , the f i g u r e in p a r e n t h e s i s being t h e n u m b e r к of equivalent
electrons.
In p e r i o d s I to III the g r o u n d c o n f i g u r a t i o n s r e m a i n t h e s a m e t h r o u g h o u t
e a c h i s o e l e c t r o n i c s e q u e n c e . On t h e o t h e r hand, in p e r i o d IVa, t h e
c o m p o s i t i o n of the ground c o n f i g u r a t i o n s c h a n g e s with i n c r e a s i n g net c h a r g e
in t h a t t h e 4 s - o r b i t s , which a r e p r e s e n t in t h e beginning of a s e q u e n c e , a r e
r e p l a c e d by 3 d - o r b i t s a s i n d i c a t e d in T a b l e VIII. T h i s t r a n s f o r m a t i o n i s
116 EDLEN

a l w a y s c o m p l e t e d in t h e t h i r d m e m b e r of e a c h s e q u e n c e and f o r the l a t t e r
p a r t of t h e p e r i o d a l r e a d y in t h e second m e m b e r . The f o l l o w i n g two p e r i o d s ,
IVb and Va, a r e in all r e s p e c t s a n a l o g o u s to III and IVa. T h e conventional
n u m b e r i n g of the p e r i o d s is c l e a r l y not t h e m o s t r a t i o n a l one f o r o u r
p u r p o s e , which h a s l e d u s to i n t r o d u c e s u b d i v i s i o n s .

(a) T w o - to t e n - e l e c t r o n s y s t e m s

A view of t h e p r e s e n t s t a t e of a n a l y s i s of s y s t e m s with up to 18 e l e c t r o n s
i s given in T a b l e IX. By u n d e r l i n i n g a s p e c t r u m s y m b o l we h a v e i n d i c a t e d
t h a t t h e a n a l y s i s i s c o m p l e t e d a s f a r a s p r a c t i c a l l y p o s s i b l e with a v a i l a b l e
l i g h t s o u r c e s . S y m b o l s a r e given in p a r e n t h e s i s f o r v e r y i n c o m p l e t e
a n a l y s e s , and an a s t e r i s k s i g n i f i e s t h a t t h e s p e c t r u m is at p r e s e n t b e i n g
investigated.
IAEA-SMR-12/4, 5 117

T A B L E VIII. GROUND CONFIGURATIONS O F ATOMS AND IONS IN T H E


F I R S T H A L F O F T H E PERIODIC SYSTEM

Period N Configuration3 Spectrum

1 Is HI, H e l l , Lilll

2 Is? Hel, Lill, Belli

3 2s L i l , Bell, Bill
2
4 2s Bel, BII, CIII

5-10 2s 2 2 p k BC1). C(2), N(3), 0 ( 4 ) , F(5), Net6)

11 3s N a l , MglI, A1III

12 3s? M g l , A1II, S i l l l

13-18 3 s2 3 p k A l ( l ) , Si(2), P(3), S(4), C K 5 ) , A K 6 )

19 4s -»3d KI, C a l l , S c I I I

20 4s 2 -»3d2 C a l , S e n , T1III, . . .

21-28 4 s 2 3 d k ' " 2 -> 3 d k S c ( 3 ) , T i ( 4 ) , V(5), C r ( 6 ) , M n ( 7 ) , Fe(8), C o ( 9 ) , Ni(10)

29 4s C u l , ZnII, G a l i i

30 4s 2 Znl, Gall, Gelll


2 k
31-36 4s 4 p G a ( l ) , G e ( 2 ) , As(3), S e ( 4 ) , Br(5), Kr(6)

37 5s -» 4d Rbl, Srll, та,...

38 5s 2 -» 4d 2 Sri, YIt, Z r l l l
k
39-46 5s24dk"- 2 - , 4 d Y ( 3 ) , Zr(4), Nb(5), M o ( 6 ) , T c ( 7 ) , Ru(8),Rh(9), P d d O )

a
T h e g r o u n d s t a t e is a c t u a l l y p r o v i d e d by 4 s 3 d 5 in CrI, by 5 s 4 d k _ 1 in N b l , M o l , Rul, RhI, a n d by
4di» in Pd I.

The t w o - e l e c t r o n s y s t e m s of t h e He s e q u e n c e a r e of s p e c i a l i n t e r e s t
f r o m the t h e o r e t i c a l point of view. T h e y a r e t h e s i m p l e s t s y s t e m s f o r
which the S c h r ö d i n g e r e q u a t i o n cannot be e x a c t l y s o l v e d and a r e , t h e r e -
f o r e , e x t e n s i v e l y u s e d f o r t e s t i n g v a r i o u s a p p r o x i m a t i o n m e t h o d s . At t h e
s a m e t i m e t h e y a r e t h e m o s t c o m p l i c a t e d s y s t e m s f o r which t h e o r e t i c a l
c a l c u l a t i o n s of the e n e r g i e s can be c a r r i e d f a r enough to c o m p e t e in
a c c u r a c y with t h e m e a s u r e m e n t s [1]. F o r h i g h e r Z t h e c a l c u l a t i o n s a r e
a c t u a l l y a h e a d of t h e o b s e r v a t i o n s . T h i s is a c h a l l e n g e to the e x p e r i m e n t e r s .
It is in the f i r s t p l a c e a q u e s t i o n of finding a d e q u a t e light s o u r c e s f o r t h e s e
hard-to-excite spectra.
T h e l o w - l y i n g c o n f i g u r a t i o n s in t h e eight s e q u e n c e s of g r o u p II c o n s i s t
of 2s and 2p e l e c t r o n s only. The t y p i c a l Z - d e p e n d e n c e of t h e r e l a t i v e
p o s i t i o n s of c o n f i g u r a t i o n s i s d e m o n s t r a t e d in F i g . 21 by t h e t e r m d i a g r a m s
f o r t h e i s o e l e c t r o n i c s p e c t r a С И, О IV and Na VII. It shows how t h e
c o n f i g u r a t i o n s 2 s 2 p 2 and 2p 3 m o v e down t h r o u g h t h e d i a g r a m and e v e n t u a l l y
f o r m with 2 s 2 2 p a w e l l s e p a r a t e d l o w - l y i n g g r o u p . This a s y m p t o t i c
a r r a n g e m e n t is r e a c h e d a l r e a d y in О IV. The t e r m s t r u c t u r e of t h e s e
118 EDLEN

T A B L E IX. S T A T E O F ANALYSIS O F SYSTEMS WITH 2 T O


18 E L E C T R O N S

Is* He I Li II Belli* (BIV) СV (N VI) .


2s Lil Bell Bill СIV NV 0 VI ,
2s2 Bel* BII* CIII NIV OV F VI *
2s2 2p В I* СП NIII* OIV F V* NeVI>;:
2
2s 2p2 CI Nil Olli* FIV * Ne V* Na VI
2s22p3 N1 Oil* Fill Ne IV* Na V Mg VI
2s2 2p4 01 F II Nelil* NaIV Mg V AlVI ,
2s2 2ps FI Nell Na III* Mg IV Al V Si VI ,
2
2s 2p6 Ne I Na II Mg III Al IV* Si V PVI .
3s Na I Mg II A1III Si IV P V* S VI
2
3s Míl A1H* Si III PIV* (SV) (Cl VI) ,
3s2 3p All Si II Pill* S IV (CIV) (Ar VI) .
3s2 3p2 Sil PII S III Cl IV (Ar V) (KVI) .
3s2 3p3 PI Sil* C1III Ar IV КV Ca VI ,
3s2 3p" SI* C1II* Ar III* К IV Ca V (Sc VI) ,
3 s2 3p5 Cli ArH К III Ca IV* (Sc V)* Ti VI .
2
3s Зрб Arl KII* Ca III Sc IV* Ti V* (v ví):

Underlined: Analysis essentially complete.


In parentheses: Analysis fragmentary.
* Work in progress.

kK
С И OIV NaVII
2s2p
2s 2p
2p
2s2p
2s1

3p
I—3s

3d В
3p 2p

В
2p>
2p3
2
2s2p
2s2p! 2s2 2p
40 2s2pz 2s'2p

• 2s'2p
50

FIG.21. S c h e m a t i c d i a g r a m s of t h e i s o e l e c t r o n i c t e r m s y s t e m s of С II, О IV and Na VII s h o w i n g t h e t r e n d


towards a h y d r o g e n i c a r r a n g e m e n t of c o n f i g u r a t i o n s w i t h i n c r e a s i n g i o n i z a t i o n .
kK
100

90

80
2р'
70

60

50 2s2p6 >
S
2 s 2p 5 .2S

J
40 P
2s2p'
3
Р
30 3
D

20
2s2p

l
10 P
2
D
2s 2s 2р 2s2 2р3 2s22p' 2s22p5
2
P -

Lil... NeVIII BeI...NaVIII BI...MgVIII CI...AIVUI NI...SÍVIII OI...PVIII FI...SVI1I


0 0.Í0 0.91 1.34 1.77 2.20 2.63

FIG.22. Observed term values of all configurations 2s m 2p 1 < 1 divided by (£ + a ) . where С = 1 - 8 and
a = 0 . 4 8 ( m - 1) +0.43k, m and k referring to the ground configurations. The first ionization l i m i t is indicated
by a cross.
120 EDLEN

FIG.23. T h e d o u b l e t s y s t e m of F 111. W a v e l e n g t h s of t r a n s i t i o n s g i v e n i n A ( a f t e r H , P a l e n i u s , Phys.


S c r i p t a 1 (1970) 115).
IAEA-SMR-12/4, 5 121

FIG.24, T h e t e r m s y s t e m of Mg II ( a f t e r P. Risberg, A r k . Fys. 9 (1955) 4 8 3 ) .

l o w - l y i n g c o n f i g u r a t i o n s g i v e s t h e c h a r a c t e r to t h e s p e c t r a of g r o u p II.
A s u r v e y pf t h e whole s e t i s given in F i g . 22, w h e r e t h e e n e r g y s c a l e h a s
b e e n n o r m a l i z e d by r e m o v i n g by a l i n e a r Z - d e p e n d e n c e .
The i n t e r v a l s within t h e g r o u n d c o n f i g u r a t i o n s a r e of p a r t i c u l a r
astrophysical significance. The e l e c t r o s t a t i c t e r m intervals appear as
t h e " f o r b i d d e n l i n e s " in t h e g a s e o u s nebulae, and t h e s p i n - o r b i t i n t e r v a l s ,
which i n c r e a s e with the f o u r t h p o w e r of the e f f e c t i v e c h a r g e eventually
r e a c h a s i z e s u f f i c i e n t to m a k e t h e m o b s e r v a b l e a s f o r b i d d e n l i n e s in t h e
solar corona.
The s p e c t r a in p e r i o d II a r e r e l a t i v e l y s i m p l e . The m a x i m u m
c o m p l e x i t y , o c c u r r i n g a r o u n d the m i d d l e of the p - s h e l l , is well i l l u s t r a t e d
by t h e t e r m d i a g r a m of F III shown in F i g . 23. It shows m a n y R y d b e r g
s e r i e s going to d i f f e r e n t l i m i t s , and t e r m s of h y d r o g e n i c o r b i t s up to 6h,
which p e r m i t an a c c u r a t e d e t e r m i n a t i o n of the s e r i e s l i m i t s .
FIG.25. T h e t e r m system of Si III ( a f t e r Y . Toresson, A r k . Fys. 18 (1960) 389).
IAEA-SMR-12/4, 5 123

(b) E l e v e n - to e i g h t e e n - e l e c t r o n s y s t e m s

T h e s t a t e of a n a l y s i s , in t h e t h i r d p e r i o d , IS! = 11 - 18, i s l e s s c o m p l e t e
t h a n in t h e p r e v i o u s one ( s e e T a b l e IX). T h e ground c o n f i g u r a t i o n s c o n s i s t
of 3s and 3p e l e c t r o n s only, and a r e c o m p l e t e l y a n a l o g o u s to t h o s e in
p e r i o d II. H o w e v e r , t h e 3d o r b i t h a s the s a m e p r i n c i p a l q u a n t u m n u m b e r
and m a y , t h e r e f o r e , t a k e p a r t in t h e f o r m a t i o n of t h e a s y m p t o t i c a l l y deep
c o n f i g u r a t i o n s . T h i s i n t r o d u c e s a s i g n i f i c a n t c o m p l i c a t i o n a s we s h a l l s e e .
The s o d i u m - l i k e o n e - e l e c t r o n s p e c t r u m of Mg II is a good e x a m p l e of
a c o m p l e t e a n a l y s i s . The d i a g r a m in Fig. 24 s h o w s how f a r t h e o b s e r v a t i o n s
go, but R i t z f o r m u l a s and t h e p o l a r i z a t i o n f o r m u l a d e r i v e d f r o m t h e o b s e r v e d
d a t a , t o g e t h e r p e r m i t an a c c u r a t e and u n l i m i t e d e x t r a p o l a t i o n of t h e l e v e l
system.
The addition of j u s t one m o r e e l e c t r o n i m m e d i a t e l y l e a d s to a c o n s i d e r -
able c o m p l i c a t i o n a s i s s e e n f r o m F i g . 25 which r e p r e s e n t s t h e t e r m s y s t e m
of Si III. The s i n g l e t and the t r i p l e t s y s t e m each c o n s i s t s of two s y s t e m s ,

FIG.26. O b s e r v e d t e r m s of t h e ( 3 , 3 ) c o n f i g u r a t i o n s in t h e M g I i s o e l e c t r o n i c s e q u e n c e . T h e first i o n i z a t i o n
l i m i t is i n d i c a t e d by a cross.
124 EDLEN

built on t h e l i m i t s 3 s 2 S and 3 p ž P , r e s p e c t i v e l y . H i g h e r up in t h e i s o e l e c -
t r o n i c s e q u e n c e one will have to c o n s i d e r the p o s s i b l e a p p e a r a n c e of a t h i r d
s y s t e m , built on 3d 2 D.
F i g u r e 26 is a n o r m a l i z e d i s o - e l e c t r o n i c d i s p l a y of t h e t e r m s a r i s i n g
f r o m the c o n f i g u r a t i o n s 3 s 2 , 3s3p, 3s3d, 3p 2 and 3p3d. The c o n f i g u r a t i o n s
3s3d and 3p2 o v e r l a p and have the s a m e p a r i t y , which r e s u l t s in a c o m p l e t e
c o n f i g u r a t i o n m i x i n g f o r t h e two J D l e v e l s . The o b s e r v a t i o n s f o r 3p3d a r e
i n c o m p l e t e , and the l a s t (3, 3 ) - c o n f i g u r a t i o n , 3 d 2 , h a s not yet been o b s e r v e d
in any of t h e s e s p e c t r a .
The a n a l o g o u s d i a g r a m f o r t h e t h r e e - e l e c t r o n s p e c t r a of t h e Al s e q u e n c e
i s shown in F i g . 27. The c o n f i g u r a t i o n s 3s3p 2 and 3 s 2 3d o v e r l a p and i n t e r a c t
s t r o n g l y . This is a l s o t h e c a s e with 3p 3 and 3s3p3d f o r which, h o w e v e r ,
the o b s e r v a t i o n s a r e v e r y i n c o m p l e t e . O t h e r c o n c e i v a b l e c o n f i g u r a t i o n s
with all e l e c t r o n s having n= 3 a r e 3 s 3 d 2 , 3p 2 3d, 3p3d 2 and 3d 3 . T h u s we
get a l t o g e t h e r 9 d i f f e r e n t c o n f i g u r a t i o n s of t h i s kind, which l e a d s to an
a s y m p t o t i c s t r u c t u r e f o r high Ç which will be quite c o m p l i c a t e d . The
h i g h e r o n e s of t h e s e c o n f i g u r a t i o n s will n e v e r be p r o m i n e n t in t h e s p e c t r u m ,

1 2 3 4 5 6 7 8 9 10 f

AI Si P S ci Ar К Ca Sc тГ
I II III IV V VI VII VIII IX X
FIG.27. O b s e r v e d t e r m s of c o n f i g u r a t i o n s w i t h n - 3 for a l l t h r e e e l e c t r o n s i n t h e AI I s e q u e n c e . E 0 is t h e
c e n t r e of g r a v i t y of 3s2 3 p 2 p ( a f t e r Ekberg a n d Svensson, Phys. S c r i p t a 2 (1970) 2 8 3 ) .
IAEA-SMR-12/4, 5 125

but t h e y m i g h t be e x p e c t e d to p r o d u c e a d e n s e b a c k g r o u n d of faint l i n e s in
the r e g i o n of t h e 3 s - 3 p and 3p-3d t r a n s i t i o n s . T h e c o m p l e x i t y i n c r e a s e s
a s we go up t h r o u g h t h e p e r i o d . T h e s i t u a t i o n in t h e t h i r d p e r i o d i s thus
in s h a r p c o n t r a s t to t h e p r e v i o u s p e r i o d , w h e r e t h e r e is a m a x i m u m of
t h r e e d e e p c o n f i g u r a t i o n s , e a c h one with a r e l a t i v e l y s i m p l e s t r u c t u r e
(cf. F i g . 22).

(c) N = 1 9 - 2 8 ; the c o n f i g u r a t i o n s 3 d k 4 s m

We now p a s s on to t h e next p e r i o d w h e r e 3 d - e l e c t r o n s f o r m t h e ground


c o n f i g u r a t i o n s and give t h e c h a r a c t e r to t h e s p e c t r a . T h e s u r v e y in
T a b l e X of t h e s t a t e of a n a l y s i s shows that p r e v i o u s l y empty p l a c e s f o r t h e
i m p o r t a n t t h i r d and f o u r t h s p e c t r a a r e beginning to be filled, t h a n k s to
r e c e n t w o r k e s p e c i a l l y at the Z e e m a n L a b o r a t o r y and the O p t i c a l I n s t i t u t e
in M a d r i d . The l a b e l " e s s e n t i a l l y c o m p l e t e " h a s h e r e a m e a n i n g t h a t i s
s o m e w h a t d i f f e r e n t f r o m t h a t in t h e p r e v i o u s p e r i o d s . E x c e p t f o r t h e f i r s t
few and t h e l a s t s e q u e n c e in t h i s p e r i o d , it is p r a c t i c a l l y i m p o s s i b l e to
m a k e a c o m p l e t e a n a l y s i s of m o r e than s o m e of t h e l o w e s t c o n f i g u r a t i o n s .
In t h e c a s e of high ionization s t a g e s t h e c o n f i g u r a t i o n s t h a t can be o b s e r v e d
in any d e t a i l a r e likely to be l i m i t e d to 3d k , 3d k _ 1 4 s and 3d k " 1 4p. T h e
o b s e r v a b l e s p e c t r u m will then c o n s i s t of two g r o u p s , one s h o r t - w a v e g r o u p
a r i s i n g f r o m ( 3 d - 4 p ) - t r a n s i t i o n s and one l o n g - w a v e group of ( 4 s - 4 p ) -
transitions.
As a p p e a r s f r o m F i g . 28 the m a x i m u m d e g r e e of c o m p l e x i t y i s r e p r e -
s e n t e d in s o m e of the i r o n s p e c t r a . The e x p e r i m e n t a l s i t u a t i o n m a y be
i l l u s t r a t e d by the f a c t t h a t in t h e g r o u p of ( 3 d 5 - 3 d 4 4 p ) - t r a n s i t i o n s in F e IV
t h e r e have b e e n m e a s u r e d about 500 lines- o v e r the r a n g e 500 Â to 700 Â.

T A B L E X. S T A T E O F ANALYSIS O F SYSTEMS WITH 19 TO


28 E L E C T R O N S

4s 3d KI Call S c III T i IV V V*

4s 2 -» 3d 2 Ca I Sell* T i III VIV Cr V *


2 3
4s 3d -» 3 d Sei Till VIII Cr I V * MnV

4s 2 3 d 2 — 3 d 4 Til VII * C r III МП IV Fe V

4s 2 3 d 3 - 3d5 VI C r II Mnlll Fe I V * (Co V)

4s 2 3 ď » - 3d s Cr I MnII Fe III (Co I V ) * (Ni V)

4s 2 3d 5 -* 3d' Mn I Fe II Colli Ni I V * (Си V)

4s 2 3d 6 -» 3d» Fe I Co I I * N i III C u IV (ZnV)


2 9
4s 3 d ' - 3d Col Ni II C u III * ZnIV (Ga V)

4s 2 3 d 8 -> 3 d 1 0 Nil Cull Znlll GaIV Ge V

Underlined: Analysis essentially c o m p l e t e .


In p a r e n t h e s e s : Analysis f r a g m e n t a r y or non-existent.
* Work i n progress.
126 EDLEN

40 -

к i= 1 2 3 4 5 6 7 8 9
n = 2 9 19 34 37 34 19 9 2

í VIII. VII VI V IV 111 II I 3dk

Fe < VII VI V IV III II I


(III) II I 3dk"2

FIG. 2 8 . T h e n u m b e r of l e v e l s a r i s i n g f r o m 3 d k for d i f f e r e n t v a l u e s of k .

In s o m e r e g i o n s t h e r e a r e m o r e than t e n o b s e r v e d l i n e s p e r a n g s t r o m unit,
and an i n s t r u m e n t with a l a r g e r d i s p e r s i o n ( h e r e it was 4 i / m m ) would
give s t i l l m o r e l i n e s , s i n c e m a n y of t h e o b s e r v e d o n e s r e p r e s e n t two o r
more unresolved transitions.
With i n c r e a s i n g e f f e c t i v e c h a r g e (f) the binding e n e r g y of 3d i n c r e a s e s
r e l a t i v e to t h a t of 4 s b e c a u s e of t h e d i f f e r e n c e in p r i n c i p a l quantum n u m b e r .
The c o n s e q u e n t c h a n g e s in t h e r e l a t i v e p o s i t i o n s of c o n f i g u r a t i o n s a r e d i s -
played in F i g . 29 w h e r e t h e l o w e s t t e r m in e a c h of the c o n f i g u r a t i o n s 3d k + 1
and 3 d k _ 1 4 s 2 h a s b e e n p l o t t e d a s a function of к and Ç by t a k i n g a s r e f e r e n c e
l e v e l t h e c e n t r e of g r a v i t y of the two t e r m s of 3 d k 4 s t h a t a r i s e f r o m the
lowest t e r m of 3 d k . T h e t e r m v a l u e s h a v e b e e n divided by (Ç + а), w h e r e
a= 0 . 6 + 0 . 1 k, in o r d e r to get a l i n e a r d e p e n d e n c e on f (or Z). The d a s h e d
l i n e s c o n n e c t c o r r e s p o n d i n g points f o r s u c c e s s i v e v a l u e s of к (or Z) at
c o n s t a n t f . They i l l u s t r a t e the r e l a t i o n s h i p s d i s c u s s e d in 1954 by C a t a l a n ,
R o h r l i c h and S h e n s t o n e . It is s t r i k i n g how t h e s t r u c t u r e in t h e f i r s t half
of the p e r i o d r e p e a t s i t s e l f in t h e s e c o n d half.
The d i a g r a m in F i g . 2 9 shows that in the n e u t r a l a t o m s 3 d k _ 1 4 s 2 i s in
g e n e r a l t h e l o w e s t c o n f i g u r a t i o n and 3d k + 1 i s f a i r l y high, while in the s e c o n d
s p e c t r a t h i s o r d e r is r e v e r s e d and 3 d k 4 s c o m p e t e s with 3d k + 1 in p r o v i d i n g
t h e ground s t a t e . F r o m the t h i r d s p e c t r u m on 3d k + 1 is d e f i n i t e l y the l o w e s t
c o n f i g u r a t i o n , while 3 d k _ 1 4 s 2 r u n s up high in t h e t e r m s y s t e m and e v e n -
tually d i s a p p e a r s .
A m o r e d e t a i l e d p i c t u r e of t h e t e r m s t r u c t u r e i s obtained by expanding
and c o m p l e t i n g t h e d i a g r a m s of F i g . 29 f o r individual i s o - e l e c t r o n i c
s e q u e n c e s . T h i s i s shown by t h e d i a g r a m s in F i g s 30 and 31 of t h e C a I -
and Ni I - l i k e s e q u e n c e s , which r e p r e s e n t t h e beginning and t h e end of t h e
p e r i o d . F o r f u r t h e r d e t a i l s s e e Ref. [4].
I A E A - S M R - 1 2 / 4 ,5 127

Call Selil... Sei Till VIII... VI Crll Mn II]... Mn ! Fell Colli... Col NiliCuIII... Cul Znll...

FIG. 2 9 . C o n d e n s e d v i e w of che r e l a t i v e p o s i t i o n s of t h e c o n f i g u r a t i o n s 3 d k 4 s m o b t a i n e d by p l o t t i n g
(E - E 0 )/(C + a ) , w h e r e E is t h e l o w e s t t e r m of 3 d k + 1 or ed^ - ! 4 s 2 , E 0 is t h e c e n t r e of g r a v i t y of t h e two t e r m s
of 3 d k 4 s b u i l t o n t h e l o w e s t t e r m of 3 d k , a n d a = 0 . 6 + 0 . 1 k.

T h e g r o u p s IVb and Va a r e quite analogous to t h e p r e v i o u s two g r o u p s


as we can s e e f r o m T a b l e VIII. E x c e p t f o r a c o n s i d e r a b l y i n c r e a s e d s p i n -
o r b i t s p l i t t i n g , the s p e c t r a have a r e m a r k a b l y s i m i l a r s t r u c t u r e . We s h a l l
l e a v e it at t h a t and p a s s on to a v e r y b r i e f s u r v e y of the s e c o n d half of t h e
periodic system.

4. 2. Ground c o n f i g u r a t i o n s of s y s t e m s with N ě 47

T h e s e c o n d half of t h e p e r i o d i c s y s t e m h o l d s p o s s i b i l i t i e s f o r a c o n -
s i d e r a b l e r e a r r a n g e m e n t of o r b i t s in the l o w - l y i n g c o n f i g u r a t i o n s .
A c c o r d i n g to a w e l l - k n o w n e m p r i c i a l r u l e , t h e l o w e s t o r b i t f o r an o u t e r
e l e c t r o n in a n e u t r a l a t o m is t h e one f o r which (a) the s u m of p r i n c i p a l
and o r b i t a l quantum n u m b e r s , n + Í , h a s t h e l o w e s t value and which (b) f o r e q u a l
v a l u e s of (n + i ) h a s the l o w e s t n. T h i s would l e a d to t h e following o r d e r
of o r b i t s in n e u t r a l a t o m s : I s , 2s, 2p, 3s, 3p, 4 s , 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, . . .
which so f a r a g r e e s with o b s e r v a t i o n s , except t h a t one 5 d - e l e c t r o n is bound
b e f o r e the f i r s t 4 f - e l e c t r o n . With i n c r e a s i n g s t a g e of ionization, h o w e v e r ,
it f o l l o w s f r o m e l e m e n t a r y a r g u m e n t s that t h e s y s t e m will a p p r o a c h t h e
h y d r o g e n - l i k e c a s e in which t h e binding e n e r g y is d e t e r m i n e d by the v a l u e
of n and f o r e q u a l n by Í , T h u s , a f t e r the 4 d - s h e l l h a s been filled at
N = 46, then 4f i s t h e o r b i t t h a t f o r high enough e f f e c t i v e c h a r g e Ç should
b e c o m e t h e m o s t tightly bound. H o w e v e r , b e f o r e that o c c u r s , the l o w e s t
p o s i t i o n will be occupied by a v a r i e t y of o t h e r o r b i t s , n a m e l y 5 s , 5p, 6s
and 5d, l e a d i n g to a s e r i e s of d r a s t i c g r o u n d - c o n f i g u r a t i o n t r a n s f o r m a t i o n s
as one goes up t h r o u g h t h e s e q u e n c e s (see T a b l e XI).
While 5s can be e x p e c t e d to hold i t s p o s i t i o n quite f a r up, t h e o r b i t 5p
will r e l a t i v e l y soon be m a t c h e d by 4f. At t h a t s t a g e a s m a l l i n c r e a s e in
128 EDLEN

FIG.30. T h e c o n f i g u r a t i o n s 3 d 2 , 3d4s and 4s z in t h e Ca I i s o e l e c t r o n i c s e q u e n c e .

e f f e c t i v e c h a r g e Ç will be s u f f i c i e n t f o r having t h e 5 p - o r b i t s all at once


r e p l a c e d by 4f [6]. In t h e Xe s e q u e n c e , f o r i n s t a n c e , t h e c o l l a p s e of the
5p s h e l l will c a u s e the s i n g l e ground l e v e l 5pS to be r e p l a c e d by t h e
h u n d r e d s of l e v e l s of 4 f 6 . T h i s d r a m a t i c event h a s b e e n o b s e r v e d by R e a d e r
and E k b e r g (unpublished). T h e y found t h e five r e s o n a n c e t r a n s i t i o n s in t h e
X e I - l i k e s p e c t r a a s o u t s t a n d i n g and e a s i l y i d e n t i f i e d l i n e s up to Ce V.
In P r VI s o m e of t h e l i n e s could still be r e c o g n i z e d , w h e r e a s t h e s p e c t r u m
of Nd had the a p p e a r a n c e of a continuum f o r m e d by i n n u m e r a b l e faint l i n e s .
A t e r m a n a l y s i s of t h i s s p e c t r u m is, of c o u r s e , i m p o s s i b l e . T h u s , f r o m
t h e p r a c t i c a l point of view, t h e Xe s e q u e n c e t e r m i n a t e s with P r VI.
In t h e following s e q u e n c e s (group Via in T a b l e XI) we find s i m i l a r
t r a n s f o r m a t i o n s with i n c r e a s i n g c o m p l e x i t y , until f o r N = 68 t h e a s y m p t o t i c
ground c o n f i g u r a t i o n h a s again r e a c h e d t h e s i m p l e c a s e of f i l l e d s h e l l s .
lAEA-SMR-12/4, 5 129

FIG.31. T h e configurations 3 d " , 3d 9 4s a n d 3 d 8 4 s 2 in t h e Ni I i s o e l e c t r o n i c s e q u e n c e .


130 EDLEN

T A B L E XI. GROUND CONFIGURATIONS FOR ATOMS AND IONS IN T H E


SECOND H A L F O F T H E PERIODIC SYSTEM
a
Period N Configuration Spectrum

С 47 5s (-> 4 f ) A g i , C d l l , InlII

Vb -j 48 5s 2 (-> 4 P ) Cdl, Inll, Snin,...


2 k 2 k k+
L 49-54 5s 5 p - > 5s 4 f (-> 4 f 2) I n ( l ) , Sn(2), Sb(3), T e ( 4 ) , 1(5), Xe(6)

55 5s 2 5 p 6 6 s - » 5s z 5рБ 5d-> 5 s 2 5 p « 4 f - > 5 s 2 4 f ( - 4 f 9 ) Csl,...


2 6 2 z 6 2 2 8 10
56 5s 5p 6s . . . -- 5s 5p 4 f 5s 4f (-> 4 f ) Bal,...

57 5s 2 5p 6 6s 2 Sd ->• . . . - 5s 2 5p6 4f 3-> 5 s 2 4 f s ( - 4 f " ) Lai, . . .

' Via
60 5s 2 5p 6 6s 2 4f4-> . . . - > 5s 2 5 p 6 4 f 6 - * 5 s 2 4 f l 2 ( ^ 4 f i 4 ) Ndl

62 5s 2 5 p 6 6 s 2 4 f 6 - » . . .-> 5 s 2 5 p 6 4 f s - » 5 s 2 4 f " SmI,...

68 5s 2 5p 6 6 s 2 4 f 1 2 - » . . . 5s 2 5p 6 4 f 1 4 Erl, . . .

Г 69 6s z 4 f i 3 - > . . .-> 4 f « 5 d T m i , У b u , LuIII

VIb i 70 6s z 4f 14 -> . . .-> 4Í 1 4 5d 2 Y b l , Lull, H f l l I , .. .

L 71-78 6s 2 5 d k - 2 -*• 5 d k Lu(3), Н Й 4 ) , T a ( 5 ) , W(6), Re(7), Os(8),


Ir(9), Pt(10)

Г 79 6s ( - 5f) A u l , HglI, T1III

Vic j 80 6s 2
(-» 5 f ) 2
H g l , T l i l , РЫН

L 81-86 6s 2 6 p k - 6s 2 5 f ! < ( - 5 f k + 2
) T l ( l ) , Pb(2), Bi(3), Po(4), A t ( 5 ) , Rn(6)

VII 87... similar to 5 5 . . .

a
In t h e first s p e c t r a of t h e l a n t h a n i d e s t h e ground s t a t e is p r o v i d e d by 6s 2 5d4f k for
Z(= N) = 5 7 , 58, 6 4 a n d by 6 s 2 4 f k + 1 in a l l o t h e r c a s e s [ 2 ] .
\

In t h e g r o u p c a l l e d VIb in T a b l e XI, c o m p r i s i n g the 10 s e q u e n c e s N = 69 - 7 8,


the g r o u n d c o n f i g u r a t i o n s a r e quite a n a l o g o u s to t h o s e in t h e p r e v i o u s two
g r o u p s of t r a n s i t i o n e l e m e n t s , except f o r t h e m o d i f i c a t i o n c a u s e d by one hole
in t h e 4 f - s h e l l in t h e v e r y beginning of s e q u e n c e 69. We note, f i n a l l y , t h a t
the e l e c t r o n i c s y s t e m s s t a r t i n g f r o m N = 79 will be c l o s e l y s i m i l a r to t h o s e
s t a r t i n g f r o m N = 47.
This s k e t c h of t h e e l e c t r o n i c s t r u c t u r e of t h e i s o e l e c t r o n i c s e q u e n c e s
t h r o u g h t h e P e r i o d i c T a b l e h a s been m a i n l y c o n c e r n e d with t h e ground
c o n f i g u r a t i o n s , which to a c o n s i d e r a b l e extent d e t e r m i n e t h e g e n e r a l
c h a r a c t e r of a s p e c t r u m . H o w e v e r , a d d i t i o n a l c o m p l e x i t i e s a r e i n t r o d u c e d
in t h e t e r m s y s t e m s by t h e e x c i t a t i o n of i n n e r s h e l l s , a s f o r i n s t a n c e
e x c i t a t i o n of 3 s 2 3 p 6 3 d k to 3 s 2 3 p 5 3 d k + 1 , f o r which the p o s s i b i l i t i e s tend to
i n c r e a s e with i n c r e a s i n g N.
IAEA-SMR-12/4, 5 131

4. 3. B r i e f s u r v e y of l i t e r a t u r e on t e r m a n a l y s i s

The r e s u l t s of the g r e a t n u m b e r of a n a l y s e s m a d e s i n c e the p u b l i c a t i o n


of C h a r l o t t e E. M o o r e ' s " A t o m i c E n e r g y L e v e l s " [8] m u s t f o r the m o s t p a r t
be r e t r i e v e d f r o m o r i g i n a l p a p e r s s c a t t e r e d in v a r i o u s p u b l i c a t i o n s . New
v e r s i o n s of t h e A E L T a b l e s a r e a s y e t a v a i l a b l e only f o r С I-VI, N IV-VII
and Si I - I V [10]. As a r e m e d y to t h i s d i f f i c u l t y c o m p r e h e n s i v e c o l l e c t i o n s
of r e f e r e n c e s to a n a l y s e s of a t o m i c s p e c t r a h a v e b e e n p r o d u c e d at t h e
US N a t i o n a l B u r e a u of S t a n d a r d s , one c o v e r i n g the l i t e r a t u r e up to 1968-69
[9] and a s e c o n d one continuing t h r o u g h J u n e 1971 [7]. A f u r t h e r c o n t r i -
bution to t h i s end m a y be found in Ref. [5] which g i v e s a l i s t of p a p e r s that
s u p p l e m e n t the i n f o r m a t i o n contained in A E L . In c o n t r a s t to t h e b i b l i o -
g r a p h i e s m e n t i o n e d above, t h i s c o m p i l a t i o n is c r i t i c a l and s e l e c t i v e in the
s e n s e that in p r i n c i p l e only t h o s e p a p e r s a r e l i s t e d which we find n e c e s s a r y
to c o n s u l t in o r d e r to obtain all i n f o r m a t i o n now a v a i l a b l e on t h e e n e r g y
l e v e l s y s t e m s of t h e s p e c t r a c o n c e r n e d . The c o m p i l a t i o n i s l i m i t e d to
Z s 28, and a s o m e w h a t a r b i t r a r y l i m i t h a s been s e t to t h e d e g r e e of
ionization. It i s c a r r i e d t h r o u g h N o v e m b e r 1972 and r e p r e s e n t s an
e n l a r g e d v e r s i o n of an e a r l i e r a t t e m p t [3] to p r o v i d e a convenient key to
the l i t e r a t u r e .

REFERENCES

[1] ACCAD, Y . , PEKERIS, C . L . , SCHIFF, В . . Phys. Rev. A 4 (1971) 516.


[2] BREWER, L . , J. O p t . Soc. A m . 61 (1971) 1101.
[3] EDLEN, В . , N u c l . Instrum. Methods, 90 (1970) 1.
[4] EDLEN, В . , O p t i c a Рига y A p l i c a d a 5 (1972) 101.
[5] EDLEN, В . , Physica Scripta 7 (1973) 93.
[6] GRIFFIN, D . C . , ANDREW, K . C . , COWAN, R . D . , Phys. Rev. П 7 (1969) 62.
[7] HAGAN, L . , MARTIN, W . C . , Bibliography o n A t o m i c Energy Levels and Spectra, N a t . Bur. S t a n d .
( U . S . ) , S p e c i a l P u b l . 363 (1972).
[8] MOORE, C . E . , A t o m i c Energy Levels, N a t . Bur. Stand. ( U . S . ) Circular 467, V o l . 1 (1949), V o l . 2 (1952),
V o l . 3 (1958).
[9] MOORE, C . E . , Bibliography of t h e Analyses of O p t i c a l A t o m i c S p e c t r a , N a t . Bur. S t a n d . ( U . S . ) ,
S p e c i a l P u b l . 306, S e c t . 1 (1968), S e c t . 2 , 3 , 4 (1969).
[10] MOQRE, C . E . , S e l e c t e d T a b l e s of A t o m i c S p e c t r a , N a t . S t a n d . Ref. Data Series. Nat. Bur. S t a n d . ( U . S . ) ,
3, Sect 1 - 4 ( 1 9 6 5 - 1 9 7 1 ) .
[11] EDLEN, В . , " A t o m i c s p e c t r a " , H a n d b . der Physik 27, Springer, Berlin (1964),
[12] EDLEN, В . , " I o n i z a t i o n p o t e n t i a l s of a t o m s and ions c o n t a i n i n g o n e to 10 e l e c t r o n s " ,
Modern Physics (BRITTIN, W . E . , ODABASI, H . , Eds), Colorado Univ. Press, Boulder (1971).
[13] EDLEN, В . , Phys. Rev. Lett. 28 (1972) 943.
[14] EDLEN, В . , Solar Physics 9 (1969) 4 3 9 .
[15] EDLEN, В . , Solar Physics 24 (1972) 356.
[16] SVENSSON, L . A . , Solar Physics 18 (1971) 232.
IAEA-SMR-12/12

LINE WIDTH AND LINE BROADENING

W.R. HINDMARSHT
Department of Atomic Physics,
University of Newcastle-upon-Tyne,
United Kingdom

Abstract

LINE WIDTH A N D LINE BROADENING.


Collision broadening, classical theory; quasi-static approximation; q u a n t u m t h e o r y of c o l l i s i o n
broadening; i n v e r s e p o w e r and L e n n a r d - J o n e s p o t e n t i a l s , i m p a c t a p p r o x i m a t i o n , quasi-static approximation,
g e n e r a l t h e o r y , r e s u l t s of m e a s u r e m e n t s , c o m p a r i s o n b e t w e e n t h e o r y and e x p e r i m e n t ; b r o a d e n i n g by c h a r g e d
p a r t i c l e s , q u a d r a t i c S t a r k e f f e c t , i n f l u e n c e of i n e l a s t i c collisions; b r o a d e n i n g t h r o u g h l i n e a r Stark e f f e c t .

1. CLASSICAL THEORY O F COLLISION BROADENING

1.1. General formulation

T h e c l a s s i c a l m o d e l t r e a t s an a t o m i c r a d i a t o r a s an e l a s t i c a l l y bound
o s c i l l a t i n g e l e c t r o n . T h e p r o b l e m of c o l l i s i o n b r o a d e n i n g i s to c a l c u l a t e
the s p e c t r u m of s u c h an o s c i l l a t o r w h e n it is d i s t u r b e d by c o l l i s i o n s with
the o t h e r a t o m s in i t s e n v i r o n m e n t . We a s s u m e t h a t the c o l l i s i o n s do not
change t h e a m p l i t u d e of the o s c i l l a t o r , but only t h e p h a s e . T h i s i s e q u i v a l e n t
to a s s u m i n g t h a t t h e t r a n s i t i o n p r o b a b i l i t y i s unchanged by the c o l l i s i o n .
The d i s p l a c e m e n t of the o s c i l l a t o r a s a f u n c t i o n of t i m e i s given by

t > 0 (1)
о

w h e r e u ' ( t ' ) i s t h e i n s t a n t a n e o u s a n g u l a r f r e q u e n c y of the o s c i l l a t i o n at


t i m e ť and Re s t a n d s f o r " r e a l p a r t o f " . T h e u n d i s t u r b e d f r e q u e n c y will
be r e p r e s e n t e d by u 0 , and the o s c i l l a t i o n b e g i n s a t t = 0. The e f f e c t of
n a t u r a l d a m p i n g is i g n o r e d . It i s , in f a c t , o f t e n n e g l i g i b l e c o m p a r e d with
c o l l i s i o n a l e f f e c t s , but in t h e i m p a c t a p p r o x i m a t i o n t h e e f f e c t s of n a t u r a l and
c o l l i s i o n a l d a m p i n g a r e a d d i t i v e . T h e i n t e n s i t y p r o f i l e I(u) of the light
e m i t t e d by t h e o s c i l l a t o r i s t h e n given by

(2)

^ I t is w i t h r e g r e t t h a t t h e p u b l i s h e r r e c o r d s t h e d e a t h of Professor H i n d m a r s h i n D e c e m b e r 1 9 7 3 .

133
134 HIND MARSH

An e q u i v a l e n t g e n e r a l e x p r e s s i o n is found by using the a u t o c o r r e l a t i o n


f u n c t i o n of t h e d i s t u r b a n c e f(t). P u t t i n g

J d t ' u ' ( t ' ) = u 0 t + 17(t)


0
w h e r e 17(t) i s t h e d e p a r t u r e in p h a s e of the p e r t u r b e d o s c i l l a t i o n f r o m t h e
u n p e r t u r b e d o s c i l l a t i o n , t h e a u t o c o r r e l a t i o n f u n c t i o n Ф(в) i s

2
Ф(в) = f(t) f(t + s) = I e i ^ 0 t e i w 0 s e i [ T i ( t + s) + j j ( t ) ]
t

+ R e Í . 'i w o S „ i [ l ) ( t + s ) - 7j(t)]
J

w h e r e I It i n d i c a t e s the a v e r a g e value o v e r a l l v a l u e s of t . The f i r s t t e r m


in t h e e x p r e s s i o n f o r ®(s) v a n i s h e s p r o v i d e d t h a t no s i g n i f i c a n t d i s t u r b a n c e
in p h a s e o c c u r s , on t h e a v e r a g e , within one c y c l e of o s c i l l a t i o n . F o r o p t i c a l
s p e c t r a , w h e r e t h e line width i s a s m a l l f r a c t i o n of t h e u n d i s t u r b e d f r e q u e n c y ,
t h i s i s a v e r y good a p p r o x i m a t i o n , but it should be noticed t h a t t h e r e s u l t s
obtained with i t s u s e c a n n o t be e x t r a p o l a t e d to give t h e c o r r e c t z e r o -
f r e q u e n c y r e s u l t s . With t h i s l i m i t a t i o n we m a y w r i t e

Ф(в) = -H Re giwos gii(t.s)

+ e- i w 0 s g-itKM)
(3)

= Ф(в) + \ř*(s)

w h e r e n(t, s) = n(t + s) - r)(t).


Since the i n t e n s i t y p r o f i l e i s the c o m p l e x F o u r i e r t r a n s f o r m of the a u t o -
c o r r e l a t i o n f u n c t i o n of the d i s t u r b a n c e we have

I (to) = M / ( s ) e l a J S ds + / Ф* (s)e l w s ds (4)

1.2. The i m p a c t a p p r o x i m a t i o n

T h e c h a n g e Д [^(sje" 1 " 0 5 ], not n e c e s s a r i l y s m a l l , in Sř(s)e"1WoS c o r r e -


sponding to a c h a n g e A s in s i s

A[*(s)e-iw°s] (e i A l i - l ) ] t

i , M
=|le l t [e iAl) - 1],

= -ф(в)е - i w 0 s r i At)
- Ht

where Arj = r)(t, s + A s ) - r)(t, s)


IAEA-SMR-12/4,5 135

and the s e c o n d line f o l l o w s b e c a u s e the c h a n g e s Ar] o c c u r r i n g in an o s c i l -


l a t o r p e r t u r b e d by r a n d o m c o l l i s i o n s a r e s t a t i s t i c a l l y i n d e p e n d e n t of rj,
the a c c u m u l a t e d p h a s e d i s t u r b a n c e a t t i m e s . Next we s u p p o s e t h a t t h e
p h a s e c h a n g e s Дт] a r e c a u s e d by s u c c e s s i v e c o l l i s i o n s . T h i s i s known a s
t h e i m p a c t a p p r o x i m a t i o n , and we s h a l l d i s c u s s i t s r a n g e of v a l i d i t y l a t e r .
T h e n u m b e r of c o l l i s i o n s with i m p a c t p a r a m e t e r p which o c c u r in t h e t i m e
i n t e r v a l A s i s NV2îrp dp | A s | w h e r e N i s t h e n u m b e r d e n s i t y of p e r t u r b i n g
p a r t i c l e s ; t h e f u r t h e r a s s u m p t i o n h a s b e e n m a d e t h a t the p e r t u r b i n g and
r a d i a t i n g a t o m s m o v e in s t r a i g h t l i n e s with t h e m e a n r e l a t i v e v e l o c i t y v .
Then

[eiAr> - l ] t = 2 7 r N v | A s | / [ e i , K p ) - 1] pdp
о

= - N v I A s I (ст - iCTj )

w h e r e rj(p) i s t h e p h a s e c h a n g e c a u s e d by a c o l l i s i o n of i m p a c t p a r a m e t e r p,
and

crr = 2 n J [ 1 - c o s rj(p)] pdp (5)


о

CTj = 2nJ s i n rj (p) pdp (6)


о

Therefore

L = - Nv I A s I (стг - iCTj )
*(s)e~ l a , » s

Since the a v e r a g e o v e r a l a r g e n u m b e r of c o l l i s i o n s i s i n v o l v e d , t h i s l a s t
e x p r e s s i o n c a n be t r e a t e d a s a d i f f e r e n t i a l e q u a t i o n . I n t e g r a t i o n t h e n g i v e s

Ф(э) = c o n s t a n t X exp Uiw 0 - N v ( a r - iOj ) ] | s | } (7)

T h u s the s p e c t r u m i s , f r o m E q s (4) and (7),

I(u>) = 2NVa r { ( u ) o + u + Ша.уг + {Ша!уг + ( Uo . ш + Ш а ^ + (NVtrr ) и } (8)

In o p t i c a l s p e c t r a t h e f i r s t t e r m i n t h i s e x p r e s s i o n f o r I(u) i s n e g l i g i b l e •
c o m p a r e d with the s e c o n d . T h u s

(u0 - ы + Nva ř )2 + (Nvar )2

w h e r e we have n o r m a l i z e d so t h a t
ОС

f I(u)du = 1
о
136 HIND MARSH

T h e s p e c t r a l line t h e r e f o r e h a s a L o r e n t z i a n s h a p e , but the whole line


i s s h i f t e d with r e s p e c t to t h e u n d i s t u r b e d line c e n t r e at u 0 . The quantity
a r - i n j c a n b e looked on a s a c o m p l e x c r o s s - s e c t i o n , t h e b r o a d e n i n g of
the line being a s s o c i a t e d with the r e a l p a r t of t h i s c r o s s - s e c t i o n and
t h e s h i f t with t h e i m a g i n a r y p a r t -ст ; . It i s a l s o e a s y to s e e f r o m E q s (5)
and (6) t h a t , s i n c e n(p) i n c r e a s e s r a p i d l y a s p d e c r e a s e s , t h e c o n t r i b u t i o n
to CTj a r i s e s p r e d o m i n a n t l y f r o m s m a l l v a l u e s of p while t h a t to a r a r i s e s
p r e d o m i n a n t l y f r o m l a r g e v a l u e s of p. T h i s c o r r e s p o n d s to the o r i g i n a l
p h y s i c a l i d e a of W e i s s k o p f (1933) that t h e b r o a d e n i n g a r i s e s e s s e n t i a l l y
f o r c o l l i s i o n s which c a u s e a p h a s e c h a n g e g r e a t e r t h a n about 1 r a d i a n .
To p r e s s t h i s c l a s s i c a l c a l c u l a t i o n to a n u m e r i c a l c o n c l u s i o n we m u s t
e v a l u a t e n(p) and p e r f o r m t h e i n t e g r a t i o n s in E q s (5) and (6). If t h e i n t e r -
a t o m i c p o t e n t i a l s of the u p p e r and l o w e r s t a t e s of the r a d i a t i n g a t o m and
the p e r t u r b i n g a t o m (taken to be in t h e g r o u n d s t a t e ) a r e r e s p e c t i v e l y Vu (R)
and V j i R ) , w h e r e R i s t h e d i s t a n c e b e t w e e n t h e two a t o m s , then
SO OO

4(p) = ^ / [ V u ( R ) - V , ( R ) ] d t V(R)dt

w h e r e t r e p r e s e n t s the t i m e m e a s u r e d f r o m t h e t i m e of c l o s e s t a p p r o a c h
of t h e colliding a t o m s . If we a s s u m e t h a t the a t o m s m o v e i n s t r a i g h t p a t h s
with v e l o c i t y v, then,

„2 2 2 2
R =p + v t
so that

2 Г V(R) RdR
«M - WJ (R2 - p ž )i (10)
о

We now e x a m i n e the v a l i d i t y of the i m p o r t a n t a p p r o x i m a t i o n s which have


been made.
F i r s t we c o n s i d e r t h e i m p a c t a p p r o x i m a t i o n i t s e l f . T h e c o l l i s i o n s a r e
s u p p o s e d to o c c u r s u c c e s s i v e l y and to occupy a t i m e s m a l l c o m p a r e d with
t h e t i m e b e t w e e n c o l l i s i o n s . The r a d i a t i o n e m i t t e d d u r i n g the c o l l i s i o n s
m a y then be n e g l e c t e d . Now t h e d u r a t i o n of a c o l l i s i o n i s т с ~ p / v and the
m e a n t i m e b e t w e e n c o l l i s i o n s which c a u s e b r o a d e n i n g i s 7 = (Nvo r ) _1 . We
c o m p a r e the i n t e n s i t y p e r unit f r e q u e n c y i n t e r v a l f r o m т с with t h a t f r o m т
a t a given f r e q u e n c y d i s p l a c e m e n t (uQ - u) f r o m the l i n e c e n t r e . R e m e m b e r i n g
t h a t the f o r m e r c o n t r i b u t i o n i s s p r e a d o v e r an i n t e r v a l ~ т" 1 , the r a t i o of the
two c o n t r i b u t i o n s i s a p p r o x i m a t e l y

2 2 2 2
(p/v) 7Г (U)Q - U) _ 7Tp (Up -(O)
(Nva r )-l NvCTr V2

If the i m p a c t a p p r o x i m a t i o n i s to be v a l i d t h i s r a t i o m u s t be « 1. Hence

(u 0 - u) 2 « V 2 / t t P 2 (11)
IAEA-SMR-12/4,5 137

But t h e v a l u e of u 0 - u a s s o c i a t e d with a c e r t a i n v a l u e of p i s d e t e r m i n e d
by the i n t e r a t o m i c p o t e n t i a l

u 0 - u = - V(p)/tl
6
In the s p e c i a l c a s e of the v a n - d e r - W a a l s i n t e r a c t i o n s V(p) = - Cg/R , the
inequality b e c o m e s
6/5 1/5

(12)

F o r n e u t r a l a t o m p a i r s C 6 ~ 10 5 1 e r g • cm 6 , and f o r m a n y e x p e r i m e n t s
v = 10 5 c m • s" 1 . With t h e s e v a l u e s , we find the i m p a c t r e g i o n d e f i n e d a s

I со q - и I « 3X 1 0 U r a d - s " 1 = 1,5 cm" 1

Although v a l u e s of C g and v c a n v a r y o v e r a c e r t a i n r a n g e , the i m p a c t r e g i o n


i s m o s t l y d e f i n e d by a b o u n d a r y of a few wave n u m b e r s . Notice t h a t t h i s
b o u n d a r y o c c u r s on one wing only of t h e line if the p o t e n t i a l i s e n t i r e l y
d e s c r i b e d by the v a n - d e r - W a a l s i n t e r a c t i o n . If C 6 i s p o s i t i v e (the u s u a l
c a s e ) , t h e n u 0 - ш i s p o s i t i v e and the b o u n d a r y r e f e r s to t h e low f r e q u e n c y
wing of t h e l i n e , and the i m p a c t a p p r o x i m a t i o n i s v a l i d f o r all p o s i t i o n s
on the high f r e q u e n c y wing of the l i n e . In f a c t , f o r v e r y c l o s e e n c o u n t e r s
the " r e p u l s i v e " p a r t of t h e p o t e n t i a l c u r v e c a u s e s r a d i a t i o n to be e m i t t e d
on the high f r e q u e n c y side of t h e line c e n t r e , so t h a t in p r a c t i c e an i m p a c t
b o u n d a r y a r i s e s on that side a l s o . Taking t h e L e n n a r d - J o n e s f o r m
V(p) = C 1 2 / p 1 2 - C 6 / p 6 i t t u r n s out, with t y p i c a l v a l u e s f o r the c o n s t a n t s ,
t h a t t h e i m p a c t b o u n d a r y on t h e l o w - f r e q u e n c y side i s not usually a f f e c t e d
by the p r e s e n c e of the R" 12 t e r m , and that on t h e h i g h - f r e q u e n c y s i d e the
b o u n d a r y i s d e t e r m i n e d only by t h e r e p u l s i v e t e r m . With C 12 = 10" 1 0 4 e r g - c m 1 2
and v = 10 5 c m - s 1 , we find

|u 0 - u | « 3 X 1 0 1 2 r a d - s " 1 = 15 cm" 1

A n o t h e r s p e c i a l c a s e of s o m e i m p o r t a n c e i s t h e i n t e r a c t i o n of c h a r g e d
p a r t i c l e s with a n e u t r a l a t o m . In g e n e r a l t h i s t a k e s the f o r m of a q u a d r a t i c
S t a r k e f f e c t and i s t h e r e f o r e d e s c r i b e d by the e x p r e s s i o n C 4 / R 4 . T h e
i m p a c t r e g i o n i s then d e f i n e d by the r e l a t i o n

/ \4/3 , .1/3

к @
V a l u e s of C 4 g e n e r a l l y lie in t h e r a n g e 10"39 -10" 4 2 e r g • c m 4 . We need
to d i s t i n g u i s h t h e b r o a d e n i n g due to ions, with t h e r m a l v e l o c i t i e s of s a y
2X10 cm • s in a low t e m p e r a t u r e p l a s m a , and t h a t due to t h e e l e c t r o n s
with v e l o c i t i e s of p e r h a p s 5 X 10 7 c m • s" 1 . F o r ion b r o a d e n i n g we find

u 0 - u | « 5X 10 10 - 5 X 1 0 1 1 r a d - s " 1 = 0 . 3 - 3 cm" 1
138 HIND MARSH

while f o r e l e c t r o n b r o a d e n i n g t h e r e s u l t i s

I Up - u | « 10 1 4 - 10 15 r a d • s 1
= 500 - 5000 cm" 1

F i n a l l y we e x a m i n e t h e r a n g e of v a l i d i t y of t h e i m p a c t a p p r o x i m a t i o n
when h y d r o g e n - l i k e l i n e s a r e b r o a d e n e d by e l e c t r o n s and i o n s . H e r e the
l i n e a r S t a r k e f f e c t g o v e r n s the i n t e r a c t i o n which t a k e s the f o r m C 2 / R 2 ,
and we find

F o r a h y d r o g e n a t o m C 2 ~ e 2 a 0 n ( n - l ) w h e r e n i s the p r i n c i p a l q u a n t u m
n u m b e r of t h e u p p e r l e v e l . F o r H a C , = 5X 10" 27 e r g - c m 2 . With
~ - 2 X 10 5 c m • s" 1 f o r i o n s and 5 X 10* c m • s" 1 f o r e l e c t r o n s we find

9
|Uq - u I <c 10 r a d • s" 1 = 0.005 cm" 1

f o r the i m p a c t l i m i t f o r ionic b r o a d e n i n g and

ш„ - w « 10 1 4 r a d • s" 1 = 500 cm" 1

f o r ionic b r o a d e n i n g .
Secondly we e x a m i n e the v a l i d i t y of the a s s u m p t i o n t h a t the a t o m s m o v e
in s t r a i g h t l i n e s . A r o u g h c a l c u l a t i o n c a n be m a d e to e s t i m a t e the r a n g e of
a p p l i c a b i l i t y of the s t r a i g h t - p a t h a p p r o x i m a t i o n .
T h e o r b i t will be s i g n i f i c a n t l y c u r v e d if the i m p u l s e of the f o r c e F
e x e r t e d b e t w e e n t h e colliding a t o m s b e c o m e s c o m p a r a b l e with the m o m e n t u m
of e i t h e r of t h e m . T h e r e l e v a n t r a t i o i s t h e r e f o r e , f o r n e u t r a l a t o m s ,

/Fdt ^ (dV/dR) R , g p _ S 2 Ci2 Ce


P
Mv Mv v Mv 2 n i2 " «6

w h e r e M i s the m a s s of the s m a l l e r a t o m involved. Now t h e p h a s e c h a n g e ,


calculated for straight paths, for a L e n n a r d - J o n e s potential is (Hindmarsh,
P e t f o r d and Smith, 1967)
63£ Olg 3_7T J _ Cg
1 K
256 m p H " 8 TiV p5 '

If, at the c r i t i c a l v a l u e p c of p, r) is d e t e r m i n e d e s s e n t i a l l y by the s e c o n d


t e r m , t h e n p i s a l s o so d e t e r m i n e d . We t h e n h a v e , s i n c e rj = 1 at p c ,

P® ~ c . / w
6

and
6tt 6tl6/5
Л
MVpc Mv4/5Cl/5 "" °
IAEA-SMR-12/4,5 139

on s u b s t i t u t i n g t y p i c a l v a l u e s . P a t h c u r v a t u r e i s t h e r e f o r e s m a l l . If C 6
i s s m a l l , p c i s e s s e n t i a l l y d e t e r m i n e d by the R" 12 t e r m . In t h i s c a s e we
find p ~ 1 with C 1 2 = 10" 106 e r g - c m 1 2 . We t h e r e f o r e e x p e c t p a t h c u r v a t u r e
to have a m a r k e d e f f e c t .
F o r c h a r g e d - p a r t i c l e i n t e r a c t i o n s we find f o r the q u a d r a t i c S t a r k e f f e c t
interaction

10
P ~ Mv2/3 c i / 5 ~ "3 - 10 2
" for ions

% 0.3 - 3.0 for electrons

and f o r t h e l i n e a r S t a r k e f f e c t i n t e r a c t i o n

2ft 2 1 n -4 , .
10 for ions
MC 2
1 for electrons

We t h e r e f o r e e x p e c t t h a t c u r v a t u r e of the o r b i t s i s i m p o r t a n t f o r i m p a c t
b r o a d e n i n g by e l e c t r o n s but not f o r b r o a d e n i n g by i o n s . A f u n d a m e n t a l
point which a r i s e s h e r e i s how to c o m b i n e t h e p o t e n t i a l s f o r the two l e v e l s
of the r a d i a t o r which a r e involved in the t r a n s i t i o n , s i n c e the c l a s s i c a l
p a t h will not be the s a m e f o r both l e v e l s . T h i s h a s b e e n d i s c u s s e d by
F i u t a k and C z u c h a j (1970) who point out t h a t the condition p « 1 f o r s t r a i g h t
p a t h s i s e s s e n t i a l l y t h e s a m e a s the condition f o r t h e p e r t u r b e r m o t i o n to
be d e s c r i b e d c l a s s i c a l l y at all (see s e c t i o n 2). Although S c h ü l l e r and V o d a r
(1960) have c a l c u l a t e d t h e e f f e c t of c u r v a t u r e of the o r b i t s f o r a S u t h e r l a n d
t y p e of p o t e n t i a l , and find s i g n i f i c a n t e f f e c t s in c e r t a i n c r i c u m s t a n c e s , a
g r e a t e r e f f o r t i s p r o b a b l y not w o r t h while u n l e s s a f u l l q u a n t u m m e c h a n i c a l
treatment is used.
T h i r d l y we m e n t i o n the p r o b l e m of v e l o c i t y a v e r a g i n g . In m o s t w o r k
t h i s i s a c h i e v e d by t h e s i m p l e d e v i c e of w r i t i n g v , the m e a n t h e r m a l r e l a t i v e
s p e e d of t h e r a d i a t i n g and p e r t u r b i n g a t o m s w h e r e v e r t h e v e l o c i t y e n t e r s
the c a l c u l a t i o n . ,This i s c l e a r l y not c o r r e c t . It i s a r e l a t i v e l y s i m p l e m a t t e r
to a v e r a g e the p h a s e s h i f t e x p r e s s i o n s o v e r a M a x w e l l i a n v e l o c i t y d i s t r i b u t i o n ,
and t h i s in f a c t m a k e s only a s m a l l d i f f e r e n c e to the n u m e r i c a l r e s u l t s . The
r e a l d i f f i c u l t y i s t h a t if r i g o r o u s l y c o r r e c t v e l o c i t y a v e r a g i n g i s to be c a r r i e d
out, the t h e r m a l (Doppler) b r o a d e n i n g of t h e s p e c t r a l line cannot be t r e a t e d
s e p a r a t e l y f r o m the c o l l i s i o n b r o a d e n i n g a s i s u s u a l l y done. T h i s q u e s t i o n
h a s b e e n s t u d i e d by G e r s t o n and F o l e y (1968). who r e f e r to the e a r l i e r w o r k
of Dicke (1953) and W i t t k e and Dicke (1956) on " p r e s s u r e n a r r o w i n g " . The
e s s e n t i a l point i s t h a t if the m e a n f r e e path of t h e r a d i a t i n g a t o m s f o r c o l -
l i s i o n s w h i c h change t h e i r d i r e c t i o n b e c o m e s m u c h s m a l l e r t h a n t h e w a v e l e n g t h
of t h e r a d i a t i o n , t h e D o p p l e r s h i f t induced in one p o r t i o n of a c y c l e of the
r a d i a t i o n t e n d s to c a n c e l t h e s h i f t f r o m a n o t h e r p o r t i o n . The e f f e c t i v e
D o p p l e r width i s t h e n m u c h r e d u c e d , and p r o v i d e d the o r d i n a r y c o l l i s i o n
b r o a d e n i n g i s not too g r e a t , a n e t n a r r o w i n g with i n c r e a s i n g p r e s s u r e c a n
o c c u r o v e r a c e r t a i n p r e s s u r e r a n g e . T h i s i s not u s u a l l y the c a s e in o p t i c a l
s p e c t r a , but at m u c h l o w e r f r e q u e n c i e s t h e p h e n o m e n o n i s w e l l known.
140 H I N D MARSH

1.3. The quasi-static approximation

The q u a s i - s t a t i c approximation t a k e s into account r a d i a t i o n emitted


a t a l l t i m e s , but d o e s not m a k e a F o u r i e r a n a l y s i s . T h e i n t e n s i t y a t an
a n g u l a r f r e q u e n c y u i s t h u s p r o p o r t i o n a l to t h e f r a c t i o n of t h e t o t a l t i m e
w h i c h the a t o m s p e n d s i n r a d i a t i n g at t h a t f r e q u e n c y . If t h e i n s t a n t a n e o u s
f r e q u e n c y i s r e p r e s e n t e d by u - L)q + Au t h e n t h e q u a s i - s t a t i c t h e o r y g i v e s

I (Ди) ос P ( A u )

w h e r e Р(Аы) i s t h e p r o b a b i l i t y of o c c u r r e n c e of t h e f r e q u e n c y d i s p l a c e m e n t
Au.
We w i s h to e v a l u a t e t h e o c c u r r e n c e p r o b a b i l i t y P ( A u ) in t e r m s of t h e
i n t e r a t o m i c p o t e n t i a l . T h i s t y p e of c a l c u l a t i o n w a s f i r s t p e r f o r m e d by
H o l t s m a r k (1919) f o r the s p e c i a l c a s e of b r o a d e n i n g by c h a r g e d p a r t i c l e s
(where the i n t e r a c t i o n is e i t h e r the linear or the quadratic Stark effect)
and by M a r g e n a u (1932) f o r the g e n e r a l c a s e of s c a l a r l y a d d i t i v e i n t e r a c t i o n s .
We show h e r e t h e c a l c u l a t i o n s f o r the l a t t e r c a s e .
I m a g i n e a t o t a l of N T p e r t u r b e r s in a s p h e r i c a l v e s s e l of r a d i u s R 0 ,
c e n t r e d a b o u t t h e r a d i a t i n g a t o m . The p r o b a b i l i t y of f i n d i n g a p e r t u r b e r
in t h | s p h e r i c a l . s h e l l d e f i n e d by R and R + dR i s 4TR 2 dR3N T /(47rR 3 0 ) =
3 N T R d R / R 0 . T h u s we h a v e t h a t

R d R (14)
Р(Ди) o c I j ( | r / i i)
1
0 Aw

w h e r e R j i s t h e p o s i t i o n of i - t h p e r t u r b e r , a n d t h e i n t e g r a t i o n i s o v e r t h o s e
positions which yield the c o r r e c t p e r t u r b a t i o n Au. The i n t e g r a l can,
h o w e v e r , be w r i t t e n in s u c h a f o r m t h a t i t g o e s o v e r a l l s p a c e w i t h the u s e
of a D i r i c h l e t f a c t o r

J s i n (xd(Au)) e i ň x dx

whe r e
i
Г2 == ^ Y , v ( R i )
" л и

i-1

T h i s f a c t o r t a k e s t h e v a l u e я w h e n fî = 0, i . e . w h e n the t o t a l f r e q u e n c y
d i s p l a c e m e n t i s A u , and i s z e r o e l s e w h e r e ; s c a l a r a d d i t i v i t y h a s b e e n
a s s u m e d at t h i s p o i n t . We m a y t h e r e f o r e w r i t e
R
o Ro
P(Au)dAu = 3 J . . . . J ГR
Г -r-,2
; R „2
;... R „2
N _ d R i d R 2 • • • dR N
o o о

s i n (xd(Au)) e iňx

R
/ \N T °
f _3 > T
( -53-J
: d(Au) J \J R' dReinKJX/"| e"ix^dx
VR 0 -OO 0
IAEA-SMR-12/4,5 141

It i s c o n v e n i e n t to i n t r o d u c e t h e f u n c t i o n

U(x) = f ( 1 - e i V ( R ) x / n ) R 2 dR (15)
0

i n w h i c h c a s e we h a v e

Р(Ды) = / (1 - 3 U ( X ) / R q ) N t e" i x A w dx (16)

Next we allow N T and R 0 to t e n d to i n f i n i t y , with the c o n d i t i o n t h a t


N T / 3 7tR 0 = N. T h i s i s r e a d i l y a c h i e v e d by m e a n s of t h e e x p r e s s i o n

lim ( 1 - 3U(x)/R3 f T
= l i m ( l - 4TTU(X)N/N X ) N T = E " 4 Ï Ï U ( X ) N

We t h e r e f o r e h a v e
CO

, Г -4nU(x)N -ixAw
Р(Ди) = / e e dx

T h e i n t e g r a l m a y b e e x p r e s s e d in a m o r e c o n v e n i e n t f o r m by w r i t i n g

4?rU(x)N = A(x) + i B ( x ) (17)

Then, r e c a l l i n g that U(-x) = U*(x),we obtain

I (Au) ос Р(Ды) = / e _ A ( x ) c o s { B ( x ) + х Д ы } dx (18)

2. Q U A N T U M T H E O R Y O F COLLISION BROADENING

2.1. General formulation

W e t u r n now t o a n e x p o s i t i o n of t h e q u a n t u m t h e o r y of c o l l i s i o n
b r o a d e n i n g . It i s i m p o r t a n t at t h e o u t s e t to u n d e r s t a n d t h e e s s e n t i a l
d i f f e r e n c e s b e t w e e n t h e c l a s s i c a l and q u a n t u m t r e a t m e n t s of t h e p r o b l e m .
We c o n s i d e r q u a n t u m e f f e c t s i n t h e p e r t u r b i n g and r a d i a t i n g a t o m s s e p a r a t e l y .
The i n t e r a c t i o n between t h e m i s a l r e a d y in effect t r e a t e d quantum-
m e c h a n i c a l l y i n t h e c l a s s i c a l t h e o r y , f o r V(R) c a n be t h e r e s u l t of a
q u a n t u m c a l c u l a t i o n , p r o v i d e d both s t a t e s of t h e r a d i a t o r c a n b e c o n s i d e r e d
s t a t i o n a r y on t h e t i m e s c a l e of a c o l l i s i o n .
F i r s t we e x a m i n e w h e t h e r t h e p a t h of a p e r t u r b e r r e l a t i v e to a r a d i a t o r
c a n be a d e q u a t e l y d e s c r i b e d by a c l a s s i c a l o r b i t . The r e l e v a n t p a r a m e t e r
h e r e i s t h e r a t i o of t h e de B r o g l i e w a v e l e n g t h of the a t o m to t h e m i n i m u m
i n t e r a t o m i c d i s t a n c e . T h i s l a t t e r q u a n t i t y i s d e f i n e d s i m p l y by t h e i m p a c t
p a r a m e t e r f o r the c r i t i c a l "Weisskopf" phase change. C l o s e r collisions,
of c o u r s e , o c c u r , but s i n c e t h e y c a u s e l a r g e r t h a n c r i t i c a l p h a s e c h a n g e s
i n t h e r a d i a t i o n , t h e e x a c t p h a s e c h a n g e and t h e d e t a i l s of t h e c o l l i s i o n
142 H I N D MARSH

have no e f f e c t on t h e line p r o f i l e . The condition f o r the c l a s s i c a l p a t h


a p p r o x i m a t i o n to b e v a l i d f o r m o s t c o l l i s i o n s i s , then,

<K p o r
l b c (3MkT)i/2 < < : Pc
(As we have a l r e a d y pointed out, t h i s i s a l s o the condition which e n s u r e s
t h a t t h e path i s s t r a i g h t . ) Taking the w o r s t c a s e , we have to d e a l with
e x p e r i m e n t s at a t e m p e r a t u r e of, say, 2 0 K with h e l i u m a s the p e r t u r b e r .
F o r t h i s c a s e t h e condition b e c o m e s
p » 3 A
It i s quite p o s s i b l e f o r t h i s condition not to be v e r y w e l l s a t i s f i e d , although
m o s t e x p e r i m e n t s a r e c a r r i e d out at t e m p e r a t u r e s of at l e a s t s e v e r a l
h u n d r e d Kelvin, in which c a s e no d i f f i c u l t y a r i s e s . F o r c o m p l e t e g e n e r -
ality, h o w e v e r , t h e q u a n t u m d e s c r i p t i o n of t h e c o l l i s i o n o r b i t s m u s t be
u s e d . When b r o a d e n i n g i s due to e l e c t r o n s t h e s a m e s i t u a t i o n a r i s e s .
Secondly, t h e q u e s t i o n a r i s e s w h e t h e r t h e use of the c l a s s i c a l e l e c t r o n
o s c i l l a t o r r a t h e r t h a n a r e a l a t o m to d e s c r i b e the e m i s s i o n o r a b s o r p t i o n
of r a d i a t i o n i s s a t i s f a c t o r y . It i s well known t h a t t h i s s i m p l e c l a s s i c a l a t o m
c o r r e s p o n d s c l o s e l y to a r e a l a t o m with only two e n e r g y l e v e l s , o r w h e r e
the two e n e r g y l e v e l s involved in the t r a n s i t i o n c o n c e r n e d a r e c o m p l e t e l y
uncoupled f r o m a l l o t h e r l e v e l s . E x c e p t w h e r e t h e r e i s d e g e n e r a c y , o r ,
what a m o u n t s to the s a m e thing, w h e r e the c o l l i s i o n i t s e l f c a u s e s t r a n s i t i o n s
b e t w e e n e n e r g y l e v e l s of t h e r a d i a t o r , we e x p e c t t h i s a p p r o x i m a t i o n to be
v e r y good. Two kinds of d e g e n e r a c y a r e c o n c e r n e d ; one i s the u n i v e r s a l
d e g e n e r a c y a s s o c i a t e d with t h e q u a n t u m n u m b e r m , and the o t h e r the m u c h
r a r e r a c c i d e n t a l d e g e n e r a c y w h e r e l e v e l s with d i f f e r e n t v a l u e s of o t h e r
q u a n t u m n u m b e ' r s have the s a m e , o r n e a r l y t h e s a m e , e n e r g y . If c o l l i s i o n -
i n d u c e d t r a n s i t i o n s o c c u r , we e x p e c t t h a t not only w i l l t h e d a m p i n g c o n s t a n t
of the line be c h a n g e d , but a l s o t h e s h a p e will no l o n g e r be L o r e n t z i a n .
T h i s i s c l e a r f r o m the c l a s s i c a l analogue, in which the c o l l i s i o n s c a u s e
coupling b e t w e e n the o s c i l l a t i o n c o n c e r n e d and o t h e r m o d e s of o s c i l l a t i o n
of the s y s t e m .
The q u a n t u m - m e c h a n i c a l analogue of E q . (2) i s

I(w) ô(io-u l f ) | < f | d | i > | 2 p. (19)


if
w h e r e the i n i t i a l and f i n a l s t a t e s |i)> and | f У a r e the t i m e - d e p e n d e n t s t a t e
f u n c t i o n s r e f e r r i n g to t h e whole s y s t e m of r a d i a t o r s and p e r t u r b e r s .
ô (u - u i f ) i s the D i r a c 6 - f u n c t i o n , which t a k e s the v a l u e 1 when ш = u. f
and i s z e r o e l s e w h e r e ; p t i s t h e n u m b e r d e n s i t y of r a d i a t o r s in the s t a t e
J i)>, and d i s t h e e l e c t r i c dipole m o m e n t .
No f u r t h e r p r o g r e s s c a n be m a d e without i n t r o d u c i n g | i > and |f)>
e x p l i c i t l y . At t h i s point we abandon a wholly g e n e r a l t r e a t m e n t , and
invoke t h e c l a s s i c a l p a t h a p p r o x i m a t i o n .

2.2. The c l a s s i c a l path a p p r o x i m a t i o n

We b e g i n by w r i t i n g the H a m i l t o n i a n f o r the c o m p l è t e s y s t e m a s

H = HA + H p + V
IAEA-SMR-12/4,5 143

w h e r e H A , H p and V a r e r e s p e c t i v e l y the H a m i l t o n i a n s f o r the r a d i a t i n g


a t o m , t h e p e r t u r b e r s and t h e i n t e r a c t i o n b e t w e e n t h e r a d i a t o r and p e r t u r b e r s ,
and the w a v e f u n c t i o n f o r t h e s y s t e m a s

* ( t ) = X(t) Ф (t) (20)

w h e r e x(t) and $(t) a r e r e s p e c t i v e l y the t i m e - d e p e n d e n t w a v e f u n c t i o n s f o r


the r a d i a t o r and the p e r t u r b e r s ; x(t) d e p e n d s on t h e c o - o r d i n a t e s of t h e
r a d i a t o r only and ф(t) on t h o s e of the p e r t u r b e r s only. T h i s w a v e f u n c t i o n
i g n o r e s t h e i n t e r a c t i o n b e t w e e n r a d i a t o r and p e r t u r b e r s , and t h i s i n f l u e n c e
m u s t be e v a l u a t e d by p e r t u r b a t i o n t h e o r y . The w a v e f u n c t i o n d e s c r i b i n g
the m o t i o n of the p e r t u r b e r s o b e y s t h e t i m e - d e p e n d e n t S c h r ö d i n g e r e q u a t i o n

d<Mt)
m dt
H p <Mt)

To find t h e e q u a t i o n obeyed by x(t), we m u l t i p l y E q . (20) by </>*(t) and i n t e g r a t e


over the p e r t u r b e r c o - o r d i n a t e s x :

X(t) = Ф Ю Ф * (t) d x D

f r o m w h i c h we obtain

d X ( t ) _
0 ( t ) H p * * ( t ) d x „ + / (HA + H + v)4>(tW4t)dxB (21)
dt

= [H A + v(t) ] x(t)
where
v(t) = / ф* (t) V<i>(t)dx (22)

We c a n t h e r e f o r e p r o c e e d a s though the a t o m i c wave f u n c t i o n x(t) i s s u b j e c t


to a t i m e - v a r y i n g p e r t u r b a t i o n g i v e n by v(t), and in t h e c l a s s i c a l - p a t h
a p p r o x i m a t i o n (that i s with the ф{t) a s s u m e d to be l o c a l i z e d wave p a c k e t s )
v(t) i s g i v e n s i m p l y by the c l a s s i c a l p o t e n t i a l d e s c r i b i n g the r a p i d l y v a r y i n g
i n t e r a c t i o n b e t w e e n the r a d i a t o r and p e r t u r b e r s .
T h e e f f e c t of the p e r t u r b e r s m a y then be t a k e n into a c c o u n t by w r i t i n g
a t i m e - d e v e l o p m e n t o p e r a t o r T^ w h i c h a c t s on the p e r t u r b e d a t o m i c w a v e
f u n c t i o n x(t) and i s d e f i n e d by

[HA + v(t)]TA(t)

As in the c l a s s i c a l t r e a t m e n t we w o r k in terms of the a u t o c o r r e l a t i o n


f u n c t i o n $ ( s ) , and we s e e t h a t the q u a n t u m m e c h a n i c a l a n a l o g u e of E q . (3) i s

Ks) | d T A ( t , s ) | f f > < f f | d T*(t, s ) | a > + c. c. (23)


Z[<
w h e r e TA (t, s) = TA (t + s) - T A (t), a l a b e l s the u p p e r s t a t e s and a the l o w e r
s t a t e s of the a t o m i c t r a n s i t i o n , t h e a v e r a g e i s t a k e n o v e r a l l t i m e s t and c . c .
144 H I N D MARSH

s t a n d s f o r c o m p l e x c o n j u g a t e . T o c l a r i f y s t i l l f u r t h e r t h e a n a l o g y w i t h the
c l a s s i c a l e x p r e s s i o n , we s e p a r a t e the t i m e - d e p e n d e n t f r o m the t i m e -
i n d e p e n d e n t f a c t o r s , and w r i t e $ ( s ) in t h e e x p a n d e d f o r m

>(s) <a|d|a><ß|d|b><b|TA(t, s)|a><a|T*(t,s)|8> +c.c. (24)


abaß

If t h e r e i s only a s i n g l e u p p e r s t a t e | a^> and a s i n g l e l o w e r s t a t e


i n v o l v e d , ' t h e r e i s only one t e r m in t h e s u m m a t i o n and (24) r e d u c e s to

Ф(в) = | < a | d | û r > 12 [<O|T* (t, s ) | o - > < a | T A (t, s ) | a > + c . c . ] (25)

w h i c h , a p a r t f r o m a n u m e r i c a l f a c t o r , i s e q u i v a l e n t to E q . (3).
It i s c o n v e n i e n t f o r f u r t h e r d e v e l o p m e n t to w o r k with t h e t i m e - e v o l u t i o n
o p e r a t o r in an i n t e r a c t i o n r e p r e s e n t a t i o n . W e w r i t e

U(0, s) = exp ( i H A s / t i ) T ( 0 , s)

T h i s i s p r e c i s e l y a n a l o g o u s to t h e d e v i c e of w o r k i n g with Sř(s)e" lw ° s in t h e
c l a s s i c a l t r e a t m e n t . We then have

m f = exp ( i H A s / t l ) v ( s ) e x p ( - i H A s / î l ) U = v ' ( s ) U

T h i s e q u a t i o n i s s o l v e d by the s t a n d a r d p e r t u r b a t i o n e x p a n s i o n
S S Î!

,
U(0, s) = 1 - (i/ti) fv'(s1)ds1 + (i/bf Jv'(s1)ds1fv {s2)ds2 + ...
o o o

w h i l e i n t e r m s of U(s) t h e c o r r e l a t i o n f u n c t i o n b e c o m e s

i(Es Eb)t/n
Ks) = ^ < a | d | o r > < 0 | d | b > e " < a | u * ( t , s ) | ß > < b | u ( t , s ) | a> + c . c .
abaß
(26)

2.3. The impact approximation

T h e c a l c u l a t i o n of t h e a v e r a g e in t h e i m p a c t a p p r o x i m a t i o n f o l l o w s
v e r y c l o s e l y t h e c l a s s i c a l c a l c u l a t i o n . T h e c h a n g e ДФ(в) in ®(s) i s w r i t t e n
down; it i n v o l v e s A [ U ( t , s ) ] t w h i c h i s e v a l u a t e d w i t h t h e u s e of the i m p a c t
a p p r o x i m a t i o n , n a m e l y t h a t t h e two f a c t o r s i n A l U ( t , s ) ] t =
[U(t, s)(U(t, s + Д в ) - l ) ] t a r e s t a t i s t i c a l l y i n d e p e n d e n t , and t h a t the p h a s e
c h a n g e s a r e c a u s e d by s u c c e s s i v e c o l l i s i o n s . J u s t a s in t h e c l a s s i c a l c a s e
t h e l i n e p r o f i l e i s L o r e n t z i a n p r o v i d e d t h e r e i s no o v e r l a p p i n g of l i n e s ,
and t h e d a m p i n g c o n s t a n t and s h i f t a r e given by
OO

7 = 2ïtNv f { 1 - e'"1'^ cosfrij - щ)} pdp (27)


о
IAEA-SMR-12/4,5 145

ß = 2 t N v J е'^'Ъ sin(r)i - rj f ) pdp (28)


о

where

< a | S a>
(29)
<»|S

and

v'is^dSj
ß v'(s2)ds2 + . . (30)

i s t h e p e r t u r b a t i o n e x p a n s i o n of t h e S - m a t r i x , d e f i n e d by

S = U(oo, - co)

In t h e s e e x p r e s s i o n s , /л r e p r e s e n t s i n e l a s t i c and r) e l a s t i c (phase changing)


c o l l i s i o n s . If the i n e l a s t i c c o l l i s i o n s a r e i g n o r e d , ц = 0, and t h e e x p r e s s i o n s
f o r 7 and ß r e d u c e to t h o s e obtained with the use of c l a s s i c a l t h e o r y . In
t h i s c a s e the p h a s e c h a n g e s c a n b e c a l c u l a t e d without r e s o r t to p e r t u r b a t i o n
theory.
T h e n e g l e c t of i n e l a s t i c c o l l i s i o n s is c e r t a i n l y j u s t i f i a b l e f o r f o r e i g n -
g a s b r o a d e n i n g w h e r e t h e e n e r g y l e v e l s of t h e r a d i a t i n g a t o m a r e so f a r
s e p a r a t e d t h a t the f r e q u e n c i e s p r e s e n t in the c o l l i s i o n , of the o r d e r of the
r e c i p r o c a l of the d u r a t i o n of the collision, a r e s m a l l e r than t h o s e which
c o r r e s p o n d to the e n e r g y - l e v e l s e p a r a t i o n s . S c h u l l e r and O k s e n g o r n (1969)
have i n v e s t i g a t e d the c a s e of t h e alkali a t o m s with t h e i r f i n e - s t r u c t u r e
d o u b l e t s , but have c o n c l u d e d t h a t the i n e l a s t i c c o l l i s i o n s c a u s e a s i g n i f i c a n t
c o n t r i b u t i o n to the b r o a d e n i n g and s h i f t only i n t h e c a s e of l i t h i u m . T h e
f u n d a m e n t a l r e a s o n f o r t h i s i s t h a t , although the c r o s s - s e c t i o n f o r i n e l a s t i c
c o l l i s i o n s i s quite l a r g e f o r t r a n s i t i o n s between c e r t a i n f i n e - s t r u c t u r e
c o m p o n e n t s , i t i s , e x c e p t f o r l i t h i u m , s i g n i f i c a n t l y s m a l l e r than t h a t f o r
p h a s e c h a n g e s of o r d e r unity ( i . e . t h e Weisskopf c r o s s - s e c t i o n ) .
The s i t u a t i o n i s quite d i f f e r e n t f o r b r o a d e n i n g by e l e c t r o n s . H e r e
i n e l a s t i c c o l l i s i o n s a r e o f t e n of d e c i s i v e i m p o r t a n c e , s i n c e the d u r a t i o n
of t h e c o l l i s i o n s i s m u c h s m a l l e r a s a r e s u l t of the m u c h h i g h e r t h e r m a l
v e l o c i t y of t h e e l e c t r o n s . In t h e c a s e of h y d r o g e n l i n e s , w h e r e t h e b r o a d e n i n g
by the e l e c t r o n i s s u p e r i m p o s e d on the e f f e c t of the q u a s i - s t a t i c f i e l d of the
i o n s , o v e r l a p p i n g of l i n e s o c c u r s a l s o , and r e c o u r s e m u s t be m a d e to
E q . (26).
If f o r t h i s o r any o t h e r r e a s o n t h e l i n e s of a s p e c t r u m o v e r l a p , E q s (27)
and (28) f o r 7 and ß a r e no l o n g e r v a l i d . O f f - d i a g o n a l e l e m e n t s of t h e
S - m a t r i x n e e d to be c a l c u l a t e d , and the m a t r i x f o r the whole s y s t e m of
o v e r l a p p i n g l e v e l s d i a g o n a l i z e d . The line p r o f i l e s a r e not L o r e n t z i a n , n o r
in g e n e r a l a r e they s i m p l y the s u m of the L o r e n t z i a n p r o f i l e s of e a c h c o m -
ponent in the o v e r l a p p i n g s y s t e m . L i t t l e d e t a i l e d e x p e r i m e n t a l o r t h e o r e t i c a l
i n v e s t i g a t i o n of such c a s e s h a s b e e n c a r r i e d out f o r n e u t r a l - a t o m b r o a d e n i n g
but m u c h m o r e h a s b e e n done f o r b r o a d e n i n g by c h a r g e d p a r t i c l e s .
146 HIND MARSH

3. INVERSE P O W E R AND L E N N A R D - J O N E S P O T E N T I A L S

3.1. The impact approximation

With the a s s u m p t i o n s of t h e i m p a c t a p p r o x i m a t i o n , c l a s s i c a l c o l l i s i o n -
b r o a d e n i n g t h e o r y , and a l s o q u a n t u m t h e o r y if c o l l i s i o n - i n d u c e d t r a n s i t i o n s
a r e i g n o r e d , s h o w s t h a t the s p e c t r a l l i n e will a l w a y s be L o r e n t z i a n i n s h a p e ;
t h e h a l f - i n t e n s i t y width and s h i f t , h o w e v e r , a r e s e n s i t i v e to t h e c h o i c e of
p o t e n t i a l . R e c a l l i n g the r e s u l t s of s e c t i o n 1, we have

7 = NvOj
and
ß = NVOi

w h e r e crr and Oj a r e given by E q s (5) and (6).


How the v a l u e s of 7 and ß depend on V(R) i s e x a m i n e d below.
(a) C o n s i d e r V(R) = ± C p R p . F o r t h i s g e n e r a l i n v e r s e - p o w e r p o t e n t i a l ,
i n t e g r a t i o n of E q . (10) by p a r t s y i e l d s t h e r e s u l t

f r o m w h i c h i t f o l l o w s that
, \ 2/(p -1) r -|2/(p-l) . N

and
= [ш]
ст. = a. t a n - ^ Ц - (32)
1 г P_1

p r o v i d i n g t h a t p > 3. The sign of crr i s a l w a y s p o s i t i v e ; t h e sign of ст4


i s t h e s a m e a s t h a t of V(R). C l e a r l y t h e n , the r a t i o \ß/y\ i s t a n (7г/(p - 1)).
T h e c o n n e c t i o n b e t w e e n W e i s s k o p f 1 s s i m p l i f i e d t r e a t m e n t , which g i v e s
a z e r o s h i f t , and t h e m o r e d e t a i l e d r e s u l t s of the L i n d h o l m - F o l e y t r e a t m e n t
d e s c r i b e d h e r e , m a y be u n d e r s t o o d r e a d i l y . W e i s s k o p f a s s u m e s only s t r o n g
c o l l i s i o n s to be e f f e c t i v e (that i s , c o l l i s i o n s f o r which rj > 1 r a d i a n , and
p < po. w h e r e n(p 0 ) = 1) a n d n e g l e c t s e n t i r e l y the e f f e c t of w e a k c o l l i s i o n s .
Now f o r a s t r o n g c o l l i s i o n , c o s rj(p) and s i n rj(p') a r e r a p i d l y o s c i l l a t i n g
f u n c t i o n s which a v e r a g e a p p r o x i m a t e l y to z e r o . T h u s , s t r o n g c o l l i s i o n s
give y x 7rNvpp and ß ~ 0. T h e w e a k , d i s t a n t c o l l i s i o n s , on t h e o t h e r hand,
c a u s e s m a l l p h a s e s h i f t s , s o t h a t c o s n ( p ) ~ 1 and sinr)(p) ~ rj(p); f r o m this it
f o l l o w s t h a t y ~ 0 and ß ~ 27rNv<r)X w h e r e <(г)У i s t h e m e a n p h a s e s h i f t
o c c u r r i n g b e t w e e n two s t r o n g c o l l i s i o n s . C l o s e c o l l i s i o n s , t h e n , c a u s e
m o s t of t h e b r o a d e n i n g of t h e line and the d i s t a n t c o l l i s i o n s a r e r e s p o n s i b l e
f o r the s h i f t .
(b) C o n s i d e r V(R) = - C 6 R . Substitution of p = 6 and t h e a s s u m p t i o n of
t h e n e g a t i v e s i g n in (a) l e a d s i m m e d i a t e l y to the e x p e c t e d b r o a d e n i n g and
s h i f t f o r a v a n - d e r - W a a l s p o t e n t i a l so that
, 2/5 3/5
7 = 4.08 (C 6 /tl) v N
and
ß = -2.96 ( C 6 / î ï ) 2 / V / 5 N
IAEA-SMR-12/4, 5 147

and t h e r a t i o 2 T / ß = - 2 . 8 . It w a s in f a c t t h e f a i l u r e of m a n y o b s e r v a t i o n s
to p r o d u c e a r a t i o i n e v e n a p p r o x i m a t e a g r e e m e n t w i t h t h i s w h i c h l e d s o m e
i n v e s t i g a t o r s to e x p l o r e t h e p o s s i b i l i t i e s of t h e L e n n a r d - J o n e s p o t e n t i a l ,
(c) C o n s i d e r V(K) = C 1 2 R " 1 2 - C 6 R " 6 . T h e L i n d h o l m - F o l e y t h e o r y i n t h e
i m p a c t a p p r o x i m a t i o n w a s d e v e l o p e d f o r the L e n n a r d - J o n e s (12, 6)
p o t e n t i a l by B e h m e n b u r g (1964) and i n d e p e n d e n t l y by H i n d m a r s h , P e t f o r d
and S m i t h (1967). H e r e w e h a v e

. _ 6 3 7Г С12 л . п 37Г Сб -5
ч(р)
" 256 " Т К "

ч 2/5

7 = 4* NV 3 / 5 (С 6 / Ü ) 2 / 5 В (а) (33)

and
\ 2/5
/я V 3 / 5
ß = 2ТГ ( I L ) т (С6 /П)2/5 S(«) (34)
7

f o l l o w i n g t h e n o t a t i o n of H i n d m a r s h e t a l . , w i t h

B ( a ) = / x s i n 2 { | ( a x " n -x" 6 )} dx (35)

S (a) = / x s i n {QX" 11 - x 5} dx (36)


о
and
\ll/5
63тг / 8 _6/5,6/5 _ , Ul/5
« = 7ГГ7Г I •=— J Vv TF
TL C . _J C/ С, .' (37)
256 V 3 7Г/ " 12 / 6

T h e f u n c t i o n s B(A) and S(A) a r e t a b u l a t e d b y t h e s e a u t h o r s f o r a w i d e r a n g e


of v a l u e s of a ; we show t h e m h e r e i n g r a p h i c a l f o r m i n F i g . 1, a l o n g w i t h
t h e f u n c t i o n (1/2)S(û')/B(Q'), w h i c h i s t h e r a t i o ß / y . In o r d e r to i n t e r p r e t
e x p e r i m e n t a l r e s u l t s in t e r m s of a (12, 6 ) - p o t e n t i a l , t h i s l a t t e r c u r v e i s
u s e d w i t h t h e e x p e r i m e n t a l r a t i o to d e t e r m i n e a a n d h e n c e S (a) and B ( A ) .
T h e n , w i t h the. u s e of e i t h e r of t h e m e a s u r e d v a l u e s -y/N o r ß / N , C 6 and C 1 2
a r e found b y a s t r a i g h t f o r w a r d c a l c u l a t i o n . U n f o r t u n a t e l y , t h e o s c i l l a t o r y
c h a r a c t e r of t h e f u n c t i o n s S and В s o m e t i m e s l e a d s to a m b i g u o u s r e s u l t s ,
a l t h o u g h i t i s o f t e n p o s s i b l e to d e d u c e the a p p r o p r i a t e p a i r of c o n s t a n t s .
(d) F i n a l l y w e c o n s i d e r V^R) = C 1 2 R" 12 - Cg R" 8 - C 6 R"6 . T h e e f f e c t
of t h e d i s p e r s i o n t e r m - C 8 R h a s b e e n i n v e s t i g a t e d by H i n d m a r s h , du
P l e s s i s a n d F a r r (1970). T h e p h a s e s h i f t f u n c t i o n b e c o m e s

„ ( P ) = Ü l l £12 - n _ 5» Ç a -7 . Çj g
256 îlv P 16 tiv P
8 "hv

Hence
/ 3 \2/ 5

3 / 5
= 4 N V (С6/Й)2/БВ(АГ,?) (38)
148 H1NDMARSH

a n d
4 2/5

ß = 2ТГ [2fJ NV 3 / 5 (C 6 /tl) 2 / 5 S ( e . Ç) (39)

where

B ( a , I) = / X sin2 l ( o x " u - ? x " 7 - x " 5 ) d x (40)

and

S ( a , i ) = J X s i n ( a x " 1 1 - f x " 7 - x" 5 )dx (41)


0

(42)

Since it i s c l e a r l y i m p o s s i b l e to deduce a l l t h r e e c o n s t a n t s f r o m t h e two


m e a s u r e d q u a n t i t i e s 7 and ß, H i n d m a r s h et a l . u s e a t h e o r e t i c a l m e t h o d
f o r e v a l u a t i n g the p a r a m e t e r c 8 / c j ^ 5 f o r e a c h c a s e i n v e s t i g a t e d , u s i n g a s
a b a s i s t h e w o r k of D a v i s o n (1968), and r e q u i r i n g only t h e k n o w l e d g e of
t h e q u a n t u m n u m b e r s n* and Í f o r the two s t a t e s i n v o l v e d in t h e t r a n s i t i o n .
T h e n f o r a g i v e n f , t h e f u n c t i o n s S and В c a n be c o m p u t e d and t h e c o n s t a n t s
C 6 and C 1 2 d e d u c e d e x a c t l y a s i n (c).

Lo
9,O «
FIG.l. F u n c t i o n s B(ot) and S ( a ) versus logu, a .
IAEA-SMR-12/4,5 149

3.2. The q u a s i - s t a t i c a p p r o x i m a t i o n

In t h i s a p p r o x i m a t i o n the i n t e n s i t y of r a d i a t i o n at any f r e q u e n c y i s
p r o p o r t i o n a l to the p r o b a b i l i t y of o c c u r r e n c e of that f r e q u e n c y . Including
the e f f e c t of m u l t i p l e i n t e r a c t i o n s (with the a s s u m p t i o n of s c a l a r additivity
of the f r e q u e n c y p e r t u r b a t i o n s ) t h e r e s u l t of t h e s e c a l c u l a t i o n s i s given
by B q . (18). We now apply t h i s r e s u l t to s o m e s p e c i f i c i n t e r a t o m i c
potentials.

(a) V(R) = ± C p R" p . P r o v i d e d t h a t p > 3, we have, u s i n g E q s (15) and (17),

47TN 3/Р
A(x) + iB(x) = exp Ь * { 2 - - (Ср/*) г(1Л |x|3/p
p/J

a r e s u l t o b t a i n e d by p a r t i a l i n t e g r a t i o n . F u r t h e r p r o g r e s s r e q u i r e s the
c h o i c e of a s p e c i f i c v a l u e f o r p, u n l e s s we c o n f i n e o u r a t t e n t i o n to the wing
of the l i n e . In t h i s c a s e we need c o n s i d e r the n e a r e s t - n e i g h b o u r i n t e r a c t i o n
only. If then t h e f r e q u e n c y p e r t u r b a t i o n Ди = u - u 0 i s c a u s e d by a single
p e r t u r b e r at R, t h e i n t e n s i t y in t h e r a n g e u, to + du m a y be equated to t h e
p r o b a b i l i t y of finding a lone p e r t u r b e r in t h e r e g i o n R, R + dR.
Thus
3+p

I(Au)dAu oc R 2 dR к | Д и | P
dAu (43)

(b) V(R) = - C 6 R~6 . T h e i n t e g r a l 1(Ды) now t a k e s the v a l u e 0 if u i s


p o s i t i v e (since all p e r t u r b a t i o n s a r e to low f r e q u e n c i e s ) and t h e v a l u e

1(Ди) (С 6 /-Ц) 1 / 2 ы|Ди|" 3 / 2 exp [ - 4 ? r C 6 N 2 / 9R] Ди |] (44)

if Ди i s n e g a t i v e .
T h e i n t e n s i t y m a x i m u m o c c u r s at

2
A i W - f ^ N (45)

showing t h a t the q u a s i - s t a t i c s h i f t i s p r o p o r t i o n a l to the s q u a r e of the


p e r t u r b e r d e n s i t y f o r a v a n - d e r - W a a l s i n t e r a c t i o n . (This c o n t r a s t s with
t h e l i n e a r d e p e n d e n c e of t h e i m p a c t s h i f t . ) On t h e high f r e q u e n c y side of
t h e m a x i m u m the i n t e n s i t y drop i s p r e d o m i n a n t l y e x p o n e n t i a l ; in the f a r
l o w - f r e q u e n c y wing t h e v a r i a t i o n i s p r o p o r t i o n a l to Ди
(c) V(R) = C 1 2 R " 1 2 - C 6 R" 6 . T h e m o r e d i f f i c u l t p r o b l e m of c a r r y i n g
out the q u a s i - s t a t i c t h e o r y f o r a L e n n a r d - J o n e s p o t e n t i a l w a s f i r s t solved
by B e r g e o n , Robin, and V o d a r (1952) and B e r g e o n (1954), who r e s t r i c t e d
t h e i r c a l c u l a t i o n s to the r e g i o n of high p e r t u r b e r d e n s i t y b e c a u s e of c o m p u -
t a t i o n a l d i f f i c u l t i e s . R e c e n t l y t h i s w o r k h a s b e e n extended by F a r r and
H i n d m a r s h (196 8) to t h e l o w - d e n s i t y r e g i o n .
A s b e f o r e , t h i s w o r k i s done with the a s s u m p t i o n t h a t t h e i n d i v i d u a l
f r e q u e n c y p e r t u r b a t i o n s m a y be added s c a l a r l y . It i s c o n v e n i e n t to d e s c r i b e
the p o t e n t i a l in t e r m s of i t s r a d i u s and depth p a r a m e t e r s , cr and e
respectively, where

<r= ( C 1 2 / C 6 ) 1 / 6 , e = iCg/C12
150 HIND MARSH

and t h e n to w o r k i n t e r m s of t h e r e d u c e d v a r i a b l e s

t 2 = 4 e x , r) = Дсо/4е, 5 = TTNCT3/3

If we d e f i n e a f u n c t i o n
-l
A'(x) + iB'(x) = [ A(x) + iB(x)]6

it i s p o s s i b l e to w r i t e E q . (18) in the f o r m

I (Ли) = I t e"6A'Ct) c o s { 6 B ' (t) + nt2} dt

apart f r o m a constant factor.


T h e f u n c t i o n A' (t) + iB'(t) i s given by
00

A'(t) + i B ' ( t ) = - t ^ ^ j t k +

k=0

-0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3
T)
FIG.2. l o g I ( n ) versus т]. ( a ) f o r & = 0 . 0 1 ;
IAEA-SMR-12/4,5 151

T h e i n t e g r a l 1(Ди) c o n v e r g e s only slowly, e s p e c i a l l y at low v a l u e s of


p e r t u r b e r d e n s i t y (low 6), and c a n only be e v a l u a t e d a f t e r a lengthy n u m e r i c a l
c o m p u t a t i o n , d u r i n g which it i s n e c e s s a r y to u s e an a s y m p t o t i c a p p r o x i m a t i o n
f o r A and В at l a r g e v a l u e s of t . T h e p r o f i l e s c o m p u t e d by H i n d m a r s h et a l .
a r e shown in F i g s 2(a), (b) and (c). V e r y r e c e n t l y M a h a n (1972) h a s
found an a n a l y t i c a l e x p r e s s i o n f o r t h e l o w - d e n s i t y a p p r o x i m a t i o n . T h e
m o s t n o t e w o r t h y f e a t u r e of t h i s c a l c u l a t i o n i s t h a t at low 6, s a t e l l i t e b a n d s
a p p e a r on t h e l o w - f r e q u e n c y wing at f r e q u e n c i e s c o r r e s p o n d i n g to u 0 - e ,
u0 - 2 e , T h e y a r e , of c o u r s e , h e r e p r e d i c t e d to be m u c h s h a r p e r
t h a n t h e o b s e r v e d s a t e l l i t e f e a t u r e s , a s no i m p a c t b r o a d e n i n g i s i n c l u d e d
in t h e c a l c u l a t i o n .
H o w e v e r , it i s c l e a r t h a t the a p p e a r a n c e of t h e s e b a n d s , at l e a s t in
s o m e c a s e s , i s a p u r e l y s t a t i s t i c a l p h e n o m e n o n , a r i s i n g f r o m the f a c t t h a t
the p o t e n t i a l g o e s t h r o u g h a m i n i m u m at an e n e r g y c o r r e s p o n d i n g to a
f r e q u e n c y of u 0 - e .

-0.6 -0.5 -0.Д -Ü3 -0.2 -0.1 0.0 0.1 0.2 0.3

ÎI
BIG. 2. ( c o n t ' d ) (b) for 6 = 0 . 0 2 ;
152 HIND MARSH

3.3. General theory

T h e d i f f i c u l t i e s i n h e r e n t i n a t h e o r y of p r e s s u r e b r o a d e n i n g , which
d e s c r i b e s t h e s h i f t , width and shape of a s p e c t r a l l i n e u n d e r a l l c o n d i t i o n s
and which i s not s u b j e c t to the r e s t r i c t i o n s of e i t h e r the i m p a c t o r q u a s i -
s t a t i c a p p r o x i m a t i o n s , a r e s u c h that no g e n e r a l a n a l y t i c a l e x p r e s s i o n f o r
the line s h a p e c a n be found. An a p p r o x i m a t e solution i s a c h i e v e d if t h e
following a s s u m p t i o n s a r e m a d e :
(1) T h e a t o m i c r a d i a t i o n s u f f e r s f r e q u e n c y c h a n g e s , and t h e r e f o r e p h a s e
c h a n g e s , a s a r e s u l t of c o l l i s i o n s b e t w e e n r a d i a t o r s and p e r t u r b e r s .
(2) P e r t u r b e r s , w h i c h a r e d i s t r i b u t e d r a n d o m l y i n s p a c e , follow s t r a i g h t
p a t h s with c o n s t a n t v e l o c i t y r e l a t i v e to the o p t i c a l l y a c t i v e a t o m s .
(3) T h e d u r a t i o n of a c o l l i s i o n i s p r o p o r t i o n a l to t h e i m p a c t p a r a m e t e r .
(4) F r e q u e n c y p e r t u r b a t i o n s c a u s e d by c o l l i s i o n s which o v e r l a p in t i m e
a r e additive.
(5) T h e p h a s e c h a n g e s u f f e r e d during a c o l l i s i o n i s t a k e n to be a l i n e a r
f u n c t i o n of t i m e . T h i s i s equivalent to a p p r o x i m a t i n g t h e c o m p l i c a t e d
t i m e d e p e n d e n c e of Au(t) by a c o n s t a n t f r e q u e n c y change d u r i n g t h e
collision.

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6


T]

FIG. 2 . ( c o n t ' d ) (c) for 6 = 0 . 0 6 .


IAEA-SMR-12/4, 5 153

The t i m e - a v e r a g e d phase change i s written a s

i ! , ( t , s )
[e ] = e-G(s) + iK(s)

in which c a s e the i n t e n s i t y d i s t r i b u t i o n m a y b e w r i t t e n , f r o m E q s (3) and (4)

I(u) = f e ^ cos{K(s) + (u - u 0 ) s } d s (48)

and it can be shown ( L i n d h o l m 1945) that


о
2
(1 - c o s rjp) (s - T p ) - — sinrip + 2т р
G(s) = ^ Nvop P

00

К p s) - s) - sin s + 2s (49)
•I
+ ; N7a„ (1 - COS (Tp Kp

and
s

ъ
K(s) = ) m a p

(1 - c o s r?p) — + (s - Tp) sin Г]р
p

•^Nvop (1 - c o s к s) — + (т - s) sin к s (50)


Р Kp v

w h e r e f o r a c o l l i s i o n of i m p a c t p a r a m e t e r p, тр i s the c o l l i s i o n t i m e ,
Kp i s the p h a s e c h a n g e p e r unit t i m e during c o l l i s i o n , r]p = к р т р i s t h e
t o t a l p h a s e c h a n g e p e r c o l l i s i o n and crp = 2npůp i s the c r o s s - s e c t i o n f o r
s u c h a c o l l i s i o n . B e h m e n b u r g (1968) h a s e v a l u a t e d t h e s e e x p r e s s i o n s f o r
a L e n n a r d - J o n e s p o t e n t i a l . It should be noted t h a t the a p p r o x i m a t i o n
r e m o v e s a l t o g e t h e r t h e s a t e l l i t e band by i n s i s t i n g on a u n i f o r m r a t e of
c h a n g e of p h a s e .
A d i f f e r e n t a p p r o a c h to t h e p r o b l e m of finding a g e n e r a l t h e o r y h a s
b e e n m a d e by H i n d m a r s h and F a r r (1969). H e r e the s t a r t i n g point i s the
q u a s i - s t a t i c line p r o f i l e , c a l c u l a t e d f o r V(R) = C 1 2 R~ - C g R " 6 , which
h a s a l r e a d y b e e n d i s c u s s e d . U s i n g the f a c t t h a t a F o u r i e r a n a l y s i s of a
f i n i t e wave t r a i n of f r e q u e n c y ы a v e r a g e d o v e r r a n d o m l i f e t i m e s , y i e l d s
a L o r e n t z p r o f i l e with d a m p i n g c o n s t a n t у ( w h e r e 7" 1 i s t h e m e a n l i f e t i m e ) ,
H i n d m a r s h and F a r r give a s an a p p r o x i m a t e e x p r e s s i o n f o r the line shape

(51)
^ - / (0 u - f f l

w h e r e y(w')" 1 i s t h e m e a n d u r a t i o n of wave t r a i n s of f r e q u e n c y u 1 , and


Is (W) i s t h e q u a s i - s t a t i c i n t e n s i t y d i s t r i b u t i o n . (The c o n t i n u o u s change
i n u 1 , a s a p e r t u r b e r f l i e s p a s t an o p t i c a l l y a c t i v e a t o m , i s not, of c o u r s e ,
s t r i c t l y e q u i v a l e n t to a s e q u e n c e of v a l u e s of u' l a s t i n g f o r f i n i t e d u r a t i o n s . )
154 H I N D MARSH

F o r t h e p u r p o s e of c a l c u l a t i n g I(u) the l i n e i s d i v i d e d i n t o two m a i n


r e g i o n s , the i m p a c t r e g i o n w h e r e the q u a s i - s t a t i c calculation i s invalid,
and t h e q u a s i - s t a t i c r e g i o n w h e r e I s ( u ' ) f o r m s a s a t i s f a c t o r y s t a r t i n g p o i n t
f o r the c a l c u l a t i o n of t h e p r o f i l e . T h e b o u n d a r y b e t w e e n t h e s e two r e g i o n s
on the l o w - f r e q u e n c y wing o c c u r s at u g , w h e r e u g m a y be e s t i m a t e d a s
d e s c r i b e d i n E q . (11). T h e c o n t r i b u t i o n to I(u) f r o m w > u g (note t h a t wg < u 0 )
i s c a l c u l a t e d by t a k i n g I s (co')du' w i t h i n t h e i m p a c t r e g i o n and g i v i n g i t a
L o r e n t z i a n d i s t r i b u t i o n of w i d t h 2y and s h i f t ß c a l c u l a t e d a c c o r d i n g t o
H i n d m a r s h e t a l . (1967) f o r t h e p a r t i c u l a r i n t e r a c t i o n p o t e n t i a l u n d e r
c o n s i d e r a t i o n . Since t h e q u a s i - s t a t i c i n t e n s i t y o n t h e h i g h - f r e q u e n c y w i n g
i s v e r y low, i t m a y b e s e t e q u a l to z e r o , so t h a t t h e l i n e s h a p e I(u) i s
g i v e n by t h e e x p r e s s i o n

T h e m e a n l i f e t i m e s a s s o c i a t e d with t h e f r e q u e n c i e s u ' < и a r e e s t i m a t e d


o n t h e b a s i s of an i d e a a d v a n c e d by K u h n and L o n d o n (1934), n a m e l y t h a t
t h e t i m e - v a r y i n g f r e q u e n c y w(t) of a c o n t i n u o u s l y p e r t u r b e d w a v e t r a i n m a y
b e c o n s i d e r e d t o r e m a i n u(0) f o r so l o n g a s t h e p h a s e of u(t) d o e s not d i f f e r
f r o m w(0) by m o r e t h a n s o m e a r b i t r a r y a m o u n t . C h o o s i n g t h i s a m o u n t t o
b e 1 r a d i a n , H i n d m a r s h a n d F a r r d e f i n e t h e s e m i - l i f e t i m e T of t h e f r e q u e n c y
u(0) by t h e c o n d i t i o n
T

w(t)dt - w(0)T = 1
0
T h e n , r e p l a c i n g u(t) b y t h e f i r s t n o n - z e r o t e r m ( t e r m n) i n t h e T a y l o r
e x p a n s i o n of u(t) a b o u t t h e p o i n t t = 0, the c o n d i t i o n f o r T b e c o m e s
-|l/(n+l)
n + 1
(d n u(t)/dt") t =o J

Using this expression, the m e a n lifetimes f o r all f r e q u e n c i e s between


Ug and (Jo - e , w h e r e e i s t h e d e p t h of t h e L e n n a r d - J o n e s p o t e n t i a l , m a y
b e e s t i m a t e d by c o n s i d e r i n g only the a t t r a c t i v e p a r t of t h e p o t e n t i a l ; t h e
m e a n l i f e t i m e f o r t h e f r e q u e n c y uQ - e i s c a l c u l a t e d u s i n g t h e f u l l e x p r e s s i o n
f o r t h e p o t e n t i a l , and t h i s s a m e v a l u e i s u s e d f o r a l l f r e q u e n c i e s l e s s t h a n
u 0 - e ( f u r t h e r out on t h e l o w - f r e q u e n c y w i n g ) . T h i s l a s t a p p r o x i m a t i o n i s
not s e r i o u s a s the low v a l u e of I s (u') in t h i s r e g i o n e n s u r e s t h a t t h e m a j o r
c o n t r i b u t i o n t o I(w) c o m e s f r o m f r e q u e n c i e s g r e a t e r t h a n <Jq - e .

4. A SURVEY O F E X P E R I M E N T A L R E S U L T S F O R N E U T R A L - A T O M
BROADENING

4.1. impact region m e a s u r e m e n t s

4. 1 . 1 . Foreign-gas broadening

It i s , of c o u r s e , i n t h e i m p a c t r e g i o n w h e r e t h e e x p e r i m e n t a l s t u d y
of c o l l i s i o n - b r o a d e n e d s p e c t r a l l i n e s i s m o s t e a s i l y i n t e r p r e t e d q u a n t i t a t i v e l y .
IAEA-SMR-12/4,5 155

With the t h e o r i e s of s e c t i o n 3, it i s p o s s i b l e to d e t e r m i n e two p a r a m e t e r s


of a d i f f e r e n c e p o t e n t i a l . If one of t h e s t a t e s i s a g r o u n d s t a t e , and if the
potential for this state has been determined f r o m elastic scattering m e a s u r e -
m e n t s , t h e b r o a d e n i n g d a t a p r o v i d e the p a r a m e t e r s f o r t h e e x c i t e d s t a t e .
S e v e r a l e x p e r i m e n t a l s t u d i e s of i m p a c t - r e g i o n c o l l i s i o n b r o a d e n i n g
h a v e b e e n i n t e r p r e t e d in t e r m s of a ( 1 2 , 6 ) - i n t e r a c t i o n . T h e f i r s t of t h e s e
w a s B e h m e n b u r g ' s (1964) study of t h e s o d i u m l i n e (3 2 S!/ 2 - 3 P 3 / 2 ) p e r t u r b e d
by h e l i u m and by a r g o n . In t h e c a s e of a r g o n , the s h i f t - t o - b r o a d e n i n g r a t i o
l i e s on t h e o s c i l l a t i n g p a r t of the S ( a ) / 2 B ( a ) c u r v e , and so t h e i n t e r a c t i o n
c o n s t a n t s c a n n o t be d e t e r m i n e d u n a m b i g u o u s l y . In t h e c a s e of h e l i u m , the
m e a s u r e d C 6 of (33 ± 10)X 10" 66 J - c m 6 i s a n o m a l o u s l y l a r g e c o m p a r e d to
t h e t h e o r e t i c a l v a l u e of 2.9 X 10" 66 J - c m 6 , and t h e s h i f t to a l o w e r f r e q u e n c y
i s unusual for this p e r t u r b e r .
Smith (1967) i n v e s t i g a t e d the c a l c i u m i n t e r c o m b i n a t i o n line (4 S 0 - 4 P x )
f o r m e d i n a b s o r p t i o n i n a t m o s p h e r e s of h e l i u m , neon, a r g o n , and k r y p t o n
at t e m p e r a t u r e s of a p p r o x i m a t e l y 1030 К and p e r t u r b e r d e n s i t i e s up to
7 X 10 18 cm" 3 . In a l l c a s e s , i m p a c t r e g i o n c o n d i t i o n s w e r e w e l l s a t i s f i e d
with s h i f t and b r o a d e n i n g v a r y i n g l i n e a r l y with p e r t u r b e r d e n s i t y . The
r e s u l t s w e r e i n t e r p r e t e d using t h e v e r s i o n of H i n d m a r s h e t a l . (1967) of
the L i n d h o l m - F o l e y t h e o r y f o r a (12, 6 ) - p o t e n t i a l .

T h e following i n t e r a c t i o n c o n s t a n t s w e r e obtained:

c6 с
Atom pair
10"66 J - c m 6 10" 109 J-cm12

Ca-He 2.0 ± 0.2 0.97


Ca-Ne 1.8 ± 0.2 1. 1
Ca-Ar 10.8 ± 0 . 8 7.4
Ca-Kr 25 ± 2 54

T h e s e C 6 v a l u e s a r e a l l h i g h e r than t h e t h e o r e t i c a l v a l u e s by a f a c t o r
of about 2, a r e s u l t w h i c h i s a t t r i b u t e d by H i n d m a r s h et a l . (1970) to the
n e g l e c t of h i g h e r - o r d e r d i s p e r s i o n t e r m s in the i n t e r a t o m i c i n t e r a c t i o n
( s e e below).
A s e a r c h i n g t e s t of t h e v a l i d i t y of the (12, 6 ) - p o t e n t i a l i n the i n t e r -
p r e t a t i o n of c o l l i s i o n b r o a d e n i n g w a s applied by Vaughan and Smith (196 8),
who studied t h e r e d l i n e of k r y p t o n (4p 5 ( 2 P 3 / 2 ) 5s 3 / 2 2 - 4p 5 ( 2 P 3 / 2 ) 5p 3/2 2 )
p e r t u r b e d by low p r e s s u r e s of h e l i u m , neon, a r g o n , and k r y p t o n at t e m p e r a -
t u r e s of 80'К and 295 K. T h e y w e r e thus able to t e s t the c o m p l e x t e m p e r a t u r e
d e p e n d e n c e p r e d i c t e d by H i n d m a r s h et a l . a s w e l l a s to m e a s u r e t h e i n t e r -
a c t i o n c o n s t a n t s . T h e s h i f t - t o - b r o a d e n i n g r a t i o s at t h e two t e m p e r a t u r e s
w e r e f i t t e d a s c l o s e l y a s p o s s i b l e to the t h e o r e t i c a l S(a)/2B(a) c u r v e , with
the r e s t r i c t i o n t h a t e a c h p a i r should show the c o r r e c t t e m p e r a t u r e
d e p e n d e n c e . T h e c o r r e s p o n d i n g v a l u e s of S(a) and B(a) w e r e t h e n used
to p r e d i c t t h e t e m p e r a t u r e e f f e c t s in shift and b r o a d e n i n g i n d i v i d u a l l y .
T h e s e a r e c o m p a r e d in the following list:
ся
СП

TABLE I. R E S U L T S O F LOW-DENSITY M E A S U R E M E N T S

Carbon
Helium Neon Argon Krypton Xenon Nitrogen
tetrafluoride

Width Shift Width Shift Width Shift Width Shift Width Shift Width Shift Width Shift

Na 5896 P 1 / 2 0.742 -0.196 0.49 -0.214

5890 P 3 / 2 0.689 -0.213 0.49 -0.223

К 7699 P j / 2 1.01 -0.42 0.82 -0.36

7665 P 3 / 2 1.01 -0.36 0.82 -0.30

К 4047 P 1 / 2 1.45 0.71 2.20 -9.2 1.65 -0.83

4044 P 3 / 2 2.02 0.82 -0.16 2.58 -8.3 1. 89 -1.02

Rb 7947 P 1 / 2 0.595 +0.228 0.627

7800 P 3 / 2 0.735 -0.092 0.855

Rb 4216 P 1 ( i 2 2.77 +0.93 1.30 +0.22 2.21 -1.2 1.51

4202 P 3 / 2 1.88 +0.43 0.73 -0.16 2.56 -1.0 1.01

Cs 8943 P j y 2 +0.128 -0.04 0.30 -0.238 0.28 -0.20 0.49 -0.25 -0.29

8521 P 3 / 2 +0.015 -0.08 0.30 -0.215 0.28 -0.20 0.23 -0.25 -0.23

Cs 4593 P 1 ( / 2 +0.51 -0.70 1.1 - 0 . 62 -0.65


4555 P 3 / 2 +0.26 -0.63 3.2 -0.62 - 0 . 65

AIL units are c m " 1 ( r e l . density) 1 . Additional measurements ate reported by Ch'en et al. foi broadening by krypton in t h e 3rd and 4th Cs doublets, and shifts oř г Р 3 / 2 up to the 20th doublet. Relative
density is defined as the ratio of the actual density of the gas to the density the s a m e gas would have at 0°C and 760 Torr.
IAEA-SMR-12/12 157

Shift at 2 9 5 K / S h i f t at 80К Width at 295 K / W i d t h at 80 К

Perturber Observed Predicted Observed Predicted

He 2.62 2.16 1.87 1.73

Ne 0.93 0.84 1.67 1,70

Ar 2.29 1.79 2.07 1.64

Kr 1.47 1.43 1.48 1.43

In the c a s e of a r g o n a s e r i o u s d i s c r e p a n c y a r i s e s , which Vaughan and


Smith s u g g e s t m a y be due e i t h e r to the i n a d e q u a c y of the t h e o r e t i c a l t r e a t m e n t
f o r p o t e n t i a l s which a r e n e i t h e r d e e p l y a t t r a c t i v e n o r s h a r p l y r e p u l s i v e , o r
to the w r o n g c h o i c e of i n t e r a c t i o n p o t e n t i a l . To t e s t the l a t t e r p o s s i b i l i t y ,
they c a l c u l a t e d the S(or), B ( f f ) - c u r v e s f o r ( 1 0 , 6 ) - and (18, 6 ) - p o t e n t i a l s , but
n e i t h e r m a d e m u c h d i f f e r e n c e in the a r g o n r e g i o n . The o b s e r v e d C 6 - v a l u e s
a r e in s a t i s f a c t o r y a g r e e m e n t with the Unsold c a l c u l a t i o n s :

C6(10"66 J-cm6)

Atom p a i r Observed Predicted

Kr-He 4.5 4.7


Kr-Ne 15.9 8.6
Kr-Ar 24.5 35.4
Kr-Kr 54.6 53.8

T h e study of a l k a l i - m e t a l d o u b l e t s h a s b e e n p u r s u e d s i n c e the e a r l y
d a y s of e x p e r i m e n t a l c o l l i s i o n b r o a d e n i n g ( F u c h t b a u e r a n d ' G o s s l e r , 1933;
W a t s o n and M a r g e n a u , 1933; Hull, 1936; P e t e r m a n , 1933; Ny and
C h ' e n , 1937), and a s t r i k i n g f e a t u r e of all such m e a s u r e m e n t s i s the
e x i s t e n c e of a p p a r e n t l y u n p r e d i c t a b l e d i f f e r e n c e s b e t w e e n c o m p o n e n t s of
the s a m e doublet p e r t u r b e d by the s a m e g a s . S c h u l l e r and O k s e n g o r n (1969)
have shown t h a t t h e 2 P]y 2 c o m p o n e n t b e h a v e s a s in L i n d h o l m ' s t h e o r y , but
f o r the 2 Pg/2 c o m p o n e n t t h e r e i s a v a r i a t i o n due to the a n i s o t r o p y of the
e x c i t e d s t a t e i n t e r a c t i o n . Applying t h e i r c a l c u l a t i o n to the c a s e of the
b r o a d e n i n g of the s o d i u m r e s o n a n c e l i n e s by a r g o n , they find t h a t the
c a l c u l a t e d s h i f t s a r e in good a g r e e m e n t with t h o s e m e a s u r e d by K l e m a n
and L i n d h o l m , but t h a t t h e r e i s a d i s c r e p a n c y in t h e h a l f - w i d t h s . T h e
i n t e r f e r e n c e with the c o l l i s i o n b r o a d e n i n g p r o c e s s by c o l l i s i o n a l e x c i t a t i o n
t r a n s f e r b e t w e e n the f i n e - s t r u c t u r e l e v e l s i s r e g a r d e d by s o m e a u t h o r s a s
being f u n d a m e n t a l to t h i s "problem, and both t h e o r e t i c a l (Callaway and B a u e r ,
1965) and e x p e r i m e n t a l ( K r a u s e , 1966; J o r d a n and F r a n k e n , 1966) e v i d e n c e
shows that t h e c r o s s - s e c t i o n s f o r t h e s e two p r o c e s s e s a r e of c o m p a r a b l e
s i z e . H o w e v e r , S c h u l l e r and O k s e n g o r n (1969) show t h a t t h i s p r o c e s s
h a s a m a r g i n a l e f f e c t , m e a s u r a b l e only in l i t h i u m .
A r e c e n t c o m p r e h e n s i v e study of the p r e s s u r e b r o a d e n i n g of the f i r s t
few l i n e s of the p r i n c i p a l s e r i e s of c a e s i u m by h e l i u m , neon, a r g o n , k r y p t o n .
T A B L E II. POTASSIUM P R I N C I P A L SERIES IN He, A r , AND K r

Helium Argon Krypton

Width Shift Width Shift Width Shift

К 4044 P 3 / 2 7.08 ± 0.2 0.37 ± 0.02 8..0 ±0.1 -2.22 ± 0.03 5.50 ± 0.15 -1.97 t 0.05

К 4047 P1/2 4.94 t 0.04 1.22 i 0.02 7.54 ± 0.05 -1.75 ± 0.08 6.6 ± 0.2 - 1 . 8 4 ± 0.05

Units of ÎO" 2 0 c m " 1 ( c m " 3 ) " 1 .


IAEA-SMR-12/12 159

xenon, and c a r b o n t e t r a f l u o r i d e h a s b e e n u n d e r t a k e n by C h ' e n , G a r r e t t ,


G i l b e r t and c o - w o r k e r s (1966 I, II; 1967 III, IV; 1969 V, VI). M e a s u r e m e n t s
have b e e n m a d e at p r e s s u r e s of up t o 300 a t m in s o m e c a s e s . T h e g e n e r a l
f e a t u r e s of t h e s e r e s u l t s a r e e x p l a i n e d by r e c e n t c l a s s i c a l g e n e r a l t h e o r i e s
(see below). T h e l o w - d e n s i t y m e a s u r e m e n t s , t h e r e s u l t s of w h i c h a r e
s u m m a r i z e d in T a b l e I along with t h e r e s u l t s of s o m e of the e a r l i e r w o r k
m e n t i o n e d above, a r e not i n t e r p r e t e d q u a n t i t a t i v e l y b e c a u s e of s o m e u n u s u a l
f e a t u r e s , which i n c l u d e n o n - l i n e a r i t y of the b r o a d e n i n g - v e r s u s - d e n s i t y c u r v e s
n e a r the o r i g i n and an a p p a r e n t l y v e r y s t r o n g t e m p e r a t u r e e f f e c t on the
b r o a d e n i n g at h i g h e r d e n s i t i e s . T h e r e is a p o s s i b i l i t y t h a t both of t h e s e
e f f e c t s a r e e x p e r i m e n t a l : t h e n o n - l i n e a r i t y a r i s i n g f r o m the u n c o r r e c t e d
e f f e c t of h y p e r f i n e s p l i t t i n g and i n s t r u m e n t a l s l i t width, which a m o u n t to
s o m e 0.6 c m " 1 , and the t e m p e r a t u r e e f f e c t a r i s i n g f r o m a n a l y s i s of l i n e s
w h o s e p e a k a b s o r p t i o n i s in e x c e s s of 50%. T h e r e i s s o m e e v i d e n c e t h a t
h e a v i l y a b s o r b e d p r o f i l e s c a n c a u s e o v e r e s t i m a t e d line w i d t h s ( M c C a r t a n , 1970).
R o s t a s and L e m a i r e (1971) have m e a s u r e d t h e c a e s i u m doublet 6 2 S - 7 2 P
b r o a d e n e d by h e l i u m and a r g o n . T h e s e m e a s u r e m e n t s , m a d e at low p r e s s u r e ,
r e p r e s e n t an i m p r o v e m e n t on t h o s e of C h ' e n and G a r r e t t , and a r e quoted
in T a b l e IV.
M c C a r t a n and H i n d m a r s h (to be p u b l i s h e d ) have m a d e a d e t a i l e d i n v e s t i -
g a t i o n of the s e c o n d doublet of t h e p o t a s s i u m p r i n c i p a l s e r i e s ( ^ S ^ 5 2 P 1 / 2 3 / 2 )
f o r m e d in a b s o r p t i o n in a t m o s p h e r e s of h e l i u m , a r g o n and k r y p t o n u n d e r
s t r i c t i m p a c t - r e g i o n c o n d i t i o n s . T h e r e s u l t s of t h i s study a r e s u m m a r i z e d
in T a b l e II. It w a s found t h a t not a l l of t h e s e could be f i t t e d to the S(a)/2B(a)
c u r v e s , a f a c t which the a u t h o r s a t t r i b u t e to the i n a d e q u a c y of the " s t r a i g h t
p a t h " a p p r o x i m a t i o n in t h e s e c a s e s . The i n t e r a c t i o n c o n s t a n t s d e d u c e d
by M c C a r t a n et a l . a r e

C 6 J- c m 6 C
12 J- c m 1 2

P P P
l/2 P
3/2 l/2 3/2

He - 9.2 X 10" 65 _ 7.6 X 10" 106


Ar - 6.6 X 10~64 - 5.8X 10" 106
64 64 106
Kr 4 . 8 X 10" 4.5 X 10" 1.2 X 10" 2.3 X 10" 106

C o m b i n i n g t h e s e v a l u e s with g r o u n d - s t a t e m e a s u r e m e n t s quoted by
B e r n s t e i n and M u c k e r m a n (1967) we obtain t h e following e x c i t e d - s t a t e
constants:

12
( C 6 'exc J. c m ^ 12 )exc J - c m
P P
l/2 P
3/2 l/2 P
3/2

65
He - 9.5 X 10" - 7.6 X 10 - 1 0 6
Ar - 6.9 X 10" 64 - 5.8 X 10
-106

-106
Kr 6.2 X 10" 64 5.5 X 10" 64 1.4 X 1 0 " " 2.3 X 10
160 HIND MARSH

T h e e x p e r i m e n t a l f a c t s r e g a r d i n g c o l l i s i o n b r o a d e n i n g in a l k a l i d o u b l e t s
m a y be s u m m a r i z e d a s f o l l o w s :

(1) T h e d i f f e r e n c e in s h i f t of the f i n e - s t r u c t u r e c o m p o n e n t s d e p e n d s on
s e r i e s m e m b e r and p e r t u r b e r , not on the n a t u r e of t h e a l k a l i .
(2) W h e r e t h e r e i s a h i g h - f r e q u e n c y s h i f t , t h e 2 P x / 2 c o m p o n e n t i s shifted
m o r e t h a n the 2 P 3( / 2 c o m p o n e n t . The r a t i o i s l a r g e r f o r the f i r s t s e r i e s
m e m b e r than the s e c o n d .
(3) D i f f e r e n c e s in s h i f t s to low f r e q u e n c i e s a r e u s u a l l y s m a l l , and t h e r e
i s a p p a r e n t l y no way of knowing which c o m p o n e n t shows the s t r o n g e r
shift.
(4) T h e b r o a d e n i n g of t h e 2 P 3 / 2 c o m p o n e n t i s n o r m a l l y slightly g r e a t e r
t h a n t h a t of the 2 Р ! / 2 c o m p o n e n t , although e x c e p t i o n s a r e found.

T a b l e III s h o w s , in c o l u m n s f o u r and f i v e , the s o r t of a g r e e r n e n t which


i s found b e t w e e n t h e o r e t i c a l C 6 - v a l u e s and t h o s e deduced f r o m c o l l i s i o n -
b r o a d e n i n g e x p e r i m e n t s using the L i n d h o l m - F o l e y t r e a t m e n t f o r a ( 1 2 , 6 ) -
p o t e n t i a l . On t h e whole, the e x p e r i m e n t a l C 6 - v a l u e s e x c e e d the t h e o r e t i c a l
o n e s by f a c t o r s of about two o r t h r e e . The l a s t c o l u m n s h o w s the e x p e r i -
m e n t a l v a l u e s when a ( 12, 8, 6 ) - p o t e n t i a l i s a s s u m e d . T h e r e i s in g e n e r a l
an i m p r o v e m e n t , which l e n d s s u p p o r t to the i d e a t h a t h i g h e r t e r m s in the
d i s p e r s i o n i n t e r a c t i o n (R~8 , R" 10 . . . ) m a y not be n e g l i g i b l e in the e x c i t e d

T A B L E III. COMPARISON O F E X P E R I M E N T A L AND T H E O R E T I C A L


C6-VALUES

C6 experimental
10"65 J - c m 6
C6 theoretical
Author Line Perturber
1 0 " 65 J. c m 6 , ( 1 2 , 6) ( 1 2 . 8, 6)

(1) C a 6573 He 0.062 0.2 ±0.02 0.10 ± 0.02

(1) Ca 6573 Ne 0.113 0.18 ± 0.02 0.10 ± 0.02

(1) Ca 6573 Ar 0.46 1.08 ± 0.08 0.23 ± 0.02

(1) C a 6573 Kr 0.70 2.53 ± 0.2 0.61 ± 0.06

(2) C a 4227 He 0.30 0.3 ±0.1 0.18 ± 0.06

(3) Ar 6965 Ar 2.4 9 ±4 2.9 ± 3

(4) К 4047 Kr 38.1 52 ± 15 30 ±9

(5) Sr 4607 Ar 2.62 4.3 ±0.4 2.8 ±0.8

(6) Kr 7 6 0 1 He 0.47 0.45 ± 0.09 0.36 ± 0.07

(6) Kr 7 6 0 1 Ne 0.86 1.59 ± 0.3 0.81 ± 0.15

(6) Kr 7 6 0 1 Ar 3.54 2.45 ± 0 . 5 1.05 ± 0.2

(6) Kr 7 6 0 1 Kr 5.38 5.46 ± 1.1 4.4 ± 1

(1) S m i t h ( 1 9 6 7 ) ; (2) H i n d m a i s h ( 1 9 5 9 ) ; (3) H i n d m a r s h , T h o m a s ( 1 9 6 1 ) ; (4) M c C a l t a n ,


Hindmarsh (1969); (5) F a i r , H i n d m a r s h ( 1 9 7 1 ) ; (6) V a u g h a n , S m i t h ( 1 9 6 8 ) .
IAEA-SMR-12/12 161

T A B L E IV. COMPARISON O F C s LINE R E S U L T S

Experiment Theory
Cs l i n e Gas Rostas, L e m a i r e Roueff
(1971) (1970)

X 4593 2 y/N 8.8 ±0.5 9.2

62S1/2 - 7 2 P l / 2 He e/N +1.5 ±0.1

2y/6 + 5 . 85 +6.3

X 4555 2 y/N 6.9 ±0.4

2 2 +0.73 ± 0.05
6 Sl/2 - 7 Рз/г He ß/N

2 y/ß +9.45

X 4593 2 y/N 6.7 ±0.5 4.9

62S1/Z- 72Pl/2 Ar ß/N -1.63 ±0.05

2 у/В -4.1 -11. 6

X 4555 2 y/N 5.8 ±0.3

Z 2 -1.55 ± 0.06
6 S l / 2 - 7 P3/2 Ar ß/N

2 y/ß -3.74

2 y / N and e / N a r e in units of 10 " 2 ° c m " ' / c m " 3 .

s t a t e . F i n a l l y , the c a l c u l a t i o n s of Roueff (1970) have b e e n c o m p a r e d with


e x p e r i m e n t by R o s t a s and L e m a i r e (1971) f o r the c a e s i u m line X 4593
( 6 2 S 1 / 2 _ 7 2 P i / 2 ) b r o a d e n e d by h e l i u m and a r g o n . The c a l c u l a t i o n s , which
do not i n c l u d e s p i n - o r b i t i n t e r a c t i o n , a r e not e x p e c t e d to apply to t h e o t h e r
c o m p o n e n t of the d o u b l e t , X 4555, which w a s , h o w e v e r , a l s o m e a s u r e d .
T a b l e IV c o m p a r e s the r e s u l t s of R o s t a s and L e m a i r e with the c a l c u l a t i o n
of R o u e f f , and shows the a g r e e m e n t to be highly s a t i s f a c t o r y .

4.1.2. Resonance broadening

R e s o n a n c e - b r o a d e n i n g c a l c u l a t i o n s in the i m p a c t a p p r o x i m a t i o n p r e d i c t
that p u r e r e s o n a n c e - b r o a d e n e d l i n e s a r e L o r e n t z i a n in s h a p e with a h a l f -
i n t e n s i t y width in r a d i a n - s " 1 of
i

Z 7 ( 5 á }
V \2j' + 1 / mw 0

w h e r e N i s the a t o m d e n s i t y , fjj- and u 0 "the o s c i l l a t o r s t r e n g t h and a n g u l a r


f r e q u e n c y , r e s p e c t i v e l y , of the r e s o n a n c e line, and j, j' a r e the a n g u l a r -
m o m e n t u m q u a n t u m n u m b e r s of the g r o u n d s t a t e and r e s o n a n c e s t a t e ,
r e s p e c t i v e l y . The width i s i n d e p e n d e n t of t e m p e r a t u r e , and t h e s h i f t i s
p r e d i c t e d to be z e r o . (See the r e v i e w of r e s o n a n c e b r o a d e n i n g by Kuhn and

to

T A B L E V. DENSITY D E P E N D E N C E O F LINE BROADENING

2 y / N at 80 К 2y/ti at 280 К 6/N


Element  Transition
10cm-'(cm*3)"' ÎO" 2 0 c m " 1 ( c m " 3 ) " 1 10"20 c m " 1 ( c m ' 3 ) " 1

He 1281 2'P! - 3 ' S 0 7.85 ± 0.4 8.1 ± 0.6 0 ± 0.1

6678 2'P, - 3 ' D , 7.8 ±0.4 7.9 ± 0 . 5 0 ± 0.05

Ne 6678 4 - 2P< 6.27 ± 0.15 6.2 ± 0.3 0 ± 0.1

At 7503 'Pi - 2 Pi 15.66 ± 0 . 7 15.0 ± 0.7 0 ± 0.2

7514 ' P i - 2P5 3.6 ±0.3 3.9 ± 0.4 0.07 ± 0.03

Кг 7685 'Pi - V 10.8 ± 0.5 11.0 ± 0 . 6 0 ± 0.5

7587 3 5
Pi * P 12.8 ± 0.2 13.1 ± 0 . 6 0.1 ± 0 . 1
IAEA-SMR-12/12 163

L e w i s (1969).) T h e v a l u e of t h e c o n s t a n t kjj. d e p e n d s on j, j' and the


a p p r o x i m a t i o n s m a d e in the c a l c u l a t i o n . Some r e c e n t v a l u e s a r e :

k
l/2.3/2
k k k k
o,i l/2, 3/2 l/2,1/2 l/2,1/2
Ali, G r i e m (1965, 1966) 1 1 1 1.00
O m o n t , M e u n i e r (1968) 1.04 - - -

Stacey, C o o p e r (1969) 1.04 1.04 0.903 1.15

B e c a u s e of the d i f f i c u l t i e s of s e l f - a b s o r p t i o n in e m i s s i o n l i n e s , m o s t
m e a s u r e m e n t s m a d e d i r e c t l y on r e s o n a n c e l i n e s ( l a r g e l y in the c a s e of
alkali m e t a l s ) h a v e b e e n m a d e in a b s o r p t i o n . M o s e r and Schulz (1959) have
t a b u l a t e d the e x p e r i m e n t a l r e s u l t s a v a i l a b l e at t h a t t i m e , and d i s c r e p a n c i e s
a m o u n t i n g to s e v e r a l o r d e r s of m a g n i t u d e o c c u r b e t w e e n d i f f e r e n t e x p e r i -
m e n t s and b e t w e e n e x p e r i m e n t and t h e o r y . Since t h e n , Y a ' a k o b i (1966, 1968)
h a s m a d e m e a s u r e m e n t s on the r e s o n a n c e l i n e s of l i t h i u m , but t h e s e r e s u l t s
a l s o s e e m to be not v e r y q u a n t i t a t i v e .
A m o r e a c c u r a t e t e c h n i q u e i n v o l v e s t h e i n d i r e c t study of the b r o a d e n i n g
of a r e s o n a n c e l e v e l by m a k i n g m e a s u r e m e n t s on an e m i s s i o n line w h o s e
l o w e r s t a t e i s t h e r e s o n a n c e l e v e l . Q u a n t i t a t i v e r e s u l t s w e r e f i r s t obtained
t h i s way by H i n d m a r s h and T h o m a s (1961), who i n v e s t i g a t e d the s e l f -
b r o a d e n i n g i n a r g o n and w e r e able to e s t i m a t e t h e o s c i l l a t o r s t r e n g t h of
the r e s o n a n c e line X 1048 by studying the s e l f - b r o a d e n i n g of the line X 8264.
L e w i s , Ř e b b e c k , and Vaughan (1969) adopted the s a m e m e t h o d and m e a s u r e d
t h e r e s o n a n c e b r o a d e n i n g of t h e 4 2 P s t a t e s of p o t a s s i u m by studying i n
e m i s s i o n the l i n e s (4 2 P 1 / 2 3 / 2 - n 2 S 1 / 2 , n = 6, 7, 8). T h i s gave the v a l u e s
k = 3 k = 1 2 4 3 w i t h t h e r a t i к
l/2,3/2 ^ ^ i °- ' l/2,l/2 " ± °- ' ° 1/2,3/г/к1/2,1/2 =
1.09'± 0.06. Kuhn and h i s c o - w o r k e r s (Kuhn, Vaughan, 1964; Kuhn,
L e w i s , 1967; Vaughan, 1966a, b, 1968; S t a c e y , Vaughan, 1964) have m a d e
a m a j o r i n v e s t i g a t i o n of r e s o n a n c e b r o a d e n i n g in the i n e r t g a s e s h e l i u m ,
neon, a r g o n , and k r y p t o n u s i n g t h i s i n d i r e c t t e c h n i q u e , with the o b j e c t of
t e s t i n g the r e s u l t s of t h e o r y . In all c a s e s studied the v a r i a t i o n of h a l f -
width with d e n s i t y w a s v e r y c l o s e to l i n e a r o v e r a d e n s i t y r a n g e of
10 16 - 4X 10 17 c m " 3 . The r e s u l t s obtained f o r l i n e s l e a d i n g to the u p p e r
s t a t e of a s t r o n g r e s o n a n c e line a r e given in T a b l e V.
In all c a s e s t h e r e i s l a r g e b r o a d e n i n g , no m e a s u r a b l e s h i f t and no
m e a s u r a b l e t e m p e r a t u r e e f f e c t . O t h e r l i n e s w e r e m e a s u r e d which a r e
t r a n s i t i o n s to a w e a k r e s o n a n c e l e v e l , and t h e s e show 5 - 1 0 t i m e s s m a l l e r
b r o a d e n i n g , an i n c r e a s e of b r o a d e n i n g with t e m p e r a t u r e and a n o n - z e r o
s h i f t ; in t h e s e l i n e s a h i g h e r - o r d e r i n t e r a c t i o n i n t e r f e r e s with the r e s o -
nance broadening.
An i n t e r e s t i n g p h e n o m e n o n h a s shown up in t h e s e r a r e - g a s e x p e r i m e n t s ,
n a m e l y t h a t the L o r e n t z width e x t r a p o l a t e d to z e r o d e n s i t y i s s i g n i f i c a n t l y
h i g h e r than the e x p e c t e d n a t u r a l width. T h i s " e x t r a p o l a t i o n a n o m a l y " h a s
b e e n e x p l a i n e d by Kuhn, L e w i s , and Vaughan (1965) i n t e r m s of an a d d i t i o n a l
coupling width.
1 6 4 HIND MARSH

RELATIVE DENSITY OF ARGON

FIG.3. C a e s i u m l i n e shift versus r e l a t i v e argon d e n s i t y .

4.2. Non-impact region measurements

Since M i n k o w s k i (1935) f i r s t showed t h a t t h e i n t e n s i t y d i s t r i b u t i o n i n


t h e f a r l o w - f r e q u e n c y wing of t h e s o d i u m r e s o n a n c e l i n e s p e r t u r b e d by
a r g o n w a s of t h e GJ" 3/ ' 2 -form, n u m e r o u s e x p e r i m e n t s h a v e p r o v i d e d d a t a
c o n c e r n i n g t h e n o n - i m p a c t r e g i o n of p r e s s u r e b r o a d e n i n g ; we d i s c u s s h e r e
only a few of t h e m o r e r e c e n t of t h e s e .
G r a n i e r and h i s c o - w o r k e r s have p r e s e n t e d , i n a s e r i e s of p a p e r s
(1961, 1963, 1 9 6 5 a , 1966a, b), the r e s u l t s of a s t u d y of t h e i n f l u e n c e
of p e r t u r b e r m a s s and t e m p e r a t u r e on t h e b r o a d e n i n g and s h i f t of t h e
r e s o n a n c e l i n e s of m e r c u r y and the a l k a l i m e t a l s at high p e r t u r b e r d e n s i t y ,
and h a v e c o m e to the c o n c l u s i o n t h a t , e s p e c i a l l y w h e n d e a l i n g with l i g h t
a t o m s , r e p u l s i v e f o r c e s c a n n o t b e n e g l e c t e d . T h i s r e s u l t , of c o u r s e ,
p a r a l l e l s t h e w o r k of B e h m e n b u r g and H i n d m a r s h i n t h e i m p a c t r e g i o n .
C h ' e n 1 s w o r k h a s b e e n i n t e r p r e t e d by B e h m e n b u r g (196 8), who h a s
c o n s i d e r e d t h e e f f e c t s of b o t h n e o n and a r g o n . F i g u r e s 3 and 4 s h o w ,
IAEA-SMR-12/12 165

RELATIVE DENSITY OF ARGON

FIG.4. C a e s i u m l i n e h a l f - i n t e n s i t y w i d t h versus r e l a t i v e a r g o n d e n s i t y .

r e s p e c t i v e l y , t h e s h i f t and t h e h a l f - i n t e n s i t y width of t h e c a e s i u m l i n e
(6 2 S Q - 6 2 Р 1 ( , 2 ) a s a f u n c t i o n of r e l a t i v e d e n s i t y of a r g o n ( d e n s i t y r e l a t i v e
to t h a t at N. T . P . ) o b t a i n e d e x p e r i m e n t a l l y by C h ' e n and c a l c u l a t e d by
B e h m e n b u r g . The C 6 and C 1 2 v a l u e s u s e d in t h e c a l c u l a t i o n a r e o b t a i n e d
by B e h m e n b u r g f r o m t h e l o w - d e n s i t y m e a s u r e m e n t s ( c o r r e c t e d f o r t h e
e f f e c t s of h y p e r f i n e s t r u c t u r e and s l i t width) u s i n g the w e l l - e s t a b l i s h e d
(12, 6) i m p a c t t h e o r y .
M c C a r t a n et a l . h a v e , in c o n t r a s t to C h ' e n , s t u d i e d a l o w - f r e q u e n c y
wing p r o f i l e at low p e r t u r b e r d e n s i t y , but at s u c h l a r g e d i s p l a c e m e n t s
f r o m t h e u n p e r t u r b e d l i n e t h a t t h e i m p a c t t h e o r y i s no l o n g e r a p p l i c a b l e .
U s i n g t h e t h e o r y of H i n d m a r s h et a l . , t h e y h a v e i n t e r p r e t e d t h e s h a p e of
t h e (4 2 S 1 y 2 - 5 2 P 1 / 2 ) a b s o r p t i o n l i n e of p o t a s s i u m b r o a d e n e d by k r y p t o n a s
a r i s i n g f r o m a (12, 6 ) - i n t e r a c t i o n p o t e n t i a l w h e r e

e = 27 ± 1 cm" 1

CT = (8.0 ± 0.3) X 10" 8 c m


166 HIND MARSH

which i s in e x c e l l e n t a g r e e m e n t with t h e i m p a c t r e g i o n r e s u l t that

e = 25 ± 2 cm" 1

a = (8.0 ± 0.3) X 10" 8 c m

F i g u r e 5 s h o w s t h a t t h e c a l c u l a t e d and e x p e r i m e n t a l p r o f i l e s a r e in v e r y
good a g r e e m e n t o v e r an i n t e n s i t y r a n g e of at l e a s t f o u r o r d e r s of m a g n i t u d e ,
including the p r o m i n e n t s a t e l l i t e band at about 25 cm" 1 f r o m the c o r e . The
c o n t r i b u t i o n to the p r o f i l e beyond the band i s a l m o s t e n t i r e l y due to " i m p a c t "
b r o a d e n i n g of t h e band i t s e l f , due to the f i n i t e d u r a t i o n of the wave t r a i n s
a b s o r b e d at t h a t f r e q u e n c y . T h e r e i s s o m e i n d i c a t i o n of a f e a t u r e at about
50 c m " 1 , which would be e x p e c t e d on the b a s i s of t h e q u a s i - s t a t i c c a l c u l a t i o n
of F a r r e t a l . (1968) which p r e d i c t s s a t e l l i t e s at 2, 3 . . .

FIG.5. E x p e r i m e n t a l i n t e n s i t y d i s t r i b u t i o n of t h e p o t a s s i u m l i n e a t X 4047 Â in an a t m o s p h e r e of k r y p t o n
(red wing). T h e solid l i n e is t h e p r e d i c t e d s h a p e using e = 27 c m " 1 and о = 8 Â. P o s i t i o n in c m " 1 r e l a t i v e
to t h e u n p e r t u r b e d l i n e .
IAEA-SMR-12/12 167

T h i s w o r k h a s r e m o v e d any s e r i o u s doubt a s to t h e n a t u r e of t h e a l k a l i -
r a r e - g a s l o w - f r e q u e n c y b a n d s , of which a g r e a t n u m b e r of o b s e r v a t i o n s
have b e e n m a d e and s e v e r a l t h e o r i e s a d v a n c e d . The e s s e n t i a l e x p e r i m e n t a l
f a c t s about s u c h b a n d s , a l l of which a r e c o n s i s t e n t with t h e t h e o r y of
H i n d m a r s h et a l . , a r e a s follows:

(1) S a t e l l i t e s a r e m o r e l i k e l y to be o b s e r v e d t h e h i g h e r the p o l a r i z a b i l i t y
of t h e p e r t u r b e r s ( i . e . the l a r g e r the v a l u e of a d ) .
(2) At high p r e s s u r e s t h e b a n d s b e c o m e d i f f u s e and d i s a p p e a r .
(3) T h e p o s i t i o n of t h e s a t e l l i t e r e l a t i v e t o t h e m a i n line i s a l m o s t i n d e -
p e n d e n t of p r e s s u r e and t e m p e r a t u r e ( s e e , f o r e x a m p l e , G r a n i e r and
G r a n i e r , 1966c).
(4) T h e b a n d s a r e usually s e v e r a l wave n u m b e r s wide e v e n at low p r e s s u r e s ,
but t h e i n t e n s i t y d r o p s s h a r p l y on the l o w - f r e q u e n c y side of t h e s a t e l -
l i t e . In g e n e r a l , t h e m o r e d i s t a n t the band the m o r e d i f f u s e it i s .

T h e r e m a i n i n g f e a t u r e of f o r e i g n - g a s - b r o a d e n e d s p e c t r a l l i n e s which
i s to b e d i s c u s s e d i s the a p p e a r a n c e , usually at high p e r t u r b e r d e n s i t y ,
of s a t e l l i t e b a n d s on the h i g h - f r e q u e n c y wing of a c o l l i s i o n - b r o a d e n e d l i n e .
M o s t w o r k on t h i s topic h a s b e e n c a r r i e d out on the r e s o n a n c e l i n e s of
xenon, m e r c u r y , and t h e a l k a l i m e t a l s . T h e m a i n f e a t u r e s of t h e s e b a n d s a r e :

(1) They a r e fainter than low-frequency bands.


(2) T h e h e a v i e r t h e p e r t u r b e r , t h e c l o s e r the h i g h - f r e q u e n c y band i s to
t h e m a i n line, although in g e n e r a l they a r e m u c h f u r t h e r f r o m t h e
l i n e c e n t r e than l o w - f r e q u e n c y b a n d s .
(3) F o r a g i v e n a t o m p a i r , t h e h i g h - f r e q u e n c y band s e p a r a t i o n i s l e s s
f o r h i g h e r m e m b e r s of t h e p r i n c i p a l s e r i e s , and low s e r i e s m e m b e r s
u s u a l l y show a second, f a i n t e r band.
(4) S t r u c t u r e i s o c c a s i o n a l l y o b s e r v e d (Robin, 1957).
(5) T h e p o s i t i o n of t h e h i g h - f r e q u e n c y band a p p e a r s to be t e m p e r a t u r e and
p r e s s u r e d e p e n d e n t ( B e s o m b e s et a l . , 1969).

C h ' e n and W i l s o n (1961) and C h ' e n , Atwood and W a r n o c k (1961) give


a c o m p r e h e n s i v e s u r v e y of band p o s i t i o n s .
T h e t h e o r e t i c a l u n d e r s t a n d i n g of the h i g h - f r e q u e n c y s a t e l l i t e b a n d s
i s so f a r v e r y i n c o m p l e t e . T h e p o s s i b i l i t y t h a t , like the l o w - f r e q u e n c y
b a n d s , they a r i s e f r o m t u r n i n g p o i n t s in t h e d i f f e r e n c e p o t e n t i a l c a n n o t
be r u l e d o u t . T h e d i f f i c u l t y i s t h a t r a t h e r l i t t l e i s known about t h e d e t a i l e d
shape of t h e i n t e r a t o m i c p o t e n t i a l at t h e c l o s e d i s t a n c e s which m u s t be
r e s p o n s i b l e f o r t h e f o r m a t i o n of h i g h - f r e q u e n c y b a n d s .

5. BROADENING BY CHARGED P A R T I C L E S

5.1. B r o a d e n i n g t h r o u g h the q u a d r a t i c S t a r k e f f e c t

T h i s type of b r o a d e n i n g o c c u r s in a p l a s m a w h e r e both i o n s and e l e c t r o n s


a r e p r e s e n t . We b e g i n by m a k i n g s o m e e s t i m a t e s of the m a g n i t u d e s of the
w i d t h s c a u s e d by both t y p e s of p e r t u r b e r i n a t y p i c a l p l a s m a w h e r e the
e l e c t r o n v e l o c i t y i s 5 X 1 0 7 c m • s ' 1 and t h e ion v e l o c i t y 2 X 10 5 c m • s " 1 .
168 HIND MARSH

The e l e c t r o n d e n s i t y we t a k e to be 10 15 cm" 3 . It i s e a s y to show f r o m


E q . (31) t h a t

7 = 11.4 (C 4 /Ti) 2 / 3 v 1 / 3 N e (54)

f o r t h e R" 4 i n t e r a c t i o n which h o l d s h e r e . (We a r e at t h i s s t a g e i g n o r i n g


i n e l a s t i c c o l l i s i o n s . ) T h u s we find, with C 4 = 1СГ39 e r g - c m 4 , that
7 — 5 X 10 10 r a d • s" 1 = 0 . 3 c m " 1 f o r e l e c t r o n s while f o r i o n s
7 ~ 5X 10 9 r a d • s" 1 = 0.03 cm" 1 . We have a l r e a d y shown in s e c t i o n 1 t h a t
the i m p a c t r e g i o n e x t e n d s to 10 14 rad • s" 1 f o r e l e c t r o n s and to 5 X 10 10 r a d • s" 1
f o r i o n s i n t h e s e c o n d i t i o n s . We conclude, t h e r e f o r e , t h a t such a s p e c t r a l
line s u f f e r s i m p a c t b r o a d e n i n g by both e l e c t r o n s and i o n s , the f o r m e r being
m u c h the m o r e i m p o r t a n t . If, h o w e v e r , Ne i s i n c r e a s e d by a f a c t o r of
10 to 10 16 cm" 3 , q u a s i - s t a t i c b r o a d e n i n g by the i o n s will s t a r t to be s i g n i f i -
c a n t . Indeed a s y m m e t r y of t h e l i n e s f o r m e d at high e l e c t r o n and ion
densities has often been observed.
We t h u s n e e d an e x p r e s s i o n for the q u a s i - s t a t i c b r o a d e n i n g due to the
i o n s . F o r the f a r wing of the line, f o r m e d by n e a r e s t - n e i g h b o u r i n t e r a c t i o n s
E q . (43) c a n be t a k e n o v e r d i r e c t l y , giving
i i" 7 / 4
I(Au)dAcooc | Д и | dAu (55)
-1/3
Since t h e a v e r a g e d i s t a n c e b e t w e e n the i o n s m u s t be of o r d e r N e it i s
e a s y to s e e t h a t the width of t h e line i s ~ ( C 4 / t l ) N 4 / 3 ~ 10 s r a d • s " 1 . T h i s
i s s m a l l c o m p a r e d with t h e i m p a c t width due to the e l e c t r o n s , but it
i n c r e a s e s m o r e r a p i d l y with i n c r e a s i n g N e . At Ne ~ 10 17 cm" 3 t h e two
b e c o m e c o m p a r a b l e , and g r e a t e r than the i m p a c t b r o a d e n i n g by t h e i o n s .
We c o n c l u d e , t h e r e f o r e , t h a t at low e l e c t r o n d e n s i t y i m p a c t b r o a d e n i n g
by e l e c t r o n s i s the d o m i n a n t influence on the l i n e - w i d t h , but at h i g h e r
d e n s i t i e s q u a s i - s t a t i c b r o a d e n i n g by i o n s b e c o m e s s i g n i f i c a n t . It m u s t
a l s o be n o t i c e d t h a t t h e i m p a c t b r o a d e n i n g by i o n s m a y not a l w a y s be
negligible.
5.2. I n f l u e n c e of i n e l a s t i c c o l l i s i o n s

The e x p r e s s i o n f o r 7 and ß given i n E q s (27) and (28) allow t h e p o s s i b i l i t y


of i n e l a s t i c c o l l i s i o n s , although they involve the c l a s s i c a l p a t h a p p r o x i m a t i o n
f o r the p e r t u r b e r s . A f i r s t a p p r o x i m a t i o n i s not d i f f i c u l t to obtain if we
r e s t r i c t o u r s e l v e s to the c a s e w h e r e only the u p p e r l e v e l s u f f e r s p e r t u r b a t i o n .
In t h i s c a s e we e a s i l y find (by putting /uf = 17 f = 0 in E q s (27) and (28) and
expanding the e x p o n e n t i a l in E q . (29)

7 = 27rN e v J 11 - e"Mi c o s r i i i p d p
0

1
2írNe v / e sin r); • pdp

+ ir) = v
»i i *Ï J '<sl)dsi +
J V ( s 1 ) d s 1 j V ( s 2 )ds 2
IAEA-SMR-12/12 169

Since we a r e dealing with the q u a s i - s t a t i c S t a r k e f f e c t the f i r s t - o r d e r


p e r t u r b a t i o n v a n i s h e s . It i s t h e n e a s y to obtain

(55a)

(56)

A
x x
F(x) = 1 x [e" Ei(x) - e E i ( - x ) ] , Ei(x) = J y dt

w h e r e the s u m m a t i o n s a r e o v e r a l l s t a t e s | s^> of t h e p e r t u r b e d a t o m .
Noticing t h a t C4 = 2 c s , we c a n e a s i l y see the e f f e c t of t h e i n e l a s t i c c o l -
s
l i s i o n s . T h e y a r e u n i m p o r t a n t f o r p » ps and a r e in any c a s e d o m i n a t e d
by t h e i n f l u e n c e of the s t a t e with l a r g e s t p s , t h a t i s the c l o s e s t - l y i n g s t a t e .
A s u m m a t i o n a l s o h a s to be p e r f o r m e d o v e r the S t a r k c o m p o n e n t s of the
s p e c t r a l line c o n c e r n e d .
C a l c u l a t i o n s b a s e d on t h e s e s i m p l e c o n s i d e r a t i o n s a g r e e to within 10%
with m o r e e l a b o r a t e n u m e r i c a l c a l c u l a t i o n s and with o b s e r v a t i o n . C o r r e c t
a v e r a g i n g o v e r the M a x w e l l i a n d i s t r i b u t i o n of v e l o c i t i e s i s of s o m e
importance.

5.3. I n f l u e n c e of the i o n s

W h e r e the i o n s b r o a d e n e n t i r e l y t h r o u g h the q u a s i - s t a t i c e f f e c t all


t h a t i s r e q u i r e d to i n c l u d e t h e i r r e l a t i v e l y s m a l l c o n t r i b u t i o n i s a s i m p l e
folding of the s t a t i c and i m p a c t p r o f i l e s .

5.4. C o m p a r i s o n with e x p e r i m e n t

T a b l e VI s h o w s how t h e s e r e l a t i v e l y s i m p l e c a l c u l a t i o n s a g r e e with
e x p e r i m e n t and with m o r e e l a b o r a t e c a l c u l a t i o n s .

5.5. B r o a d e n i n g t h r o u g h t h e l i n e a r Stark e f f e c t

We now t u r n to t h e p r o b l e m of c a l c u l a t i n g the b r o a d e n i n g of h y d r o g e n -
like l i n e s due to the i o n s and e l e c t r o n s in a p l a s m a . T h i s i s a q u e s t i o n
which r a i s e s a n u m b e r of unique and v e r y d i f f i c u l t p r o b l e m s , and it i s
only p o s s i b l e h e r e to s u m m a r i z e the p r o g r e s s so f a r m a d e .
We have a l r e a d y shown t h a t in any n o r m a l line p r o f i l e the ionic
b r o a d e n i n g w i l l be q u a s i - s t a t i c and t h e e l e c t r o n i c b r o a d e n i n g i s i m p a c t in
c h a r a c t e r . We need t h e r e f o r e to e s t i m a t e t h e m a g n i t u d e s of t h e s e two
-a
О

T A B L E VI. C A L C U L A T E D AND E X P E R I M E N T A L VALUES O F VARIOUS He I LINES

Line c4. N, G r i e m , Kolb, Simple


Experiment
10 ^ 10" T, К Baranger, O e r t e l formulas
(Â)
 Transition erg-cm4 cm"3 (Â) (Ä)

5016 2 1 S - 3'P -1334 1.65 25 000 6. 5 -4.8 7.2 -6 7.2 -4.7

4713 23P - 43S 1250 1.3 20 000 7 6 7.6 8.9 8.5 5.7

4713 2SP - 4 3 s 1250 0.25 30 000 1. 5 1.5 1.4 1.4 1.5 1.1
s 3
3889 2 S - 3 P 264 1.5 25 000 2 1.2 2.1 1.1 2.7 1
IAEA-SMR-12/12 171

e f f e c t s . T h e q u a s i - s t a t i c p r o b l e m w a s solved long ago by H o l t s m a r k (1919)


and it i s s u f f i c i e n t to quote the r e s u l t

(57)
.^-VJnfl, \cn lV-9Lo/

w h e r e I a 6 i s t h e i n t e n s i t y and ( C 2 ) a g / Z e i s t h e S t a r k c o e f f i c i e n t f o r t h e
S t a r k c o m p o n e n t aß of t h e l i n e , and t h e f u n c t i o n

W(ß) / х s i n x exp - ( x / ß ) 3 / 2 dx (58)

W i t h 2/3
/ \
ZeN2/3
•Ш
E 0 = 2тг[ -h j

Two a p p r o x i m a t e e x p r e s s i o n f o r W(ß) a r e

W(ß) = 1.496 ß"5/2 (1 + 5 . 1 0 7 ß'3/2+ 1 4 . 9 3 ß'3 + .. .) ß » l (59)

W(ß) = 4 ~ ß 2 ( ! - 0.463 ß 2 + 0.1227 ß* - . . . ) ß « 1 (60)


о 71

E q . (59) g i v e s t h e s a m e r e s u l t a s E q . (43) with p = 2 f o r the v e r y f a r wing


of t h e l i n e . T h e o r d e r of m a g n i t u d e of the width i s e a s i l y found without
d e t a i l e d c a l c u l a t i o n s , f o r t h e m e a n d i s t a n c e b e t w e e n t h e i o n s ~ N ; 1 / 3 and
the m e a n p e r t u r b a t i o n i s t h e r e f o r e ~ (C2 /h)N 2 / / 3 in a n g u l a r f r e q u e n c y u n i t s .
Now C 2 ~ e 2 a 0 n ( n - 1) a s we have a l r e a d y pointed out s o t h a t , f o r H 0
and N e = 10 1 5 c m ' 3 , the width of the line i s ~ 10 1 1 r a d - s " 1 , o r 0.5 c m " 1 .
Next we w i s h to e s t i m a t e the m a g n i t u d e of t h e i m p a c t b r o a d e n i n g by
e l e c t r o n s ; E q . (30a) g i v e s f o r t h e c l a s s i c a l p h a s e s h i f t , with p = 2,
the r e s u l t

Ç2
-hv

Therefore

7 = 27rNev 1 - cos pdp = 47rNeV J sin 2 pdp

It i s e a s y to s e e t h a t t h i s i n t e g r a l d i v e r g e s : at l a r g e p t h e i n t e g r a l v a r i e s
a s p'1, t h u s c a u s i n g a l o g a r i t h m i c d i v e r g e n c e a t t h e u p p e r l i m i t . A s i m p l e
way out of t h e d i f f i c u l t y i s to cut off the i n t e g r a l at s o m e u p p e r l i m i t p m .
B e a r i n g in m i n d that the v a l u e of the i n t e g r a l with an u p p e r l i m i t of p0
(the W e i s s k o p f r a d i u s ) i s about ?rp2 Nv we have
172 HIND MARSH

A l o g i c a l c h o i c e f o r p i s the Debye r a d i u s ( k T / 4 î r e 2 N e which m e a s u r e s


t h e d i s t a n c e at which an ion i s shielded f r o m m o r e d i s t a n t e l e c t r o n s by the
i n t e r v e n i n g i o n s . At N e = 10 1 5 c m " 3 , T = 5 0 0 0 K , V - 5 X 1 0 7 c m - s " 1 ,
C 2 = 10" 26 e r g • cm 2 , we find p 0 ~ 3 X 10" 1 c m , p m ~ 1.4 X 10"5 c m . Hence
the p r i n c i p a l c o n t r i b u t i o n to c u r v e s f r o m the s e c o n d t e r m of E q . (61), and
7 ~ 5 X 10 1 0 r a d • s " 1 . T h i s i s c o m p a r a b l e with the s t a t i c c o n t r i b u t i o n due
to the i o n s .
T h e d e t a i l e d c a l c u l a t i o n s a r e e x t r e m e l y involved, and m a n y p o i n t s of
p r i n c i p l e a r i s e . B u t the r e a d e r m u s t r e f e r to the l i t e r a t u r e f o r f u r t h e r
i n f o r m a t i o n . Good s t a r t i n g p o i n t s a r e " P l a s m a S p e c t r o s c o p y " by H . G r i e m
(1964) and c h a p t e r 10 of " i n t r o d u c t i o n to the T h e o r y of A t o m i c S p e c t r a "
by I . I . S o b e l ' m a n (1972).

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IAEA-SMR-12/12

RADIOFREQUENCY SPECTROSCOPY

A. KASTLER
Laboratoire de physique,
Ecole normale supérieure,
Paris, France

Abstract
RADIOFREQUENCY SPECTROSCOPY.
1. Introduction; 2. Special features of RF transitions (Predominance of induced emission ; Electric
dipole transitions and magnetic dipole transitions ; The width and shape of RF lines ; The Doppler width ; The
natural line width; Broadening effects) ; 3 . Short historical survey ; 4 . Production and detection of RF
transitions; The two classes of detection methods: change in the wave properties and change in the properties
of matter (Rabi*s detection method of molecular beams; The optical detection method of RF resonances;
Orientation or polarization and alignment; Atomic orientation and magnetization at thermal equilibrium;
Detection by transfer of angular momentum ; Detection by nuclear physics techniques ; The electronic detection
methods of RF resonances) ; 5. The behaviour of paramagnetic atomic states in a constant field and in a
radiofrequency field (Definitions; Behaviour of an atomic system in a constant field; Behaviour of a collection
of many identical paramagnetic atoms in a constant field ; Behaviour of a collection of atoms in an RF field ;
Classical theory of the motion of a spin submitted to a constant field and an RF field) ; 6 . Results (Study of
pure Zeeman intervals; Fine-structure intervals of the n = 2 l e v e l of the hydrogen a t o m ; Hyperfine-structures
in atomic ground states; Muonium e " / j + ; Positronium e " e + ) ; 7. Conclusions.

1. INTRODUCTION

We u s e f o r r a d i o f r e q u e n c y t h e a b b r e v i a t i o n R F . An e l e c t r o m a g n e t i c
(e. m . ) w a v e c a n b e c h a r a c t e r i z e d b y its f r e q u e n c y v e x p r e s s e d in h e r t z (Hz),
o r by t h e w a v e n u m b e r a = v/c in c m " 1 , or b y t h e w a v e l e n g t h \ = I/o = c/v
i n v e r s e l y p r o p o r t i o n a l t o v. We a l s o u s e t h e " w a v e v e c t o r " к = 2ira and the
c i r c u l a r f r e q u e n c y и = 2nv, a n d w r i t e k= ( u / c ) . We a r b i t r a r i l y l i m i t " H e r t z i a n
w a v e s " at v - 10 1 2 Hz ( I T H z ) , w h i c h c o r r e s p o n d s t o A = 0.30 m m . Higher
f r e q u e n c i e s b e l o n g to t h e i n f r a - r e d s p e c t r u m .
In t h e H e r t z i a n s p e c t r u m we m a y d i s t i n g u i s h c o n v e n t i o n a l l y

Audiofrequencies RF Microwaves

i/ < 1 0 4 Hz 10 4 -> 10 9 Hz 109-1012Hz

R F s p e c t r o s c o p y i s c o n c e r n e d w i t h t h e i n t e r a c t i o n of m o n o c h r o m a t i c e . m .
w a v e s , R F r a d i a t i o n , with m a t t e r ( a t o m s , m o l e c u l e s , n u c l e i , c o n d e n s e d
m a t t e r ) . We o b s e r v e s p e c t r a l t r a n s i t i o n s b e t w e e n q u a n t u m s t a t e s g o v e r n e d
by t h e B o h r r e l a t i o n

hi/0=Ea - E j = Д Е

175
176 KASTLER

We c a l l t h e m r a d i o f r e q u e n c y r e s o n a n c e s . To be in the H e r t z i a n r a n g e they
m u s t c o r r e s p o n d to s m a l l e n e r g y i n t e r v a l s , v < 10 12 Hz o r X> 0.30 m m .

v = 1 T e r a h e r t z = 10 12 Hz

is e q u i v a l e n t t o A E = 4.2 X 10 eV. T h e p r i n c i p a l s p e c t r a l t r a n s i t i o n s studied


a r e p u r e r o t a t i o n a l l i n e s of m o l e c u l e s in t h e m m and cm w a v e l e n g t h r e g i o n s ,
e l e c t r o n i c p a r a m a g n e t i c r e s o n a n c e ( E P R ) f o r the r e g i o n s

X = 10 c m v = 3 GHz

and X = 3 cm v = 10 GHz

n u c l e a r m a g n e t i c r e s o n a n c e (NMR) f o r

1 to 100 MHz (X= 300 m to 3 m )

T h e t r a n s i t i o n s s t u d i e d in a t o m s c o r r e s p o n d to Z e e m a n i n t e r v a l s a r t i f i c i a l l y
p r o d u c e d by applied m a g n e t i c f i e l d s ( m a g n e t i c r e s o n a n c e t r a n s i t i o n s ) o r to
n a t u r a l f i n e s t r u c t u r e and h y p e r f i n e s t r u c t u r e (HFS) i n t e r v a l s . T h e " n o r m a l "
Z e e m a n s p l i t t i n g is 1.4 MHz in a field of 1 g a u s s , which c o r r e s p o n d s to
2.8 GHz in a field of 2000 g a u s s .

2. S P E C I A L F E A T U R E S O F R F TRANSITIONS

2.1. P r e d o m i n a n c e of induced e m i s s i o n

E i n s t e i n d i s t i n g u i s h e s two e m i s s i o n p r o c e s s e s : s p o n t a n e o u s e m i s s i o n and
induced e m i s s i o n . T h e r a t e is given by

Bp
" c3" 1 ^

A is the r a t e of s p o n t a n e o u s e m i s s i o n and Bp„ is the r a t e of e m i s s i o n induced


by the s p e c t r a l r a d i a t i o n d e n s i t y pv~ dp/dv. In the o p t i c a l r a n g e , pv and X a r e s m a l l ,
and t h e d o m i n a n t p r o c e s s — except in l a s e r s — is s p o n t a n e o u s e m i s s i o n ,
which d e t e r m i n e s the l i f e t i m e of excited s t a t e s of a t o m s .
In the R F r a n g e , X is l a r g e and we a r e able to g e n e r a t e H e r t z i a n
w a v e s of l a r g e pv. The d o m i n a n t p r o c e s s i s induced e m i s s i o n . Spontaneous
e m i s s i o n is n e g l i g i b l e , e x c e p t in a s t r o p h y s i c s .
A c o n s e q u e n c e of t h i s i s that we c a n s o l v e m o s t p r o b l e m s of i n t e r a c t i o n
of r a d i a t i o n and m a t t e r by c l a s s i c a l c a l c u l a t i o n s . It can b e shown t h a t , if
s p o n t a n e o u s e m i s s i o n c a n b e n e g l e c t e d , the e x p e c t a t i o n v a l u e s f o r m a c r o -
s c o p i c q u a n t i t i e s c a l c u l a t e d by quantum m e c h a n i c s a r e i d e n t i c a l with t h e
r e s u l t s of c l a s s i c a l t h e o r y . An e x a m p l e of s u c h a c l a s s i c a l t r e a t m e n t is the
t h e o r y of m a g n e t i c r e s o n a n c e of spins in c o n d e n s e d m a t t e r l e a d i n g to the
" B l o c h e q u a t i o n s " . Induced e m i s s i o n i s the e q u i v a l e n t of n e g a t i v e a b s o r p t i o n .
T h e n e t e f f e c t d e p e n d s on the population d i f f e r e n c e b e t w e e n the l o w e r and
u p p e r e n e r g y l e v e l s of the t r a n s i t i o n .
IAEA - S M R - 1 2 / 9 177

2.2. E l e c t r i c dipóle and m a g n e t i c dipole t r a n s i t i o n s

A n o t h e r s p e c i a l f e a t u r e of R F t r a n s i t i o n s is that in t h e R F r a n g e we
have to d e a l with m a n y t r a n s i t i o n s of the type of m a g n e t i c dipole t r a n s i t i o n s ,
w h e r e a s in t h e o p t i c a l r a n g e t h i s type is s e l d o m found and the c o r r e s p o n d i n g
t r a n s i t i o n s a r e v e r y weak. M o s t of the s p e c t r a l t r a n s i t i o n s o b s e r v e d in the
o p t i c a l r a n g e a r e e l e c t r i c dipole t r a n s i t i o n s and c o r r e s p o n d to the r a d i a t i o n
of an e l e c t r i c dipole.
T h i s e l e c t r i c dipole b e t w e e n two s t a t e s Ej and E ; is given by the
e x p r e s s i o n (its x - c o m p o n e n t )

R, , = e Ф, x d x d y d z , w h e r e Ú is the w a v e - f u n c t i o n of s t a t e E,
J J ' J J

The y - and z - c o m p o n e n t s a r e given by analogous e q u a t i o n s . T h i s c a l c u l a t i o n


l e a d s to the s e l e c t i o n r u l e s and p o l a r i z a t i o n r u l e s . T r a n s i t i o n s b e t w e e n
l e v e l s of the s a m e p a r i t y a r e f o r b i d d e n as e l e c t r i c dipole t r a n s i t i o n s .
Once Pjj is known, we obtain the E i n s t e i n c o e f f i c i e n t s by

B
B - i î i2 P 2 - A - ^ - ^ - P 2
" 3 h j* ' 3h C3

E l e c t r i c dipole t r a n s i t i o n s in the R F region a r e the r o t a t i o n a l l i n e s of m o l e -


c u l e s p o s s e s s i n g a p e r m a n e n t dipole and t h e i n v e r s i o n line of NH 3 . M a g n e t i c
dipole t r a n s i t i o n s obey o t h e r s e l e c t i o n r u l e s and o c c u r b e t w e e n l e v e l s of the
s a m e p a r i t y . T h e y a r e r e l a t e d to the change in m a g n i t u d e or in s p a c e d i r e c -
tion of the m a g n e t i c m o m e n t ß of the atom, and o c c u r in m a g n e t i c r e s o n a n c e s
and in f i n e s t r u c t u r e and HFS r e s o n a n c e s .

2.3. T h e width and s h a p e of r a d i o f r e q u e n c y l i n e s

In t h e o p t i c a l r a n g e the width of n a r r o w s p e c t r a l l i n e s of c o n v e n t i o n a l
light s o u r c e s (gas d i s c h a r g e s ) is d e t e r m i n e d by t h e D o p p l e r e f f e c t .
T h e i n t e n s i t y d i s t r i b u t i o n in an e m i s s i o n o r a b s o r p t i o n line is given by

I.. = I,О EX log 2


P • ' i ?

F o r v-v0 ± 5 / 2 , we have Iv = I0/2. T h e Doppler s h a p e is a G a u s s i a n s h a p e


and б is the width at half i n t e n s i t y . In Fig. 1 6/v0= 0.78 X 1 0 " 6 ^ T / M is given a s
a f u n c t i o n of a b s o l u t e t e m p e r a t u r e and m o l e c u l a r m a s s of the g a s m o l e c u l e s .
T h e r e l a t i v e Doppler width is the s a m e f o r a l l s p e c t r a l l i n e s e m i t t e d o r
a b s o r b e d by t h e s a m e a t o m s o r m o l e c u l e s . In t h e o p t i c a l r a n g e (У 0 ~1О 15 HZ)
it is of the o r d e r б = 10 9 Hz o r 1 GHz. F o r s m a l l R F f r e q u e n c i e s the D o p p l e r
width b e c o m e s v e r y s m a l l and often n e g l i g i b l e , c o m p a r e d with o t h e r b r o a d e n i n g
e f f e c t s . F o r R F l i n e s the line width is m o s t l y d e t e r m i n e d e i t h e r by the
" n a t u r a l line width" o r by r e l a x a t i o n . The n a t u r a l line width c o m e s f r o m t h e
f a c t that the t i m e of i n t e r a c t i o n b e t w e e n the a t o m and the e . m . wave i s
l i m i t e d .to t i m e т a s shown in F i g . 2.
178 KASTLER

FIG.l. Shape of RF line (Gaussian), frequency versus intensity.

A t r u n c a t e d m o n o c h r o m a t i c s i n u s o i d a l wave is — a s shown by F o u r i e r
a n a l y s i s — t h e e q u i v a l e n t of the s u p e r p o s i t i o n of w a v e s of a f r e q u e n c y
interval

1 2LR
sOU) = T- or * V =
Б
T

which l e a d s to ô E = ftôw =ÍIT" 1 o r 6Ет =fi. T h i s is H e i s e n b e r g ' s f o u r t h


u n c e r t a i n t y r e l a t i o n . T h e f i n i t e l i f e t i m e of an e n e r g y l e v e l т l e a d s to a
s p r e a d i n g of the e n e r g y of t h i s level. A s p e c t r a l line i s a t r a n s i t i o n b e t w e e n
two l e v e l s , E j and E 2 , v = l / h ( E j - E 2 ) and t h e c o r r e s p o n d i n g u n c e r t a i n t y i s

1 1" i
ôv= i(6E1 + ÔE 2 )= ± — + —
LVstJ 2тг - T 1 T
2-

If t h e two l i f e t i m e s a r e e q u a l ( Z e e m a n l e v e l s )

6v = - i -
7ГТ

M o r e g e n e r a l l y , we will c a l l т the " c o h e r e n c e t i m e " . T h i s i s the f o r m u l a


f o r the n a t u r a l line width of m a g n e t i c r e s o n a n c e in an e x c i t e d s t a t e . F o r a
g r o u n d - s t a t e r e s o n a n c e , т is t o b e i d e n t i f i e d with the " t r a n s v e r s e r e l a x a t i o n
IAEA - S M R - 1 2 / 9 179

t i m e " T 2 : 6 v = 1 /7гТ2 . T h e s h a p e c o n n e c t e d to t h i s n a t u r a l width is a


Lorentz shape,

I=

w h e r e 6' = öv.
B r o a d e n i n g o c c u r s a l s o by r a d i o f r e q u e n c y p o w e r and by c o l l i s i o n s
(pressure broadening).

3. SHORT HISTORICAL SURVEY

T h e f i r s t R F t r a n s i t i o n o b s e r v e d (1934) was the i n v e r s i o n band of NH 3


in t h e 1 . 2 5 - c m w a v e l e n g t h r a n g e , w h e r e it was d i s c o v e r e d by C l e e t o n and
W i l l i a m s . It w a s e x p e c t e d f r o m t h e a n a l y s i s of the i n f r a - r e d r o t a t i o n l i n e s
of t h e s e m o l e c u l e s in 1933. E a c h of t h e s e l i n e s i s a doublet as p r e d i c t e d by
D e n n i s on.
In 1938 Rabi (Columbia U n i v e r s i t y ) s t a r t e d h i s m o l e c u l a r b e a m m e t h o d
of m a g n e t i c r e s o n a n c e . But the l a r g e - s c a l e d e v e l o p m e n t of R F s p e c t r o s c o p y
s t a r t e d in 1944-45 with the invention of e l e c t r o n i c d e t e c t i o n t e c h n i q u e s :

(1) T h e a p p l i c a t i o n of r a d a r t e c h n i q u e s to the study of m o l e c u l a r t r a n s i t i o n s


in the m i c r o w a v e r e g i o n .
(2) T h e d i s c o v e r y of E P R ( E l e c t r o n P a r a m a g n e t i c R e s o n a n c e ) by Z a v o i s k y
in K a z a n .
(3) T h e d i s c o v e r y of NMR ( N u c l e a r M a g n e t i c R e s o n a n c e ) s i m u l t a n e o u s l y ,
by P u r c e l l , T o r r e y and Pound at H a r v a r d , and by F e l i x B l o c h and his
c o l l a b o r a t o r s in S t a n f o r d .

4. PRODUCTION AND D E T E C T I O N OF R F TRANSITIONS

4.1. Production

T r a n s i t i o n s a r e p r o d u c e d by i n t e r a c t i o n of a t o m s o r m o l e c u l e s with a
m o n o c h r o m a t i c e. m . wave p r o d u c e d by a g e n e r a t o r . R F g e n e r a t o r s have
b e e n d e v e l o p e d f o r the p u r p o s e s of r a d i o c o m m u n i c a t i o n s (1 to 100 MHz), of
t e l e v i s i o n (100 MHz - 1 GHz), and r a d a r (3 to 10 GHz). In the R F r e g i o n
L - C c i r c u i t s a r e u s e d ; in t h e m i c r o w a v e r e g i o n wave guide t e c h n i q u e s and
r e s o n a n c e c a v i t i e s h a v e b e e n d e v e l o p e d . T h e m a t t e r u n d e r i n v e s t i g a t i o n is
s u b m i t t e d e i t h e r t o a p r o g r e s s i v e e . m . wave o r to a s t a n d i n g wave ( c o n d e n s e r +
s e l f - i n d u c t i o n c o i l , r e s o n a n c e cavity).

4.2. Detection

The m e t h o d s of d e t e c t i o n c a n b e divided into two c l a s s e s . D u r i n g t h e


i n t e r a c t i o n b e t w e e n m a t t e r and r a d i a t i o n at r e s o n a n c e , both t h e p r o p e r t i e s
of the m a t t e r and t h e p r o p e r t i e s of the r a d i a t i o n a r e m o d i f i e d . In one c l a s s
180 KASTLER

F (
21 A • V2

~ T -v2

FIG.3. Schematic representation of Rabi 1 s molecular-beam device.

of d e t e c t i o n m e t h o d s one o b s e r v e s the change p r o d u c e d on the wave or on the


R F c i r c u i t g e n e r a t i n g the w a v e . T h e s e m e t h o d s of d e t e c t i o n a r e c a l l e d
e l e c t r o n i c d e t e c t i o n m e t h o d s . In the o t h e r c l a s s , one o b s e r v e s the c h a n g e
p r o d u c e d on t h e a t o m s o r m o l e c u l e s . We d e a l f i r s t with t h e l a t t e r m e t h o d s .

4.3. Rabi's detection method using molecular beams

M o l e c u l a r b e a m s in v a c u u m w e r e p r o d u c e d f i r s t by L o u i s D u n o y e r in
1911. T h e y w e r e u s e d by S t e r n to e s t a b l i s h the M a x w e l l d i s t r i b u t i o n law of
t h e r m a l v e l o c i t i e s and, in 1922, in the S t e r n - G e r l a c h e x p e r i m e n t , giving
the e x p e r i m e n t a l proof of s p a c e q u a n t i z a t i o n of a t o m s in a m a g n e t i c f i e l d .
F i g . 3 s h o w s t h e s c h e m e of R a b i ' s d e v i c e .
Atoms e s c a p e f r o m a h e a t e d oven o r a g a s c h a m b e r О t h r o u g h a s m a l l s l i t Fj
into a v a c u u m . T h e a p e r t u r e of the b e a m is l i m i t e d by a s e c o n d l a r g e r s l i t ,
F 2 , allowing an a n g u l a r a p e r t u r e of 2 a . A and В a r e t h e g a p s of two m a g n e t s
p r o d u c i n g n o n - h o m o g e n e o u s m a g n e t i c f i e l d s of the s a m e d i r e c t i o n , p e r p e n d i -
c u l a r to t h e m e a n r a y of t h e b e a m , but of opposite g r a d i e n t s . T h e f o r c e
e x e r t e d on a p a r a m a g n e t i c a t o m is F z = J u z (3H/3z) w h e r e /J z is the z - c o m p o n e n t
of the m o m e n t . It p r o d u c e s a c u r v a t u r e of the a t o m i c p a t h , c u r v a t u r e of
o p p o s i t e d i r e c t i o n in the A and В f i e l d s . A s l i t S b e t w e e n the two gaps s e l e c t s
a t o m s which a r e f o c u s s e d on a d e t e c t o r D, counting the a t o m s a r r i v i n g on it.
If now, in the S - r e g i o n , a m a g n e t i c r e s o n a n c e t r a n s i t i o n is p r o d u c e d by an
R F f i e l d , t r a n s i t i o n s o c c u r and, as a r e s u l t , the path of a t o m s h a v i n g u n d e r -
gone t r a n s i t i o n s i s changed in the gap B, and t h e s e a t o m s do not r e a c h the
d e t e c t o r . M a g n e t i c r e s o n a n c e is m o n i t o r e d by a d e c r e a s e in the s i g n a l at D.
F i g u r e 20 s h o w s an NMR s i g n a l of 7 L i in L i C l m o l e c u l e s . The R F f r e q u e n c y
applied is v = 3.518 MHz and the m a g n e t i c f i e l d HQ is swept t h r o u g h r e s o n a n c e
which o c c u r s at 2134 G a u s s . In this c a s e the r e s o n a n c e f r e q u e n c y v0 is a

2 w e = to0 = yH 0 and 7 = Hj/ift

/Uj can b e c a l c u l a t e d and e x p r e s s e d in juN u n i t s :

UM = ; r ! i r - = = 5.049 X Ю" 24 e r g6 // gs a u s s
2MH 1840

[MB = B o h r ' s m a g n e t o n ] .
IAEA - S M R - 1 2 / 9 181

63P, - о
--1

TX CT 2537Â

e'Sn-L • 0 GROUND STATE

FIG.4. Excited state of the Hg a t o m (excitation by тг-polarized light at 2537 A)-

i 6 8 10 12 U 16
GAUSS

FIG.5. EPR absorption detected by m e c h a n i c a l torque on the substance DPPH (after G. Alzetta and A. Gozzini,
Proc. 12-th C o l l . AmpĚre, Bordeaux 1963. North Holland Publ. (1964) 209.)

4.4. T h e o p t i c a l d e t e c t i o n m e t h o d of R F r e s o n a n c e s

T h i s m e t h o d i s s u i t a b l e f o r s t u d y i n g r e s o n a n c e s in e x c i t e d s t a t e s of
a t o m s . It i s p o s s i b l e , e i t h e r by o p t i c a l e x c i t a t i o n ( s p a c e - d i r e c t e d and
p o l a r i z e d l i g h t ) o r by e l e c t r o n - i m p a c t e x c i t a t i o n w i t h a u n i d i r e c t i o n a l e l e c t r o n
b e a m , t o a c h i e v e s e l e c t i v e p o p u l a t i o n of Z e e m a n l e v e l s of the e x c i t e d s t a t e .
T h i s g i v e s r i s e to p o l a r i z a t i o n of t h e o p t i c a l l i n e s e m i t t e d and t o s p a c e -
a n i s o t r o p y of the l i g h t e m i s s i o n . By R F r e s o n a n c e b e t w e e n Z e e m a n l e v e l s
o r H F S l e v e l s of the e x c i t e d s t a t e , t h e light e m i t t e d i s d e p o l a r i z e d and t h e
r e s o n a n c e c a n be d e t e c t e d in t h i s w a y .

E x a m p l e : B r o s s e l ' s d o u b l e r e s o n a n c e e x p e r i m e n t on t h e e x c i t e d s t a t e of
t h e Hg a t o m ( F i g . 4). H g - v a p o u r i s e x c i t e d b y т т - p o l a r i z e d l i g h t of 2537 A.
M a g n e t i c r e s o n a n c e g i v e s r i s e to t h e e m i s s i o n of a - l i g h t w h o s e i n t e n s i t y I a
c a n b e m e a s u r e d a s a f u n c t i o n of t h e f i e l d H 0 . F o r v = 144 M H z , r e s o n a n c e
o c c u r s at 69 g a u s s . W e h a v e t o d e a l h e r e with a t r i g g e r d e t e c t i o n .
182 KASTLER

A t o m i c " o r i e n t a t i o n " and " a l i g n m e n t " . Atomic orientation or polarization


is d e f i n e d by the d e g r e e of o r i e n t a t i o n

+J

XmNir
J +J

I».
-J

In this f o r m u l a , J is the i n t e r n a l quantum n u m b e r , m the m a g n e t i c quantum


n u m b e r and N m the population of a Z e e m a n s u b - l e v e l . O r i e n t a t i o n c a n be
obtained by o p t i c a l e x c i t a t i o n with c i r c u l a r l y p o l a r i z e d light. Such light
c a r r i e s a n g u l a r m o m e n t u m which, by the a b s o r p t i o n p r o c e s s , is t r a n s f e r r e d
to the a t o m s . E x c i t a t i o n with s p a c e - d i r e c t e d n a t u r a l light, o r with l i n e a r l y -
p o l a r i z e d light, o r with e l e c t r o n i m p a c t l e a d s to " a l i g n m e n t " , which is
e q u i v a l e n t to " a n i s o t r o p y " . T h e d e g r e e of a l i g n m e n t is d e f i n e d by

+J

/ т 2 \ J ( J + 1> -I J ( J + 1)
^ z/ " 3
I N„

O r i e n t a t i o n or a l i g n m e n t can be t r a n s f e r r e d to the g r o u n d s t a t e of a t o m s by
the optical pumping technique.

O r i e n t a t i o n p r o d u c e s a m a c r o s c o p i c a n g u l a r m o m e n t u m in a v a p o u r

= NPJh
IAEA - S M R - 1 2 / 9 183

- ж -
I ^TO
AMPLIFIER
hrw^
SIGNAL
GENERATOR
4- CABLE

II
/77777 ПЯЛЛР

FIG.7. Purcell's balanced bridge technique.

and an a s s o c i a t e d m a c r o s c o p i c m a g n e t i c m o m e n t

NPm = N P g J n B

At t h e r m a l e q u i l i b r i u m in a m a g n e t i c f i e l d

E„\ ( pHX
N m = c o n s t X exp p j - J = К exp m J k T .

T h i s l e a d s , if E m « kT, to P = ( p H / J k T ) ( E m 2 / 2 J + 1 ) and, a s
+J

IJ
m =
J( J + 1 )(2 J- i )

We d e f i n e x0 = •stí?/H a s p a r a m a g n e t i c s u s c e p t i b i l i t y .

4.5. M a g n e t i c r e s o n a n c e d e t e c t e d by the t r a n s f e r of a n g u l a r m o m e n t u m

We s h a l l s e e l a t e r on that if we apply, to a p a r a m a g n e t i c s u b s t a n c e in
c o n d e n s e d s t a t e at e x a c t r e s o n a n c e , an R F f i e l d 2 H 1 c o s u 0 t , the p o w e r
t r a n s m i t t e d to the s u b s t a n c e in unit t i m e is given by

H 21 T
W = x —-—
0 0 2 2
1 + y HT T
1 1 2
184 KASTLER

w h e r e Tj and T 2 a r e , r e s p e c t i v e l y , t h e l o n g i t u d i n a l and t r a n s v e r s e
r e l a x a t i o n t i m e s . T h e s a t u r a t i o n f a c t o r is d e f i n e d as

2
1 + 7 H 2 T i T2

T h i s p o w e r i s c o n v e r t e d into h e a t and, in p r i n c i p l e , the heat p r o d u c t i o n


could be u s e d f o r the d e t e c t i o n of r e s o n a n c e . T h i s would be a " c a l o r i m e t r i c
method".
In 1936, G o r t e r , at L e i d e n , t r i e d to d e t e c t NMR by this m e t h o d . He
f a i l e d and c o r r e c t l y a t t r i b u t e d this n e g a t i v e r e s u l t to a v e r y long T j r e l a x a t i o n
t i m e ; s o the s a t u r a t i o n f a c t o r s and the h e a t g e n e r a t e d a r e v e r y s m a l l in
this case.
F o r e a c h a b s o r b e d R F photon of e n e r g y ftu>0, an a n g u l a r m o m e n t u m h
i s t r a n s f e r r e d to t h e s a m p l e . This a n g u l a r m o m e n t u m t r a n s f e r ( d P / d t )
p r o d u c e s a t o r q u e Г on the s a m p l e :

_ dP W TT2 ^
= =
dT ~ *oVoT2 s

T h i s t o r q u e h a s b e e n m e a s u r e d by Gozzini on the D P P H m a g n e t i c r e s o n a n c e
(Fig. 5).

4.6. D e t e c t i o n of m a g n e t i c r e s o n a n c e by n u c l e a r p h y s i c s t e c h n i q u e s

A n o t h e r m e t h o d of d e t e c t i o n of R F r e s o n a n c e s is to m o n i t o r the change
of population of m s t a t e s by the change in e m i s s i o n r a t e of n u c l e a r p a r t i c l e s
in d i f f e r e n t d i r e c t i o n s of s p a c e . We s h a l l s e e two e x a m p l e s of this when we
s h a l l r e p o r t on t h e s t u d i e s of m a g n e t i c r e s o n a n c e in p o s i t r o n i u m and in
muonium.

4.7. T h e e l e c t r o n i c d e t e c t i o n m e t h o d s of R F r e s o n a n c e s

T h e s e m e t h o d s a r e b a s e d on the f a c t that the i n t e r a c t i o n b e t w e e n the


e. m . wave and m a t t e r , which c o n s i s t s in an e x c h a n g e of e n e r g y , c h a n g e s
t h e p r o p e r t i e s of the wave and c h a n g e s a l s o the p r o p e r t i e s of the R F c i r c u i t
p r o d u c i n g the wave. An a b s o r p t i o n of e. m . e n e r g y by m a t t e r is e q u i v a l e n t
to a l o s s of e n e r g y of t h e c i r c u i t and c o r r e s p o n d s to an i n c r e a s e of i t s
resistance.
To an a b s o r p t i o n band in t h e f r e q u e n c y s c a l e is c o n n e c t e d .a c u r v e of
a n o m a l o u s d i s p e r s i o n , shown in Fig. 6.
T h e d i s p e r s i o n e f f e c t c o r r e s p o n d s t o a c h a n g e in the c a p a c i t y С o r in the
s e l f - i n d u c t i o n c o e f f i c i e n t L of the RF c i r c u i t . T h e s e c h a n g e s can b e d e t e c t e d
by v e r y s e n s i t i v e e l e c t r o n i c m e t h o d s , e . g . with the help of P u r c e l l ' s
b a l a n c e d b r i d g e t e c h n i q u e (Fig. 7).
T h e two s i g n a l s a r r i v i n g at В a r e of e q u a l a m p l i t u d e , but opposite in
p h a s e and give r i s e to d e s t r u c t i v e i n t e r f e r e n c e . A d i s t u r b a n c e in one of the
c i r c u i t s , p r o d u c e d by the r e s o n a n c e , c h a n g e s the b r i d g e e q u i l i b r i u m and
g i v e s r i s e to a s i g n a l . T h e s a m p l e s t u d i e d is p l a c e d i n s i d e the induction
IAEA - S M R - 1 2 / 9 185

c o i l of one of the two c i r c u i t s in t h e gap of an e l e c t r o m a g n e t (Fig. 8).


A n o t h e r p o s s i b i l i t y is F e l i x B l o c h ' s m e t h o d of " n u c l e a r induction"
(Fig. 9). It u s e s two i n d e p e n d e n t L - C c i r c u i t s with o r t h o g o n a l c o i l s , t h e i r
m u t u a l induction c o e f f i c i e n t M b e i n g z e r o . T h e i n t r o d u c t i o n of m a t t e r in the
c o m m o n p a r t s of the two c o i l s L-l and L 2 , and the a p p l i c a t i o n of a s t e a d y f i e l d H 0 ,
p e r p e n d i c u l a r to t h e s h e e t and to t h e two coil a x e s , p r o d u c e s a n o n - z e r o
induction e f f e c t when r e s o n a n c e i s r e a l i z e d . T h i s m e t h o d is b a s e d on the
f a c t that the m a g n e t i c m o m e n t induced in the m a t t e r by the l i n e a r R F f i e l d
2Щ c o s u t is a r o t a t i n g m o m e n t in the p l a n e p e r p e n d i c u l a r to HQ.

5. THE BEHAVIOUR O F PARAMAGNETIC ATOMIC S T A T E S IN A


CONSTANT F I E L D AND IN A RADIOFREQU-ENCY F I E L D

5.1. Definitions

We c a l l " p a r a m a g n e t i c " an a t o m i c s t a t e p o s s e s s i n g an a n g u l a r m o m e n t u m
p and a m a g n e t i c m o m e n t ju which a r e c o - a x i a l . We w r i t e ju = 7p, which
d e f i n e s 7, c a l l e d " g y r o m a g n e t i c r a t i o " .

i 1 l e
F o r a f r e e e l e c t r o n | p| = — h and,u = ц в = — — h
186 KASTLER

T h e two a x i a l v e c t o r s , p and ^ a r e in o p p o s i t e d i r e c t i o n s .
For an e l e c t r o n o r b i t р { = ih and = i-/u B w h e r e i is the a z i m u t h a l
quantum number.
For an o r b i t t h e g y r o m a g n e t i c r a t i o is

7c = =
2m 0 " 2m,

F o r the electron spin % = e / m 0 = - | e | / m 0 . The Lande factor g is


d e f i n e d b y I 7 I = g ( e / 2 m 0 ) . F o r o r b i t s , g = l ; f o r e l e c t r o n s p i n s , g = 2.
M o r e g e n e r a l l y , f o r an a t o m i c s t a t e , J = E + § d e f i n e s the t o t a l a n g u l a r
m o m e n t u m Jft. T h e m a g n e t i c m o m e n t a s s o c i a t e d with it is p j = - g j J/uB ,
w h e r e gj is g i v e n by L a n d é ' s f o r m u l a

J ( J + 1 ) + S (S + 1) - L ( L + 1 )
g
J 2J(J+1 )

L = EJ2 b e i n g the r e s u l t a n t of the o r b i t a l m o m e n t s of a l l e l e c t r o n s , and S = E s


t h e r e s u l t a n t of t h e i r s p i n m o m e n t s . F o r s i n g l e t t e r m s the r e s u l t a n t of
e l e c t r o n s p i n s i s S = 0. We h a v e J = L and g= 1. F o r p u r e s p i n s t a t e s
( S - s t a t e s ) we h a v e L = 0 and J = S, g= 2. T h i s is in p a r t i c u l a r the c a s e of the
g r o u n d s t a t e s of t h e H - a t o m and of t h e a l k a l i a t o m s which a r e in a s t a t e
2
S I : L = 0, J = S = 1 / 2 .

5.2. B e h a v i o u r of an a t o m i c s y s t e m in a c o n s t a n t m a g n e t i c field

The L a r m o r p r e c e s s i o n . L e t u s t a k e H0 in the z - d i r e c t i o n of a fixed


c o - o r d i n a t e s y s t e m and c a l l t h e x y - p l a n e the " e q u a t o r i a l p l a n e " . T h e f i e l d
H0 e x e r t s on a m a g n e t i c m o m e n t a t o r q u e

b i x i i ,

A c c o r d i n g to a t h e o r e m of m e c h a n i c s , Г = ( d p / d t ) ; p = ( l / y ) ß g i v e s
(1 /7)(dju/dt) = (i X H 0 ; dß = у ц X H Q d t i s a v e c t o r p e r p e n d i c u l a r to t h e p l a n e
П, Й (Fig. 10).
[Г I = ju H 0 s i n a and |clju| = ß s i n e dö if d6 is the a n g u l a r p r e c e s s i o n of
ц in t i m e dt a r o u n d H 0 : &ÍH-S d0 = y # HQ ßin-a dt.
u 0 = ( d 0 / d t ) = 7 H 0 i s t h e a n g u l a r s p e e d o r the c i r c u l a r f r e q u e n c y of the
" L a r m o r p r e c e s s i o n " of ц and p a r o u n d H 0 ,
The s e n s e of t h i s p r e c e s s i o n can be s e e n f r o m t h e f r a m e in F i g . 11.
We r e t a i n the r u l e that f o r an . e l e c t r o n the s e n s e of p r e c e s s i o n is t h a t of
t h e e l e c t r i c c u r r e n t in the c o i l c r e a t i n g the f i e l d H 0 . If we d e f i n e t h i s s e n s e
a s the p o s i t i v e s e n s e , we have f o r e l e c t r o n s u 0 > 0, but y< 0, s o we h a v e to
w r i t e u 0 = - 7 HQ.
IAEA - S M R - 1 2 / 9 187

The r o t a t i n g f r a m e . We i n t r o d u c e a r o t a t i n g f r a m e OXYZ h a v i n g Z = z ,
which r o t a t e s a r o u n d the z - a x i s with a n g u l a r v e l o c i t y 10 ( F i g . 12). F o r an
o b s e r v e r in t h e r o t a t i n g f r a m e , the a n g u l a r v e l o c i t y of the L a r m o r p r e c e s s i o n
s e e n by h i m i s r e d u c e d to w0 -to. He c o n c l u d e s t h a t the m a g n e t i c f i e l d he
s e e s in the z - d i r e c t i o n i s

<y U <y <Y

If и = u 0 t h e m a g n e t i c f i e l d v a n i s h e s f o r h i m . But n o t e t h a t t h i s c o n c l u s i o n
h a s n o a b s o l u t e m e a n i n g . It d e p e n d s on the 7 - v a l u e of the s t a t e c o n s i d e r e d .

5.3. B e h a v i o u r of a c o l l e c t i o n of m a n y p a r a m a g n e t i c a t o m s in a m a g n e t i c
f i e l d Hn

E a c h a t o m h a s a m o m e n t jÜ, but the m o m e n t s m a y h a v e d i f f e r e n t


o r i e n t a t i o n s in s p a c e . T h e bulk m a c r o s c o p i c m o m e n t i s M = ЕД. If n o f i e l d
is p r e s e n t , M = 0, which c o r r e s p o n d s to r a n d o m s p a c e o r i e n t a t i o n .
188 KASTLER

FIG.13. Precession of atomic magnetic moment.

FIG. 14. Frame used in classical phenomenological theory.

In A f i e l d H 0 || OZ we have M = М г f o r s y m m e t r y r e a s o n s . At t h e r m a l
e q u i l i b r i u m , 'M z = ХоЩ. T h i s d e f i n e s the p a r a m a g n e t i c s u s c e p t i b i l i t y

J+1
у = T4T
N ß—2
3J kT

It e x p r e s s e s C u r i e ' s law. M z i s called the " l o n g i t u d i n a l m a g n e t i c m o m e n t " .


T h e m a g n e t i c m o m e n t of e a c h a t o m h a s a l s o a t r a n s v e r s e c o m p o n e n t which
p r e c e s s e s a r o u n d H 0 with t h e L a r m o r s p e e d u 0 = 7H 0 (Fig. 13). But if the
only a c t i o n on the a t o m i c m o m e n t s is that of a c o n s t a n t f i e l d HQ. the r e s u l t a n t
M t = E/I t is in g e n e r a l v a n i s h i n g f o r s y m m e t r y r e a s o n s . T h e p h a s e s of
p r e c e s s i o n of the a t o m s a r e d i s t r i b u t e d at r a n d o m . We s a y the a t o m s
precess "incoherently". T h e r e exist p r o c e d u r e s for c r e a t i n g a coherence
of p h a s e a m o n g the p r e c e s s i n g a t o m s . In this c a s e ïvlt = E/Üt is d i f f e r e n t f r o m
z e r o . T h e m a c r o s c o p i c m o m e n t M t p r e c e s s e s with the L a r m o r s p e e d u 0 = -7H 0
a r o u n d H 0 . We s p e a k of a " c o h e r e n t " p r e c e s s i o n . If the c a u s e of c o h e r e n c e
is s u d d e n l y s u p p r e s s e d , t h e individual m o m e n t s l o s e t h e i r c o h e r e n c e and the
t r a n s v e r s e m o m e n t M t d e c l i n e s a s an e x p o n e n t i a l f u n c t i o n of t i m e and

dMt_ Mj
"ďt T„
IAEA - S M R - 1 2 / 9 189

2H,

FIG.15. Field rotation (amplitude 21-Ij) in coherence with w .

d e f i n e s a " t r a n s v e r s e r e l a x a t i o n t i m e T 2 " , often called s p i n - s p i n r e l a x a t i o n


time.
If the l o n g i t u d i n a l m o m e n t M z i s suddenly d i s t u r b e d (for e x a m p l e , by a
sudden c h a n g e of t h e f i e l d v a l u e H 0 ) it r e t u r n s to its e q u i l i b r i u m v a l u e
e x p o n e n t i a l l y , a c c o r d i n g to a d i f f e r e n t i a l equation of t h e f o r m

dM,"Z _ M z (t) - Mo
~dt

T j is c a l l e d the " l o n g i t u d i n a l r e l a x a t i o n t i m e " o r the " s p i n - l a t t i c e r e l a x a t i o n


t i m e " . In g e n e r a l T 2 š T x .

5.4. B e h a v i o u r of a c o l l e c t i o n of a t o m s in an R F field

If a r a d i o f r e q u e n c y field is i n t r o d u c e d , it p r o d u c e s , at r e s o n a n c e ,
t r a n s i t i o n s b e t w e e n q u a n t u m s t a t e s of a t o m s . T h e s e m a g n e t i c dipole
t r a n s i t i o n s a r e s t u d i e d in q u a n t u m m e c h a n i c s , which e s t a b l i s h e s f o r m u l a s f o r
the t r a n s i t i o n p r o b a b i l i t i e s m m±l.
In t h e R F r e g i o n t h e n u m b e r of photons p r e s e n t is a l w a y s v e r y l a r g e and
s p o n t a n e o u s e m i s s i o n is n e g l i g i b l e . It c a n be shown that in t h i s c a s e 1 t h e
e x p e c t a t i o n v a l u e s obtained f o r m a c r o s c o p i c q u a n t i t i e s •\MZ)> and ^ M ^ a r e
i d e n t i c a l to t h e v a l u e s c a l c u l a t e d by a s s u m i n g a c l a s s i c a l b e h a v i o u r of t h e s e
quantities.
We s h a l l d e v e l o p a c l a s s i c a l p h e n o m e n o l o g i c a l t h e o r y (Fig. 14):
A c o l l e c t i o n of p a r a m a g n e t i c a t o m s (or ions o r nuclei) p l a c e d in a c o n s t a n t
f i e l d H 0 || Oz, p o s s e s s e s a l o n g i t u d i n a l m a g n e t i c m o m e n t Й 2 = M 0 = X q H q . At
t i m e t= 0 we i n t r o d u c e an R F f i e l d H x = 2HX c o s u t p a r a l l e l to the x - a x i s . What
will h a p p e n ? T h e r e c t i l i n e a r o s c i l l a t i n g field of a m p l i t u d e 2H;! c a n b e c o n -
s i d e r e d as a c o h e r e n t s u p e r p o s i t i o n of two r o t a t i n g f i e l d s , e a c h of a m p l i t u d e
Hj, r o t a t i n g in the e q u a t o r i a l x y - p l a n e in o p p o s i t e d i r e c t i o n s : one c l o c k - w i s e ,
the o t h e r a n t i - c l o c k w i s e . T h e y r o t a t e in p h a s e c o h e r e n c e with a n g u l a r
s p e e d ±io ( F i g . 15). An o b s e r v e r in a f r a m e r o t a t i n g at s p e e d ш (the s a m e
as t h e s p e e d of one of t h e s e f i e l d s ) w i l l s e e t h i s field Hj as a fixed c o n s t a n t

1
A. Abragam, T h e Principles of Nuclear Magnetism, Clarendon Press (1961), chapters II and 1П.
190 KASTLER

f i e l d i n t h e X - d i r e c t i o n of h i s r o t a t i n g f r a m e X Y Z . In t h e Z - d i r e c t i o n he
s e e s the field

to
H' = H n + -

T h e r e s u l t a n t of t h e s e two f i e l d s i s a f i e l d H £ff (H e f f e c t i v e ) in t h e X Z - p l a n e
of m a g n i t u d e

1/2

H eff

m a k i n g , with t h e Z - a x i s , a n a n g l e given by t a n 6 = (Hj/Hq) + u / y ) . F o r t h i s


o b s e r v e r t h i s f i e l d i s a s t e a d y f i e l d and in h i s f r a m e h e w i l l o b s e r v e t h e
L a r m o r p r e c e s s i o n of M a r o u n d H eff w i t h s p e e d и = - 7 H e f f .
At e x a c t r e s o n a n c e (и =ш0) t h e f i e l d c o m p o n e n t in the Z - d i r e c t i o n i s
H 0 + ( u 0 / 7 ) = 0 a s u 0 = ~ 7 H 0 . So, in t h i s c a s e , t h e only f i e l d s e e n by t h e
o b s e r v e r i s Hj|| OX, and f o r h i m t h e L a r m o r p r e c e s s i o n of M t a k e s p l a c e
in t h e Z Y - p l a n e with a n g u l a r s p e e d Uj = - y Hj. T h i s m o t i o n i s c a l l e d the
"nutation motion".
After a time

t - i l l - "
1
"l 21 7 I H 1

t h e l o n g i t u d i n a l m o m e n t M z i s t r a n s f o r m e d into a t r a n s v e r s e m o m e n t M t = My
a l o n g OY. If at t h i s t i m e t j we cut off t h e R F f i e l d , we h a v e p e r f o r m e d a
"90° p u l s e " and M t w i l l , in t h e l a b o r a t o r y f r a m e , m a k e a " f r e e p r e c e s s i o n "
and d e c a y with r e l a x a t i o n t i m e T 2 . But if the R F a c t i o n g o e s on, a f t e r t i m e
t 2 = 2 t 1 ; t h e m o m e n t b e c o m e s a l o n g i t u d i n a l m o m e n t in t h e - Z - d i r e c t i o n . We
h a v e , if we s t o p R F p o w e r at t i m e t 2 , p e r f o r m e d a 180° p u l s e . If we s t o p
t h e R F p o w e r at t h i s t i m e , M z w i l l r e t u r n to i t s e q u i l i b r i u m v a l u e M Q in t h e
f i e l d H 0 with r e l a x a t i o n t i m e T ^ Q u a n t u m m e c h a n i c a l l y a 180° p u l s e c o r r e s -
ponds to a "population i n v e r s i o n " .

5.5. C l a s s i c a l t h e o r y of the m o t i o n of a s p m - s u b m i t t e d t o a c o n s t a n t f i e l d
and an R F f i e l d

L e t u s now c o n s i d e r t h e c a s e of a p e r m a n e n t a p p l i c a t i o n of t h e R F f i e l d and
e s t a b l i s h by c a l c u l a t i o n t h e b e h a v i o u r of Й in a s t e a d y - s t a t e s i t u a t i o n . 2
T h i s w i l l l e a d u s t o t h e B l o c h e q u a t i o n s . We e s t a b l i s h t h e s e e q u a t i o n s in t h e
r o t a t i n g f r a m e X Y Z w h e r e we i n t r o d u c e t h e u n i t v e c t o r s i, j , k a l o n g t h e
a x e s X , Y , Z ( F i g . 16). T h e r e l a x a t i o n r e l a t i o n s a r e

dMx _ Mx dMy _ M^ dMz _ Mz-M0


~dt ' dt " " T2 ' ~dt %
2
We have neglected the effect of the field rotating in the opposite direction ( w « - ш 0 ). It can be shown
that it is negligible if Hj remains small (Hj « H0 ) .
IAEA - S M R - 1 2 / 9 191

We c o m b i n e t h e s e t h r e e r e l a t i o n s in w r i t i n g t h e v e c t o r - r e l a t i o n :

J k + (1)
dt т2 T2 Tl Tl

T h e e f f e c t of t h e f i e l d H e f f on M i s g o v e r n e d by t h e r e l a t i o n :

X H e f f ) = (M X 7 H e f f ) where 7Heff = (w-u 0 )k - W J

w h e r e we h a v e w r i t t e n Uj = - 7 H j . I n t r o d u c i n g Дw = u - ш0 , we o b t a i n

^ = ( M X Ï + M Y J + MZ к ) X ( Д и к - И / )

= -ДшМх]+ДшМуГ + и 1 М у к - и 1 м Д (2)

C o m b i n i n g (1) and (2) we g e t :

dM / Mx f Mv /М0 мг v
_ = ( _ _ * + дш My ) i - (лш M . - J - ^ M j i + (-S - к

We s e a r c h f o r a s t e a d y - s t a t e s o l u t i o n d M / d t = 0, s o i t s t h r e e c o m p o n e n t s
must be all zero:

(a) - М х + Т2ДшМу = 0 >М х = Т 2 Д и М у

(b) Т2 Д ш М Х - М У - WIT2MZ = 0

(c) M0-Mz + TlUlMy = 0 » M2 = M 0 + w 1 T 1 M y


192 KASTLER

I n t r o d u c i n g t h e s e v a l u e s of M and M into (b) we obtain:

M, 1 + Т 2 Д и + T T u2
2 1 2 1 "T2"lM0

T
2"l
M y = - M0
1+T® T 2 uJ

T Дьш
2 i
M - M,О о о о
1 + Т2 Ди + Т 1 Т2 ш1

м „ = м, 1 - Ti T 8 m z
1 + т 2 Дю + Т г Т 2 с

2 2
1 tTgAu)!
M
О о 2 2
1+ т2дш +TlT2Ul

We r e - i n t r o d u c e Ди = и-Ш 0 and И, = -THj. R e m e m b e r that 7 <0, SOCJ 1 >0 )


which p e r m i t s u s to w r i t e = H-l,

TJTI H
M„ = - M.
У 0 92 9 9 9
1+Т2 (и-Шо)2+Т1Т2Т2Н2

T2 Ы Н г Ы о - ц )
M* + м„
1+T ( U -CÜ„) 2 + T 1 T 2 7 2 H 2
2

1 -T 2 2 (u-u 0 ) 2
M = M,
° 1 + T 2 ( i o - U o ) 2 + T 1 T 2 72 H 2

It is c u s t o m a r y to w r i t e - M y = v and M^ = u.

5.6. D i s c u s s i o n of t h e Bloch e q u a t i o n s

We m u s t d i s c u s s t h e s e r e s u l t s . F i r s t n o t e that t h e s e m o m e n t s a r e given
in the r o t a t i n g f r a m e . So t h e t r a n s v e r s e m o m e n t M t =1 M x + jMy is r o t a t i n g
in the l a b o r a t o r y f r a m e and g i v e s r i s e to an induced e l e c t r o m o t i v e f o r c e in a
IAEA - S M R - 1 2 / 9 193

FIG. 17. P l o t of v a n d u as f u n c t i o n s of w.

coil p e r p e n d i c u l a r to the c o i l p r o d u c i n g the o s c i l l a t o r y R F f i e l d . T h i s


j u s t i f i e s B l o c h ' s d e t e c t i o n t e c h n i q u e of " n u c l e a r i n d u c t i o n " .
My is a l w a y s n e g a t i v e and h a s i t s m a x i m u m f o r u = uo.
|M J a s a f u n c t i o n of и h a s a b s o r p t i o n s h a p e .
M x is p o s i t i v e f o r u < u 0 , n e g a t i v e f o r u > u 0 and z e r o f o r ш = u 0 .
M x a s a f u n c t i o n of и h a s d i s p e r s i o n s h a p e .
With

i i ^ y , maJ
v = M,УI1 " 2
a +b (u-u0)

and

Шп-Ы
u = M^ - c o n s t X 2
a + b (u - wQ )

we can r e p r e s e n t v and u as f u n c t i o n s of и (Fig. 17). If Hj is s m a l l (if


Tj T 2 у H J « 1), we can w r i t e f o r s m a l l R F p o w e r :

T H
- Mv Mo sM i
i T2V"0)2
+

M Т 2 |т1 Н^Цр-и)
l+T2(u-u0)2

M 1-Т^(ц-Шп)2
M* = o
l+Tz2(u-u0)2
194 KASTLER

FIG.18. Rotating magnetic moment in the two frames.

T h e s e e x p r e s s i o n s do not depend on Tj . At r e s o n a n c e M z = M 0 and


M y , „jax = M 0 T 2 | ? | Hj. T h e width at half m a x i m u m of M y is

ш-ш 0 = ± 1 / T 2 o r бы = 2 / T 2 and Sv=6u/2тг = 1/тгТ 2 .

F o r high R F p o w e r , M z max at r e s o n a n c e is r e d u c e d to

M„
M.z, шах = о о
i+^T^H*

where

l + T ^ H *

is the already mentioned "saturation f a c t o r " .


T h e m a x i m u m v a l u e of the a b s o r p t i o n c u r v e b e c o m e s

M„ = МрТаЫн,
"у, max I о о
1
1 + T j Tg 7 H 2

and i t s h a l f - w i d t h is given by

\2 J T2 T2 1

w h e r e (<5ш)2 is a l i n e a r f u n c t i o n of Hj. T h i s e f f e c t is c a l l e d "power


b r o a d e n i n g " . T h e n e g a t i v e s i g n of My s i g n i f i e s t h a t d u r i n g the L a r m o r
p r e c e s s i o n in the x y - p l a n e in t h e l a b o r a t o r y f r a m e , My h a s a phase retardation
of 7t/2 with r e s p e c t to the r o t a t i n g f i e l d Hj, while M x is the rotating com-
ponent of M t in p h a s e with H j if и < u 0 , but in opposition of p h a s e with it if
IAEA - S M R - 1 2 / 9 195

m +1

FIG.19. Zeeman splitting.

и>ш 0 . T h e r o t a t i n g m a g n e t i c m o m e n t is M t = (M x and r e t a r d s with


r e s p e c t to H j by an angle cp given by

My
tan < f o r ш < u,
'0
Mv Т2Ц-и>)

See a l s o F i g . 18. We note that f o r u > u 0 the sign of M x is n e g a t i v e . The


r o t a t i n g field H j e x e r t s on the r o t a t i n g m o m e n t M t a t o r q u e

Г = M, X H ; = |M y | Hj

T h i s t o r q u e is e x e r t e d by the R F field on the s a m p l e c o n t a i n i n g the s p i n s and


can b e m e a s u r e d . The work done by H j on M t is Г m u l t i p l i e d by the angle of
r o t a t i o n , which, p e r unit t i m e , is u . The p o w e r t r a n s m i t t e d f r o m the R F
c i r c u i t to the s u b s t a n c e is

W = Ги = |М I и H j

ц т Ы Hi
W = M, 2

° l + T ^ - u ^ + T ^ H ?

It is m a x i m u m f o r u= u 0 . At t h e " a b s o r p t i o n p e a k " we define:

Wmax = M„0 ц т 2 |т| H!


l+T.T.y2^

T h e s a t u r a t i o n f a c t o r now c o m e s in and, f o r high R F power, W m a x t e n d s to


the a s y m p t o t i c v a l u e

w . м о ц о _ Mp Hp . XQHQ
vv
as » m rp
H T j ^
196 KASTLER

<
и
Q
Z

s:
о
<
>

<
о

67 68 69 70 71

MAGNETIC FIELD IN GAUSS

FIG.20. Resonance curves as obtained by Brossel.

i n d e p e n d e n t of the R F a m p l i t u d e . In t h i s l i m i t i n g c a s e the e n e r g y t r a n s f e r r e d
to the s u b s t a n c e in t i m e Т г is equal to t w i c e the m a g n e t i c e n e r g y s t o r e d in
t h e s u b s t a n c e in t h e c o n s t a n t f i e l d H n

6. RESULTS

Among the t h o u s a n d s of r e s u l t s obtained in r a d i o - f r e q u e n c y s p e c t r o s c o p y ,


we s e l e c t a few t y p i c a l o n e s : .

(a) Study of p u r e Z e e m a n i n t e r v a l s

P u r e e l e c t r o n i c p a r a m a g n e t i s m c o r r e s p o n d s to J f = 0 , I = 0. In a field H 0 ,
a J - l e v e l is split into 2 J + 1 e q u i d i s t a n t m j - s t a t e s (Fig. 19):

E = m H
I igjMB o
IAEA - S M R - 1 2 / 9 197

where
-9П -1
jUg = 0.9274096 X 10 erg • G
±65
The s e l e c t i o n r u l e Д т = ± 1 g i v e s only one r e s o n a n c e f r e q u e n c y c o r r e s p o n d i n g
to Д Е =u 0 fr = у H 0 h = g j P B H 0 . One m e a s u r e s the r a t i o w 0 /H 0 = 7 = gj juB/ii and
d e d u c e s 7, gj and jUj = 7JÏ1. E x a m p l e : the f r e e e l e c t r o n with J = s = The
r e s o n a n c e o c c u r s b e t w e e n the + 1 / 2 and - 1 / 2 s t a t e s .
Q u a n t u m e l e c t r o d y n a m i c s p r e d i c t e d f o r the e l e c t r o n spin a m a g n e t i c
m o m e n t ц 5 ф ц в . ß s = j u B ( l + f ) , w h e r e Ç should be of o r d e r 10" 3 . M e a s u r e -
m e n t s m a d e by K u s c h and F o l e y on bound e l e c t r o n s in a t o m s c o n f i r m e d t h i s
p r e d i c t i o n . M a g n e t i c r e s o n a n c e s on f r e e e l e c t r o n s w e r e obtained by D e h m e l t
u s i n g an o p t i c a l d e t e c t i o n m e t h o d . He c o n f i r m e d the v a l u e of | obtained by
K u s c h . A n o n - R F e x p e r i m e n t d e s i g n e d by C r a n e and r e a l i z e d by h i m and his
collaborators yielded

? = 1.159622 X 10" 3
±27

in good a g r e e m e n t with t h e o r e t i c a l p r e d i c t i o n s :
1 cv су2 15
i T-— + 0.3285 -Я-+ 0.13 -TT + • • • = 1.1596 „
2 -и ti2 7г 39

d e p e n d i n g on the v a l u e adopted f o r the f i n e - s t r u c t u r e c o n s t a n t a . F o r the


e l e c t r o n , ( g - 2 ) / 2 = f . T h i s is c a l l e d the (g-2) a n o m a l y .
In the c a t e g o r y of p u r e e l e c t r o n i c r e s o n a n c e s we c a n r a n g e B r o s s e l ' s
e x p e r i m e n t on E P R of the e x c i t e d s t a t e 6 3 P 1 of the even i s o t o p e s of m e r c u r y .
F o r t h i s s t a t e , J = l , he found g = 1.48 ^ 3 / 2 .
T h e r e s o n a n c e c u r v e s obtained by B r o s s e l a r e shown in F i g . 20.

P u r e n u c l e a r p a r a m a g n e t i s m . If the e l e c t r o n c o n f i g u r a t i o n h a s J = 0, it
is d i a m a g n e t i c : /Uj = 0. If t h e r e i s a n u c l e a r m o m e n t I =/= 0, we o b s e r v e , in a
field HQ, e q u i d i s t a n t n u c l e a r Z e e m a n l e v e l s m : . We c a n u s e f o r the r e s o n a n c e
interval the f o r m u l a

Д Е = u)0fi = H0 = g t pg H 0 = g l V N H 0

where
m MH
rr^- aand
nd в! = Si
Si gT —
m0

w h e r e /uN is t h e n u c l e a r m a g n e t o n . T h e n u c l e a r m o m e n t i s given by

Mi = g r i M B = g ; i ^ N

In g e n e r a l , t h e t a b l e s give (/Lij/pN) = g j l a s the n u c l e a r m o m e n t , in u n i t s of


the nuclear magneton:

juN = 5.050951 X 10" 2 4 e r g - G " 1


±50
198 KASTLER

5.585 MHz

3300 3350 3Í00 3450 3500


И (gaussl

(С)
eu
o<= r „D^OO 1

I
с
] ji*?o4ol
0
FREQL ENCY ,
6.96 MHz
1
i f f
Iii
ЭОО°

лТ I 1 E F
1 3
1625 1650 1675
MAGNETIC FIELD IN GAUSS

FIG. 21. NMR curves as obtained by Rabi.


(a) The 7 Li nucleus in LiCl molecules.
(b) The 19F nucleus in NaF molecules.
(c) Protons in the H2 molecule (orthohydrogen 1=1, J = 1 rotational state).
IAEA-SMR-L2/9 199

FREQUENCY (Hz)

FREQUENCY (Hz)

HG. 22. NMR signals of (a) 19s Hg and (b) 20I Hg (after В. Cagnac, Ann. Phys. (Paris) 6 (1961) 467).
200 KASTLER

FIG. 23. NMR Signal of protons in water.

A s i m p l e e x a m p l e is that of the f r e e n e u t r o n , on which a r e s o n a n c e


e x p e r i m e n t a n a l o g o u s to a Rabi e x p e r i m e n t h a s b e e n m a d e by Bloch and
A l v a r e z . T h e y found f o r this 1 = 1 / 2 p a r t i c l e :

= £n.= _ 1.91280

T h e NMR r e s o n a n c e of o t h e r n u c l e i h a s b e e n o b s e r v e d in d i a m a g n e t i c a t o m i c
ground s t a t e s . F i g u r e 21 s h o w s NMR r e s o n a n c e c u r v e s obtained by Rabi.
By the o p t i c a l m e t h o d , Cagnac found f o r the odd m e r c u r y i s o t o p e s
199
Hg and 2 0 1 Hg:

p 1 9 9 = + 0.497865 Mn I199=J
±6

^201 = * 0.55 1 3 44 mn I = |
±9

^ ä i . = - 1.107416 4
P
l99 ±5

F i g u r e 22 s h o w s r e s o n a n c e c u r v e s f o r 1 9 9 Hg and 201 Hg.


C a g n a c a l s o m e a s u r e d f o r both n u c l e i t h e r e l a x a t i o n t i m e s T]^ in p u r e
m e r c u r y v a p o u r in a f u s e d s i l i c a v e s s e l and found
1QQ 201
T - 3 s T^ - 0.05 s at r o o m t e m p e r a t u r e .

The s t r i k i n g d i f f e r e n c e b e t w e e n the two Тг v a l u e s can b e e x p l a i n e d by the


f a c t t h a t f o r 2 0 1 Hg r e l a x a t i o n o c c u r s by an e l e c t r i c q u a d r u p o l e i n t e r a c t i o n ,
which is a b s e n t in the c a s e of 199 Hg.
P a r a m a g n e t i c n u c l e i in d i a m a g n e t i c m o l e c u l e s a r e in g e n e r a l only
l o o s e l y bound to the m o l e c u l e and behave in an e x t e r n a l f i e l d H 0 , in a f i r s t
a p p r o x i m a t i o n , l i k e f r e e n u c l e i whose m a g n e t i c m o m e n t s c a n b e d e t e r m i n e d
by NMR e x p e r i m e n t s . E x a m p l e s : 7 L i in L i C l , o r ^ in KOH, o r p r o t o n s
IAEA - S M R - 1 2 / 9 201

in liquid w a t e r . F o r p r o t o n s in w a t e r or in o r g a n i c m o l e c u l e s t h e l o c a l f i e l d
c r e a t e d by the m o l e c u l a r s u r r o u n d i n g a d d s t o t h e e x t e r n a l f i e l d . A d i a m a g n e t i c
c o r r e c t i o n h a s t o b e a p p l i e d to c a l c u l a t e t h e t r u e p r o t o n m o m e n t .
F i g u r e 23 s h o w s an NMR s i g n a l of p r o t o n s in w a t e r .
Without t h i s c o r r e c t i o n f o r p r o t o n s in w a t e r , one m e a s u r e s

7 ' = 26 751.270 and |eL = ZjL = 4.257597 k H z - G _ 1


H
±80 ° ±13

W i t h the d i a m a g n e t i c c o r r e c t i o n we g e t :

26 751.965 and = 4.257705 k H z - G '


27Г
±80 ±13

This gives

ÍÍL = 1 2.792782
±17

T h e p r o t o n m o m e n t ц р h a s a l s o b e e n c o m p a r e d d i r e c t l y with t h e B o h r m a g -
neton :

^ = 1.52103264 X 10" 3
йв
±50

T h e c a s e of t h e H 2 m o l e c u l e s t u d i e d by the R a b i m e t h o d i s i n t e r e s t i n g .
T h e f i n e s t r u c t u r e of i t s NMR s i g n a l g i v e s i n f o r m a t i o n on t h e m a g n e t i c
i n t e r a c t i o n s in t h e m o l e c u l e . It c o r r e s p o n d s t o the J = 1 r o t a t i o n a l l e v e l of
o r t h o h y d r o g e n (I 1 + I 2 = 1). See F i g . 21c.
P a r a m a g n e t i c i o n s d i l u t e d in a d i a m a g n e t i c s o l v e n t or in d i l u t e d c r y s t a l s
a l s o b e h a v e , in f i r s t a p p r o x i m a t i o n , like f r e e m a g n e t s in t h e e x t e r n a l f i e l d H 0 ,
and t h e i r g - f a c t o r c a n be d e t e r m i n e d . F i g u r e 24 s h o w s a r e s o n a n c e s i g n a l of
Mn + + o b s e r v e d by Z a v o i s k y . He o b t a i n e d g «2. But n o t e t h a t in t h i s c a s e t h e
r e s o n a n c e s i g n a l is l a r g e , the r e l a x a t i o n t i m e T2 being v e r y s m a l l .

(b) T h e f i n e - s t r u c t u r e i n t e r v a l s of t h e n= 2 l e v e l of t h e h y d r o g e n a t o m .
The Lamb shift

T h e l e v e l n = 2 of t h e h y d r o g e n a t o m c o n t a i n s t h r e e f i n e s t r u c t u r e l e v e l s :
2 2 SI/2 ( m e t a s t a b l e ) , 2 2 P ц 2 and 2 2 P 3 / 2 . T h e e n e r g y d i f f e r e n c e b e t w e e n the
two P l e v e l s is o b s e r v e d in t h e f i n e s t r u c t u r e of t h e o p t i c a l H a l i n e . It i s of
t h e o r d e r Д с т ~ 0 . 3 3 c m - 1 ~ 10 GHz. A c c o r d i n g to D i r a c ' s t h e o r y , t h e two
l e v e l s 2 2 S 1 / 2 and 2 2 P 1 / / 2 s h o u l d b e d e g e n e r a t e . T h e y a r e n o t . L a m b and
R e t h e r f o r d (1948) h a v e m e a s u r e d t h e i r d i s t a n c e by s t u d y i n g t h e r e s o n a n c e
b e t w e e n t h e m j s t a t e s of S i / 2 and P i / 2 - ( F i g . 25). T h e s e t r a n s i t i o n s a r e e l e c t r i c
d i p o l e t r a n s i t i o n s . T h e r e s u l t of t h e i r m e a s u r e m e n t i s

2 2 S 1 / 2 - 2 2 P 1 / 2 = 1.059 004 GHz


±10
202 KASTLER

H (Oel
FIG.24. EPR signals obtained by Zavoisky (1945).
(a) EPR signal of M n H ions in S0 4 Mn at 2.75 GHz;
(b) EPR signal of C r + + + ions in CrCl s at 2.19 GHz and
(c) 2.76 GHz.
IAEA - S M R - 1 2 / 9 2 0 3

дм=о
ctě
_
l\
I\
(b) 20 -

дм=1
\
I \
УV
af

I I\
7
1 1 г"
1000 1200 1400 1600
GAUSS

FIG.25. Z e e m a n splitting and resonance signals.


2
(a) Z e e m a n splitting in magnetic field (abscissa, units of 5214 G) of the fine-structure states 2 P3/2.
2 2 S j / 2 and 2 2 Pj д of the hydrogen a t o m ;
(b) resonance signals :

a f 2 tS1/2. m = + 1 / 2 — 2 гР1/г, m = - 1 / 2

et e 2 %/г, m = + 1/2—> 2 г ? 1 / г , m = + 1/2 (after Lamb and Retherford).

It is c a l l e d the " L a m b s h i f t " and h a s b e e n explained by q u a n t u m e l e c t r o -


dynamics.

(c) H y p e r f i n e s t r u c t u r e s in a t o m i c g r o u n d s t a t e s

T h e h y p e r f i n e s t r u c t u r e (HFS) of a t o m i c e n e r g y s t a t e s is a r e s u l t of the
i n t e r a c t i o n b e t w e e n the e l e c t r o n c o n f i g u r a t i o n of the a t o m and the n u c l e a r
m o m e n t s . It o c c u r s if the n u c l e a r spin v a l u e I is d i f f e r e n t f r o m z e r o .
204 KASTLER

z
T A B L E I. H Y P E R F I N E I N T E R V A L S IN GROUND S T A T E S1/2 OF
H Y D R O G E N AND A L K A L I A T O M S

Atom Nuclear spini v t (MHz)

>H 1/2 1420.40 5 a


2
H 1 327.384
6
Li 1 228.22
7
Li 3/2 803.54
22 c
Na 3 1 220.6
23
Na 3/2 1771.75
39K 3/2 461.75
«кс 4 1285.7
41K 3/2 254.02
85
Rb 5/2 3 035.73

<"Rb 3/2 6 834.70


133
Cs 7/2 9192.7b
13
fcs C 7/2 9 724
137 c
Cs 7/2 10 126

a
This is the line of the hydrogen maser. It is also the emission line observed in radio-astronomy,
b This is the line of the caesium atomic clock which defines the time-unit.
c
Radioactive isotopes.

We h a v e s e e n t h a t an a t o m i c e n e r g y s t a t e h a s a c h a r a c t e r i s t i c J - v a l u e ,
t h e a n g u l a r m o m e n t u m of the e l e c t r o n c o n f i g u r a t i o n in t h i s s t a t e i s P = J h
and t h e a s s o c i a t e d m a g n e t i c m o m e n t i s Hj = g JjUb w h e r e ц в i s the B o h r
m a g n e t o n and g t h e L a n d é - f a c t o r of t h e s t a t e . If a n u c l e a r s p i n 1 ^ 0 e x i s t s ,
t h e a n g u l a r m o m e n t u m of the n u c l e u s I h is a l s o a s s o c i a t e d t o a n u c l e a r
m a g n e t i c m o m e n t jU; w h i c h i s v e r y s m a l l and e x p r e s s e d in n u c l e a r m a g n e t o n s
HN a s we h a v e s e e n . T h e i n t e r a c t i o n b e t w e e n t h e t w o m o m e n t s n j and щ
g i v e s r i s e t o a c o u p l i n g e n e r g y which c a n b e e x p r e s s e d b y

A i s c a l l e d the h y p e r f i n e c o u p l i n g c o n s t a n t . T h e r e s u l t i s t h a t e a c h e n e r g y
l e v e l J i s s p l i t i n t o 21 + 1 " h y p e r f i n e s u b l e v e l s " w h i c h a r e d e s i g n e d by a
h y p e r f i n e q u a n t u m n u m b e r F w h i c h c a n t a k e 21 + 1 d i f f e r e n t v a l u e s — d i f f e r i n g
b y u n i t y — b e t w e e n J - l a n d J + l . (In t h e c a s e w h e r e J < I , t h e two n u m b e r s
J and I h a v e t o be i n t e r c h a n g e d . ) F o r e x a m p l e , in t h e c a s e of the h y d r o g e n
a t o m and of t h e a l k a l i a t o m s , t h e g r o u n d s t a t e 2S^ h a s J = f and t h e t w o F - v a l u e s
a r e F - p I + i and F 2 = I - i . T h e e n e r g y d i f f e r e n c e b e t w e e n t h e s e t w o s t a t e s
Ep - Ep i s c a l l e d the " h y p e r f i n e i n t e r v a l " , and i t s r e s o n a n c e f r e q u e n c y
v0 - (Ep - Ep ) / h i s a c h a r a c t e r i s t i c f r e q u e n c y of e a c h a t o m i c s p e c i e s . S o m e
of t h e s e f r e q u e n c i e s a r e g i v e n in T a b l e I.
T r a n s i t i o n s b e t w e e n t h e s e F - l e v e l s a r e o b s e r v e d in r a d i o - f r e q u e n c y
spectroscopy.
IAEA - S M R - 1 2 / 9 205

H y p e r f i n e s t r u c t u r e s have b e e n s t u d i e d , e s p e c i a l l y by the Rabi m e t h o d ,


in the ^ j / g ground s t a t e s of a l l a l k a l i and f o r t h e d i f f e r e n t i s o t o p e s of
h y d r o g e n . T h e evolution of the m F s t a t e s of t h e s e J = 1 / 2 l e v e l s in an e x t e r n a l
f i e l d H0 is given by the B r e i t - R a b i f o r m u l a .
F o r e x a m p l e f o r 1 3 3 C s , 1 = 7 / 2 and t h e two F - l e v e l s a r e F j = 1+ 1/2 = 4
and F 2 = I - 1 / 2 = 3. T h e i r gF f a c t o r s in s m a l l f i e l d s a r e

gj 2 _ 1_
G
FJ " " G
F 2 " 21 + 1 " 8 " 4

T h e f r e q u e n c y i n t e r v a l b e t w e e n the two F - s t a t e s c o r r e s p o n d i n g to ДЕ 0 = hv 0
in a z e r o m a g n e t i c field h a s b e e n a c c u r a t e l y m e a s u r e d and can be d e t e r m i n e d
in the a t o m i c clock u s i n g c a e s i u m a t o m s to d e f i n e the t i m e unit.
T h e p r e s e n t unit of t i m e , one s e c o n d , is b a s e d on the convention

v. ( 1 3 3 Cs ) = 9 192 631 770.00 Hz

T h i s is the f r e q u e n c y m e a s u r e d b e t w e e n the two Z e e m a n s u b l e v e l s ( F , m p ) :


(4, 0) 2 (3, 0). T h i s f r e q u e n c y s h o w s a q u a d r a t i c d e p e n d e n c e on the f i e l d
Ho ' v o,o ' vo +427 H 2 • (Hz- G~2), while t h e o t h e r h y p e r f i n e t r a n s i t i o n s depend
l i n e a r l y on t h e f i e l d v a l u e .
C o n s t r u c t i n g a h y d r o g e n m a s e r , R a m s e y and c o - w o r k e r s have
m e a s u r e d , in this unit, t h e HFS i n t e r v a l s of h y d r o g e n and of t r i t i u m :

7H = 1 4 2 0 4 0 5 751.864
±1

7 = 1 516 701 470.808


T
±7

^ L = 1.067 794 514 973


7
H ±5 (10" 12 )

T h i s is p r o b a b l y the h i g h e s t p r e c i s i o n e v e r obtained in any p h y s i c a l m e a s u r e m e n t .


We m a y c o m e b a c k to Mn ++ ions at high dilution w h e r e a h y p e r f i n e s t r u c -
t u r e a p p e a r s with s i x p e a k s : 21 + 1 = 6, i n d i c a t i n g that 1 = 5 / 2 f o r t h e M n n u c l e u s
(Fig. 26).

(d) T h e m u o n i u m e /u+

M u o n i u m was d i s c o v e r e d by V e r n o n Hughes in 1957 and is an a t o m i c


s y s t e m f o r m e d by a p o s i t i v e j u - m e s o n which h a s c a p t u r e d an e l e c t r o n . It can
b e c o n s i d e r e d as a light i s o t o p e of h y d r o g e n and h a s in i t s ground s t a t e , like
h y d r o g e n , two h y p e r f i n e l e v e l s , F = 1 and F = 0. In a f i e l d H 0 the Z e e m a n
s p l i t t i n g s a r e given by a B r e i t - R a b i f o r m u l a ( F i g . 27). T h e muon m a s s
c o m p a r e d with that of the e l e c t r o n is т д / т е = 206.761 ± 0.005, the r e d u c e d
m a s s is l / й = 1/m^ + l / m e , and the R y d b e r g c o n s t a n t is RM = 109 209.12 cm" 1 ,
206 KASTLER

Л i, N

л 2 N

л
FIG.26. Paramagnetic resonance signals of Mn + + ions in aqueous solutions of S0 4 Mn. From top to bottom
concentration is reduced (N = normal solution) and ahyperfine structure with six peaks appears. 21 + 1 = 6,
nuclear spin of 55Mn : 1 = 5/2 (after Schneider and England).

c o m p a r e d with R H = 109 677.58 c m - 1 . The two h y p e r f i n e l e v e l s a r e s e p a r a t e d


by an i n t e r v a l p r e d i c t e d by c a l c u l a t i o n :

„ = I i ö 2 c ^ R » 4.524 GHz
0 h 3 'ue "
C o r r e c t i o n s of q u a n t u m e l e c t r o d y n a m i c s give vQ =4.46316 GHz. The B r e i t -
Rabi f o r m u l a c a n be w r i t t e n

ДЕ, AE„
E.F, mE
1 + 2 т р х + х"

with
(g - g )ц H
and x =
ДЕ,'о

T h e d e t e c t i o n of R F r e s o n a n c e s of m u o n i u m i s b a s e d on the following
f a c t s : T h e m u o n is p r o d u c e d by stopping pions c o m i n g f r o m a s y n c h r o -
c y c l o t r o n in a r g o n gas:

7г+ -*• + neutrino

The h a s i t s spin v e c t o r a n t i p a r a l l e l to the v e l o c i t y v e c t o r of t h e ir*, and


the f i e l d H 0 i s applied p a r a l l e l t o this s p i n v e c t o r , s o т д = + 1 / 2 . A f t e r a
m e a n life of 2.2 X 10" 6 s , the d e c a y s to

-* e + + n e u t r i n o s

T h e r e is an a s y m m e t r y of p o s i t r o n e m i s s i o n , the e m i s s i o n b e i n g f a v o u r e d
in the d i r e c t i o n of the /u+ spin (positive d i r e c t i o n of H 0 ). This is equivalent
to n u c l e a r o r i e n t a t i o n of the m u o n i u m p r o d u c e d . D i f f e r e n t c o u n t e r s m e a s u r e
IAEA - S M R - 1 2 / 9 207

m 3 = *'/2- m u =*V2

m, = • V2. nv-1/!

• mj e - ' / î . = - y2

FIG.27. Zeeman splitting in field H, as given by Breit-Rabi formula.

t h e n u m b e r of p o s i t r o n s e m i t t e d in the + H 0 and - H 0 d i r e c t i o n s . If by a
m a g n e t i c r e s o n a n c e the ц* spin is r e v e r s e d , the counting r a t e i s changed.
T h i s e f f e c t is u s e d to m o n i t o r t h e r e s o n a n c e and to d e t e r m i n e i t s f r e q u e n c y in
a f i e l d HQ. R F r e s o n a n c e s in h i g h - f i e l d (rrij,m^) and in l o w - f i e l d conditions
( F , m p ) h a v e b e e n o b s e r v e d by Hughes and h i s c o - w o r k e r s . T h e y give the
experimental values

i/Q = 4463.15 ± 0.06 MHz f r o m h i g h - f i e l d m e a s u r e m e n t s ,

and

v'o = 4463.18 ± 0.12 MHz f r o m l o w - f i e l d m e a s u r e m e n t s ,

which a r e in e x c e l l e n t a g r e e m e n t with quantum e l e c t r o d y n a m i c s .


The e x p e r i m e n t a l c o n d i t i o n s a r e the following:

(a) H i g h - f i e l d r e s o n a n c e : HQ= 5 400 g a u s s x=3.4, resonance frequency


l o c a t e d b e t w e e n 1.83 and 1.84 GHz
(b) Low-field resonance: H0=2.7 gauss

One o b s e r v e s in t h i s c a s e the t r a n s i t i o n s 1,1 ->0,0 and 1 , - 1 -» 0,0. T h e


r e s o n a n c e s a r e o b s e r v e d at d i f f e r e n t a r g o n p r e s s u r e s and one h a s to e x t r a -
p o l a t e to t h e z e r o - p r e s s u r e v a l u e .

(e) Positronium

T h i s is a s y s t e m f o r m e d by a p o s i t i v e e l e c t r o n e + and a n e g a t i v e
e l e c t r o n e". Its e x i s t e n c e w a s s u g g e s t e d by M o h o r o v i c i č in 1934. It w a s
d i s c o v e r e d by M a r t i n D e u t s c h (1951) in the annihilation p r o c e s s of p o s i t r o n s
in g a s e s , w h e r e a p r e s s u r e - i n d e p e n d e n t h a l f - l i f e of the o r d e r of 10" 7 s w a s
found. I t s B o h r l e v e l s a r e given by E n = (Rhc/n 2 ) and i t s B o h r r a d i u s i s
t w i c e that of h y d r o g e n . In i t s g r o u n d level n = 1 it e x i s t s in two d i f f e r e n t
s t a t e s , both with L = 0 (S s t a t e s ) . T h e notation u s e d f o r t h e m is 3 S j and 1 S Q .
F o r t h e o r d i n a r y , n e g a t i v e e l e c t r o n , the a n g u l a r m o m e n t u m p and the
m a g n e t i c m o m e n t ц a r e o p p o s i t e , f o r the p o s i t i v e e l e c t r o n o r p o s i t r o n , t h e
two v e c t o r s have the s a m e d i r e c t i o n .
208 KASTLER

NEGATIVE ELECTRON POSITIVE ELECTRON

P>
111
- * HI-

J
STATE S, STATE S0
OF POSITRONIUM OF POSITRONIUM

1-Й
I—

P, P2=0
Pi * P2 = 1
Ï , • M-2 = 0 Ï , + il2= 1
ORTHO- POSITRONIUM PARA-POSITRONIUM

FIG-28. Formation of ortho- and parapositronium.

If the two p a r t i c l e s c o m b i n e to f o r m p o s i t r o n i u m , they can do it in two


d i f f e r e n t m a n n e r s (Fig. 28):
(a) T h e two a n g u l a r m o m e n t a a r e p a r a l l e l , and in this c a s e the two m a g n e t i c
m o m e n t s a r e a n t i p a r a l l e l . The r e s u l t a n t a n g u l a r m o m e n t u m is

!*+!*=ft
which c o r r e s p o n d s to a s t a t e J = 1 o r a 3 S 1 s t a t e . The r e s u l t a n t m a g n e t i c
m o m e n t is z e r o . T h i s s t a t e is c a l l e d t h e " o r t h o - p o s i t r o n i u m " s t a t e .
(b) T h e two a n g u l a r m o m e n t a a r e o p p o s i t e in d i r e c t i o n and t h e two m a g n e t i c
m o m e n t s have the s a m e d i r e c t i o n :

which c o r r e s p o n d s to a s t a t e J = 0 o r a 1 S 0 s t a t e . Its r e s u l t a n t m a g n e t i c
m o m e n t i s e q u a l to two B o h r m a g n e t o n s . T h i s s t a t e is c a l l e d the
"para-positronium" state.

F i g u r e 29 shows the d i f f e r e n c e of e n e r g y of t h e s e two s t a t e s and t h e i r


b e h a v i o u r in a m a g n e t i c field HQ.
In i t s s i n g l e t s t a t e with opposite s p i n s , p o s i t r o n i u m c a n d e c a y by a
t w o - p h o t o n p r o c e s s , both photons having the e n e r g y E = hv = 0.5 MeV. To
t h i s d e c a y c o r r e s p o n d s a l i f e t i m e of L25 X 1 0 " 1 0 s . In i t s t r i p l e t s t a t e ,
p o s i t r o n i u m can d e c a y only by a t h r e e - p h o t o n p r o c e s s w h o s e p r o b a b i l i t y is
m u c h s m a l l e r and c o r r e s p o n d s to a l i f e t i m e of 1.4 X 10" 7 s .
IAEA - S M R - 1 2 / 9 209

FIG.29. Energy difference of ortho- and parapositronium, behaviour in a magnetic field.

P h o t o n s of e n e r g y s m a l l e r than 0.5 MeV, e s p e c i a l l y in t h e r a n g e


0.38 MeV, c a n o r i g i n a t e only in t h e t h r e e - p h o t o n p r o c e s s . The e n e r g y
i n t e r v a l ДЕ0 b e t w e e n the two s t a t e s is of the o r d e r of

г л 2 у ц2
AE =—TT/Ligl^ (0) = - í - j = 204.4 GHz
a
o

T a k i n g into a c c o u n t t h e q u a n t u m e l e c t r o d y n a m i c a l c o r r e c t i o n s , this v a l u e i s
changed to

A E 0 / h = 203.37 GHz (A = 1.5 m m )

G e n e r a t o r s of t h i s high f r e q u e n c y a r e not a v a i l a b l e . By applying a f i e l d H 0 ,


the two s t a t e s (1,0) and (0,0) a r e m i x e d . T h e a d m i x t u r e of the s i n g l e t s t a t e
to (1,0) s h o r t e n s t h e l i f e t i m e of the l a t t e r .
An R F r e s o n a n c e at 3 GHz in a field n e a r 9000 g a u s s p r o d u c e s the
transitions

(1, ± 1 ) - (1, 0)

and f a v o u r s the t w o - p h o t o n d e c a y p r o c e s s . T h e r e s o n a n c e c a n be m o n i t o r e d
by c o u n t e r s . T h i s R F e x p e r i m e n t m a d e in 1952 by D e u t s c h and Brown g i v e s
the r e s u l t :

v0 = ДЕд/h = 203.2 ± 0.3 GHz,

in good a g r e e m e n t with q u a n t u m e l e c t r o d y n a m i c s .
210 KASTLER

7. CONCLUSION

A s e r i e s of f e a t u r e s of R F S w e r e not m e n t i o n e d , f o r e x a m p l e the
i m p o r t a n c e of h i g h - r e s o l u t i o n NMR f o r p r o b l e m s of c h e m i c a l s t r u c t u r e , o r
t h e m e t h o d s of d y n a m i c o r i e n t a t i o n of n u c l e i , y i e l d i n g p o l a r i z e d b e a m s and
polarized targets for nuclear-physics experiments.
T h e e n o r m o u s a m o u n t of work done on E P R and NMR in liquids and s o l i d s
h a s t h r o w n light on s o l i d - s t a t e s t r u c t u r e s and on the b e h a v i o u r of p a r a -
m a g n e t i c ions and n u c l e i in condensed m a t e r i a l . R F S h a s found i t s
a p p l i c a t i o n s a l s o in r a d i o a s t r o n o m y . T h e line of a t o m i c h y d r o g e n at
1420 MHz (X = 21 c m ) i s o b s e r v e d as e m i s s i o n , line f r o m t h e h y d r o g e n c l o u d s
in the g a l a x y . I t s s y s t e m a t i c study h a s given i n f o r m a t i o n on the s p i r a l
s t r u c t u r e of our galaxy. O t h e r l i n e s , of the r a d i c a l OH and the w a t e r
m o l e c u l e , a r e o b s e r v e d in e m i s s i o n . L i n e s of m a n y r a d i c a l s and m o l e c u l e s
a r e o b s e r v e d in a b s o r p t i o n and show that t h e s e m o l e c u l e s a r e p r e s e n t in
i n t e r s t e l l a r s p a c e w h e r e they a r e p r o b a b l y s y n t h e s i z e d by p h o t o c h e m i c a l
reactions.
Let u s f i n a l l y m e n t i o n s o m e s p e c i a l l i t e r a t u r e that m a y be of i n t e r e s t
f o r the r e a d e r . In the f i e l d of m o l e c u l a r b e a m s we r e f e r to the a r t i c l e by
J . B. K e l l o g and S. M i l l m a n , " T h e m o l e c u l a r b e a m m a g n e t i c r e s o n a n c e
m e t h o d " , (Rev. Mod. P h y s . 1_8 (1946) 323) o r the book by N. F . R a m s e y ,
M o l e c u l a r B e a m s , C l a r e n d o n P r e s s (1956).
As r e g a r d s n e u t r o n NMR let us m e n t i o n F . Bloch, P h y s . Rev. 74^ (1948)
1025; s e e a l s o N. F . R a m s e y , P h y s . Rev. 179 (1969) 1285. F o r E P R we
r e c o m m e n d the book by A. A b r a g a m and B. B l e a n e y , E l e c t r o n P a r a m a g n e t i c
R e s o n a n c e of T r a n s i t i o n I o n s , C l a r e n d o n P r e s s (1970). D e t a i l s on the
L a m b s h i f t m a y b e found in W. L a m b , Rep. P r o g . P h y s . _14 (1951) 19, and on
the (g-2) a n o m a l y of t h e e l e c t r o n in H. R. C r a n e and D. T. W i l k i n s o n , P h y s .
R e v . 130 (1963) 852. As to optical m e t h o d s s e e R. B e r n h e i m , O p t i c a l
P u m p i n g , B e n j a m i n (1965); C. C o h e n - T a n n o u d j i and A. K a s t l e r , O p t i c a l
p u m p i n g " , in P r o g r e s s in O p t i c s , N o r t h Holland (1966) o r A . K a s t l e r , " O p t i c a l
m e t h o d s f o r the study of r a d i o f r e q u e n c y r e s o n a n c e s " , P h y s . Today 20^
(1967) 34. As r e g a r d s m u o n i u m and p o s i t r o n i u m we r e f e r to V . W . H u g h e s ,
" M u o n i u m " , Annu. Rev. Nucl. Sei. (1966) 445; F . J . M. F a r l e y , " E l e c t r o -
m a g n e t i c p r o p e r t i e s of the m u o n " , P r o g . Nucl. P h y s . 9^ (1964) 257 (see
pp. 263 and 281); M. D e u t s c h , "Annihilation of p o s i t r o n s " , P r o g . Nucl.
P h y s . 3^ (1956) 131.
In t h e f i e l d of r a d i o a s t r o n o m y we have to m e n t i o n M. Ryle, " R a d i o
a s t r o n o m y " , Rep. P r o g . P h y s . j_3 (1950) 184 and B. L o v e l l and J . A. Cleog,
Radio A s t r o n o m y , C h a p m a n and Hall (1952).

BIBLIOGRAPHY

GORTER, C . J . , Paramagnetic Relaxation, Elsevier (1947).

ABRAGAM, A . , The Principles of Nuclear Magnetism, Clarendon Press (1961).

TOWNES, C . H . , SCHAWLOW, A . L . , Microwave Spectroscopy, McGraw-Hill (1955),

GORDY, W., COOK, R.L., Microwave Molecular Spectra, J. Wiley (1970).

STRANDBERG, M.W. P., Microwave Spectroscopy McGraw-Hill (1955).


IAEA - S M R - 1 2 / 9 211

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INGRAM, D . J . E . , Spectroscopy at Radio and Microwave Frequencies, Butterworths (1955).

ANDREW, E.R., Nuclear Magnetic Resonance, Cambridge University Press (1955).

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STEPIN, L . D . , Quantum Radio Frequency Physics, transi, from Russian, MIT Press (1963-65).

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Press (1964).

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IAEA - S M R - 1 2 / 7

NUCLEAR E F F E C T S IN ATOMIC SPECTRA


J. BAUCHE
Laboratoire Aimé Cotton,
Orsay, France

Abstract

NUCLEAR EFFECTS IN ATOMIC SPECTRA.


Hyperfine structure ; line structure interpretation; electromagnetic properties of the nucleus; theory of
magnetic-dipole hyperfine structure (sublevels, transitions); electric-quadrupole hyperfine structure; hyperfine-
structure constants; configuration interaction; hyperfine-structure anomaly.
Isotope shift theory; co-existence of mass and field isotope shift; order-of-magnitude estimates;
King graphs; theoretical approaches.

P A R T I: HYPERFINE STRUCTURE

1. INTRODUCTION

T h i s p a p e r a i m s at d e s c r i b i n g two a t o m i c p h e n o m e n a , h y p e r -
f i n e s t r u c t u r e and i s o t o p e s h i f t , w h o s e s t u d y h a s b e e n f o r m a n y y e a r s
e x t r e m e l y u s e f u l f o r the k n o w l e d g e of n u c l e i and a t o m i c s t r u c t u r e .
T h e g r o s s p h e n o m e n o n we a r e i n t e r e s t e d in i s t h e f o l l o w i n g . W h e n
o b s e r v e d with a h i g h - r e s o l u t i o n s p e c t r o m e t e r (see p a p e r by P . Jacquinot),
e a c h a t o m i c s p e c t r a l l i n e of a g i v e n e l e m e n t r e v e a l s a " h y p e r f i n e " s t r u c t u r e ,
i. e. it a p p e a r s t h a t it i s in f a c t a g r o u p of s e v e r a l c o m p o n e n t s v e r y c l o s e •
to one a n o t h e r : F o r m o s t l i n e s t h e t o t a l w i d t h of t h e s t r u c t u r e i s of the o r d e r
of 10 m i l l i k a y s e r s (10 m K ; 1 m K = 1 0 " 3 K > l O ^ c m " 1 ) , t o a f a c t o r of 100 in
both directions.
It is w e l l known t h a t e a c h n a t u r a l c h e m i c a l e l e m e n t i s g e n e r a l l y a b l e n d
of s e v e r a l s t a b l e i s o t o p e s . One r e a s o n f o r the s t r u c t u r e o b s e r v e d i s t h a t the
l i n e d u e t o the t r a n s i t i o n b e t w e e n a g i v e n p a i r of e l e c t r o n i c l e v e l s h a s not
exactly the s a m e wave n u m b e r f o r all isotopes, as m a y be expected a p r i o r i .
This phenomenon is called "isotope shift".
By m e a n s of m a s s s p e c t r o g r a p h s , n u c l e a r p h y s i c i s t s c a n s e p a r a t e i n t o
p u r e i s o t o p e s a p p r e c i a b l e a m o u n t s of e v e r y e l e m e n t . In t h e a t o m i c l i n e s of
s u c h a n i s o t o p e , t h e r e m a y s t i l l a p p e a r s t r u c t u r e s , e s s e n t i a l l y in a l l c a s e s
of i s o t o p e s w i t h a n odd m a s s n u m b e r A. T h i s p h e n o m e n o n is p r o p e r l y c a l l e d
"hyperfine structure".

2. HYPERFINE STRUCTURE

2.1. I n t e r p r e t a t i o n of l i n e s t r u c t u r e s

T h e i n t e r p r e t a t i o n of t h e h y p e r f i n e s t r u c t u r e (hfs) p h e n o m e n o n a s a r i s i n g
f r o m t h e e x i s t e n c e of t h e n u c l e a r s p i n a n g u l a r m o m e n t u m w a s s u g g e s t e d by
P a u l i in 1924. In w h i c h way d o e s t h i s s p i n a f f e c t a t o m i c l i n e s ?

213
214 BAUCHE

Nowadays we know that a n u c l e u s is not an e l e m e n t a r y p a r t i c l e (except


the p r o t o n , t h e H 1 n u c l e u s ) but an n - p a r t i c l e s y s t e m , whose s t r u c t u r e h a s
b e e n s t u d i e d e x t e n s i v e l y f o r m a n y y e a r s . In p r i n c i p l e , we should c o n s i d e r
f o r t h e a t o m , i n s t e a d of the c l a s s i c a l p r o b l e m of one n u c l e u s and Z e l e c t r o n s ,
that of Z p r o t o n s , A - Z n e u t r o n s and Z e l e c t r o n s .
But t h i s i n c r e a s e in c o m p l e x i t y c a n b e avoided with t h e help of the B o r n -
O p p e n h e i m e r t h e o r e m . T h i s quantum t h e o r e m , which is of f u n d a m e n t a l
i m p o r t a n c e in m o l e c u l a r s p e c t r o s c o p y , a g r e e s in p a r t i c u l a r with the following
c l a s s i c a l i d e a s . C o n s i d e r two s y s t e m s of p a r t i c l e s , with i n t e r a c t i o n s b e t w e e n
p a r t i c l e s i n s i d e s y s t e m 1, i n s i d e s y s t e m 2 and b e t w e e n both s y s t e m s . If t h e
i n t e r a c t i o n s i n s i d e , s a y , s y s t e m 1 a r e s t r o n g enough f o r the r e v o l u t i o n
p e r i o d s of its p a r t i c l e s to be m u c h s h o r t e r than t h o s e in s y s t e m 2, a t i m e -
a v e r a g e d d e s c r i p t i o n of s y s t e m 1 is s u f f i c i e n t f o r studying t h e m o t i o n s of the
p a r t i c l e s of s y s t e m 2. In quantum l a n g u a g e , t h e r e v o l u t i o n t i m e is p r o p o r -
t i o n a l to the i n v e r s e of the e n e r g y . As we know t h a t t h e e n e r g i e s in n u c l e a r
p r o b l e m s a r e m e a s u r e d in MeV ( 10 6 eV), in c o n t r a s t with t h o s e in a t o m i c
s p e c t r o s c o p y (1 eV c o r r e s p o n d s to 8066 cm" 1 ), we conclude that a t i m e -
a v e r a g e d d e s c r i p t i o n of the n u c l e u s is a l l we n e e d , in a f i r s t and e x c e l l e n t
approximation.

2.1.1. E l e c t r o m a g n e t i c e x t e r n a l p r o p e r t i e s of the n u c l e u s

A n u c l e u s is b u i l t up of n u c l é o n s ( p r o t o n s and n e u t r o n s ) . E l e c t r o n s
i n t e r a c t with t h e n u c l e u s a l m o s t only t h r o u g h t h e C o u l o m b f u n d a m e n t a l f o r c e
(no n u c l e a r s t r o n g i n t e r a c t i o n b e t w e e n e l e c t r o n s and n u c l é o n s ; g r a v i t a t i o n a l
f o r c e c o m p l e t e l y n e g l i g i b l e ; n u c l e a r weak i n t e r a c t i o n n e g l i g i b l e ) . T h i s f o r c e
l e a d s to e l e c t r o s t a t i c and m a g n e t i c e f f e c t s . As the s p a t i a l e x t e n s i o n of the
n u c l e u s i s m u c h s m a l l e r than the a t o m i c d i m e n s i o n s , we can w r i t e the n u c l e a r
e l e c t r o s t a t i c and m a g n e t i c p o t e n t i a l s a s e x p a n s i o n s in t e r m s of r , t h e d i s t a n c e
to the c e n t r e of the n u c l e u s .
A s i m p l i f y i n g p r o p e r t y is t h e following. It is. known [1] that
p a r i t y is a good quantum n u m b e r f o r a t o m i c ( e l e c t r o n i c ) s t a t e s . If we n e g l e c t
the i n f l u e n c e of the s m a l l — but famous'. — weak n u c l e a r f o r c e s , which
v i o l a t e p a r i t y c o n s e r v a t i o n , p a r i t y is a l s o a good quantum n u m b e r f o r n u c l e a r
s t a t e s . It can be e a s i l y d e d u c e d that m u l t i p o l e s of odd (even) r a n k do not
o c c u r in t h e e l e c t r o s t a t i c (magnetic) e x p a n s i o n .

(a) E l e c t r o s t a t i c expansion

T h e l e a d i n g t e r m in the e x p a n s i o n of the e l e c t r o s t a t i c p o t e n t i a l in M, due


to the p r o t o n s only, is (1/47re 0 )(Ze/r)(e = 1.6 X 10" 1 9 Coulomb): the e l e c t r o -
s t a t i c m u l t i p o l e of r a n k 0 is the c h a r g e of the n u c l e u s (a m o n o p o l e , b e c a u s e
2°= 1), whose e f f e c t on t h e e l e c t r o n s i s f u n d a m e n t a l in the study of e l e c t r o n i c
s t r u c t u r e [1] and d o e s not depend on the i s o t o p e c o n s i d e r e d . H e r e we a r e not
i n t e r e s t e d in it.
T h e following t e r m is the q u a d r u p o l e t e r m , of r a n k 2 (and of o r d e r 2 2 = 4,
whence t h e n a m e ) , which i s p r o p o r t i o n a l to l / r 3 a n d d e p e n d s on the d i r e c t i o n
of О Й (O c e n t r e of t h e n u c l e u s ) .
T h e n we find the h e x a d e c a p o l e t e r m (rank 4), e t c .
IAEA - S M R - 3 2 / 7 215

(b) Magnetic expansion

F o r the m a g n e t i c v e c t o r p o t e n t i a l , the l e a d i n g t e r m is due to t h e m a g n e t i c


dipole m o m e n t of the n u c l e u s ( r a n k 1), to which the n e u t r o n s c o n t r i b u t e —
as well as the protons, whose orbital magnetic m o m e n t s also contribute —
t h r o u g h t h e i r own spin m a g n e t i c m o m e n t .
T h e n we find the octupole t e r m ( r a n k 3), e t c .

(c) O r d e r s of m a g n i t u d e of h f s i n t e r a c t i o n s

T h e r e i s an a l t e r n a t i v e and e q u i v a l e n t way to d e s c r i b e the t o t a l e l e c t r o -


m a g n e t i c i n t e r a c t i o n b e t w e e n n u c l e u s and e l e c t r o n s . I n s t e a d of e x p a n d i n g t h e
f i e l d s of t h e n u c l e u s and s t u d y i n g t h e i r i n t e r a c t i o n s with m o v i n g e l e c t r o n s ,
we m a y obtain the e l e c t r i c and m a g n e t i c f i e l d s c r e a t e d by the e l e c t r o n s in
t h e v i c i n i t y of the c e n t r e of the n u c l e u s and c o m p u t e t h e i r e f f e c t s on t h e
n u c l e a r e l e c t r i c and m a g n e t i c m o m e n t s . In this way we s h a l l f i r s t d e r i v e
o r d e r s of m a g n i t u d e f o r h f s e n e r g y e f f e c t s , and l a t e r on w r i t e the h f s
Hamiltonian.

(a) Magnetic-dipole hfs

T h e e n e r g y a s s o c i a t e d with t h e m a g n e t i c dipole m o m e n t of, the n u c l e u s


and the m a g n e t i c induction В p r o d u c e d by t h e e l e c t r o n s at the n u c l e u s is -B.
В is a p u r e l y e l e c t r o n i c quantity. In t h e a t o m , t h e f u n d a m e n t a l q u a n t i t i e s
s u f f i c i e n t to d e f i n e a t o m i c u n i t s a r e h, m ( m a s s of t h e e l e c t r o n ) and e (and
e 0 o r /u0, t h e c o n s t a n t s which c h a r a c t e r i z e t h e C o u l o m b f o r c e ; e 0 /i 0 c 2 = 1). F o r
e x a m p l e t h e a t o m i c length unit i s t h e Bohr r a d i u s a = h 2 / m e 2 = 0.529 X10~ 8 c m
(a = 4тг e0 h 2 / m e 2 if r a t i o n a l i z e d ) . F o r the a t o m i c unit of В we obtain

M0 e 3 /(47r) 2 e 0 a 2 h = e 3 / ( 4 7 r e 0 f a 2 c 2 f i

Л is a p u r e l y n u c l e a r quantity. In t h e n u c l e u s , the f u n d a m e n t a l q u a n t i t i e s
s u f f i c i e n t t o d e f i n e n u c l e a r u n i t s a r e ft, M ( m a s s of the p r o t o n ) , f (the f e r m i ;
1 f e r m i = 1 0 " 1 3 c m ; the f e r m i i s of t h e o r d e r of m a g n i t u d e of the n u c l e a r
d i m e n s i o n s , and i s conveniently i n t r o d u c e d to c h a r a c t e r i z e t h e n u c l e a r s t r o n g
i n t e r a c t i o n ) and e , e 0 and ßQ f o r e l e c t r o m a g n e t i c p r o p e r t i e s , of c o u r s e . T h e n
we find e a s i l y that a l l n u c l e a r m a g n e t i c dipole m o m e n t s a r e of the o r d e r of
t h e quantity e f t / M . M o r e p r e c i s e l y , the n u c l e a r m a g n e t o n ß N (the unit f o r the
n u c l e a r m a g n e t i c m o m e n t s ) is t r a d i t i o n a l l y d e f i n e d a s e h / 2 M .
F i n a l l y , f o r the o r d e r of m a g n i t u d e of t h e m a g n e t i c - d i p o l e h f s e n e r g y ,
we obtain e 4 /2(47re 0 ) 2 a 2 c 2 M (check t h e d i m e n s i o n ! ) , which is a p p r o x i m a t e l y
0.4 X 10" 6 eV (3 mK in wave n u m b e r s ) . Note that t h i s r e s u l t . d o e s not depend
on t h e v a l u e of the d i m e n s i o n of the n u c l e i (the f e r m i ) , and a l s o not on ft.

(ß) E l e c t r i c - q u a d r u p o l e hfs

In the s a m e way the h f s e n e r g y due to t h e i n t e r a c t i o n of the n u c l e a r


e l e c t r i c q u a d r u p o l e m o m e n t ( d i m e n s i o n : c h a r g e X a r e a ) with t h e e l e c t r i c
f i e l d a r o u n d the n u c l e u s c a n b e c o m p u t e d . E v i d e n t l y it i s a m u l t i p l e of
H ( 1 0 f / a ) 2 w h e r e H, the H a r t r e e (1 H= 219 474 K), is t h e a t o m i c e n e r g y u n i t ;
h e r e we t a k e into account the f a c t that the unit f o r n u c l e a r q u a d r u p o l e m o m e n t s
is e X b a r n (often j u s t t h e n u m b e r of b a r n s i s given; 1 b a r n = 10" 24 c m 2 = (10f) 2 ).
216 BAUCHE

We d e d u c e the value 8 m K f o r t h e o r d e r of m a g n i t u d e of e l e c t r i c - q u a d r u p o l e
h f s e n e r g y , a v a l u e c l o s e to the r e s u l t f o r m a g n e t i c - d i p o l e hfs 1 .
In t h e following, we s h a l l l i m i t o u r s e l v e s to the study of t h e s e two c o n -
t r i b u t i o n s to the h f s . The n u c l e a r m u l t i p o l e s of h i g h e r r a n k a r e of m u c h
s m a l l e r i n f l u e n c e : f o r two s u c c e s s i v e e l e c t r i c (or m a g n e t i c ) m u l t i p o l e s , the
r a t i o of t h e i r e n e r g y c o n t r i b u t i o n s is of the o r d e r ( 1 0 f / a ) 2 . Studies of t h e
m a g n e t i c - o c t u p o l e e f f e c t s , f o r e x a m p l e , can b e found in the l i t e r a t u r e [ 2 ] .
To c o n c l u d e this p a r t , we m a y note that our e v a l u a t i o n of o r d e r s of
m a g n i t u d e s h o w s that it looks a c o i n c i d e n c e t h a t t h e e f f e c t s of m a g n e t i c -
dipole and e l e c t r i c - q u a d r u p o l e h f s h a v e a l m o s t the s a m e o r d e r of m a g n i t u d e .

2.1.2. E l e m e n t a r y t h e o r y of the m a g n e t i c - d i p o l e h f s : the s u b l e v e l s

U n t i l now we have not u s e d quantum t h e o r y , u n l e s s f o r the i n t r o d u c t i o n


of h to c a l c u l a t e the o r d e r s of m a g n i t u d e . We s h a l l now give the q u a n t u m
d e s c r i p t i o n of the m a g n e t i c - d i p o l e h f s .

(a) Hamiltonian : elementary part

To obtain a f o r m a l e x p r e s s i o n f o r the e n e r g y i n t e r a c t i o n , we f i r s t have


to find that f o r the m a g n e t i c field p r o d u c e d by the m o v i n g e l e c t r o n s at the
n u c l e u s . R e s t r i c t i n g the l o c a t i o n of an e l e c t r o n to t h e o u t s i d e of the n u c l e u s
we c o n s i d e r the following c a s e s :
The f i e l d H j p r o d u c e d by the moving c h a r g e - e defined by its p o s i t i o n ?
and i t s v e l o c i t y v :

.ri r Xv e r X pх
47гН.1 = - e —s— = m r-X 3
rd

The f i e l d H2 p r o d u c e d by the m a g n e t i c dipole m o m e n t jí of the e l e c t r o n ;


t h i s m o m e n t is

-2(3 s , w h e r e ß = e h / 2 m is the B o h r m a g n e t o n

(the a t o m i c unit f o r m a g n e t i c m o m e n t s ) and s is the s p i n of the e l e c t r o n ,


s is the a n g u l a r - m o m e n t u m v e c t o r o p e r a t o r of the e l e c t r o n , such that (?) 2
h a s a s t h e only e i g e n v a l u e s ( s + l ) with s = j and s z h a s the e i g e n v a l u e s ± j
( a c t u a l l y the spin a n g u l a r m o m e n t u m i s r a t h e r h s ) .
By c l a s s i c a l e l e c t r o m a g n e t i s m one obtains

л Û -= - _
4îrHo ±L +j. 3a * * ?)
—s"
Al MО

T h e n the c o r r e s p o n d i n g H a m i l t o n i a n ( i n t e r a c t i o n e n e r g y ) is
„ — ~Mo(Hi + Нг) - /им , w h e r e jîN is the m a g n e t i c dipole m o m e n t of the
n u c l e u s . Noting that r X p = hi, w h e r e Í i s t h e ( d i m e n s i o n l e s s ) o r b i t a l

1
Actually, the values of the nuclear quadmpole moments are close to 1 barn only in the second half of
the periodic table, and closer to 0 . 1 barn for Z smaller than 30.
IAEA-SMR-12/7 217

a n g u l a r m o m e n t u m of the e l e c t r o n , and d e l e t i n g 4т ( t r a d i t i o n a l l y , the


f o r m u l a s in q u a n t u m m e c h a n i c s a r e not r a t i o n a l i z e d ) , we c a n w r i t e f o r an
a t o m with s e v e r a l e l e c t r o n s

Now we t a k e into account the f a c t t h a t , f o r t h e n u c l e u s a s w e l l as f o r


the e l e c t r o n , the m a g n e t i c m o m e n t and the a n g u l a r m o m e n t u m a r e p r o p o r -
t i o n a l to e a c h o t h e r : Ды = ( / u N / I ) ß N t , w h e r e t is the ( d i m e n s i o n l e s s ) a n g u l a r
m o m e n t u m v e c t o r . In c o n t r a s t to the c a s e of the e l e c t r o n , the p r o p o r t i o n a l i t y
c o e f f i c i e n t c o n t a i n s ß N = e h / 2 M (see 2.1.1. (c), a) i n s t e a d of ß and M n /I is not
a s i m p l e n u m b e r , but h a s to be d e t e r m i n e d e x p e r i m e n t a l l y (for e x a m p l e
M ^ / I - 5.59 f o r t h e p r o t o n ) ; h o w e v e r , f r o m the g e n e r a l p r o p e r t i e s of a n g u l a r
m o m e n t u m o p e r a t o r s , we know that I, d e f i n e d by the f a c t that the e i g e n v a l u e
of the o p e r a t o r 11 | is 1(1+1), is e i t h e r an i n t e g e r o r a " h a l f - i n t e g e r "
( r a t h e r : h a l f - o d d ) n u m b e r (for e x a m p l e it is 1 f o r the n u c l e u s 2 H and 3 / 2
f o r 7 Li).

(b) Nuclear spins

Knowing that n u c l e i a r e built up of n u c l é o n s , i . e . p r o t o n s and n e u t r o n s ,


both with spin 1 / 2 , we know f r o m an e l e m e n t a r y r e s u l t on the coupling of
a n g u l a r m o m e n t a that n u c l e i with an e v e n n u m b e r of n u c l é o n s ( e v e n - e v e n and
odd-odd n u c l e i ) have an i n t e g r a l spin w h e r e a s an odd n u m b e r of n u c l é o n s
l e a d s to a h a l f - i n t e g r a l spin. M o r e o v e r , e x p e r i m e n t a l d e t e r m i n a t i o n s have
shown t h a t a l l s t a b l e e v e n - e v e n i s o t o p e s c o r r e s p o n d to the v a l u e 1= 0, w h e r e a s '
none of the few odd-odd s t a b l e n u c l e i d o e s .
As I = 0 l e a d s to juN = 0, we s e e that m o s t i s o t o p e s with an even m a s s
n u m b e r ( n a m e l y , t h e e v e n - e v e n i s o t o p e s ) give a t o m i c s p e c t r a l l i n e s without
any m a g n e t i c - d i p o l e s t r u c t u r e (we s h a l l s e e l a t e r that 1 = 0 p r e v e n t s the
e x i s t e n c e of any h f s at all).

(c) H a m i l t o n i a n : the F e r m i c o n t a c t t e r m

T h e f o r m u l a s we h a v e u s e d above f o r the i n t e r a c t i o n b e t w e e n the n u c l e a r


point m a g n e t i c m o m e n t and the m a g n e t i c f i e l d p r o d u c e d by the e l e c t r o n s a r e
not v a l i d if we allow t h e e l e c t r o n to e n t e r t h e n u c l e u s , a s it c a n . In t h i s c a s e ,
we must c o m p u t e the i n t e r a c t i o n b e t w e e n a point c h a r g e plus a point m a g n e t i c
m o m e n t (the e l e c t r o n ) and a s m a l l (although f i n i t e ) v o l u m e with a m a g n e t i s m
d i s t r i b u t i o n . C o n s i d e r i n g the l i m i t of t h i s i n t e r a c t i o n f o r a point n u c l e u s , we
obtain [3] the s o - c a l l e d F e r m i c o n t a c t t e r m , which m u s t b e added to ,
osd
to y i e l d t h e c o m p l e t e h f s m a g n e t i c - d i p o l e H a m i l t o n i a n

H„ - ^ { Z 6(î.)sJ-ï^ X-Î

where
218 BAUCHE

and w h e r e ô (?) is not a t r u e function but a " d i s t r i b u t i o n " , with the d e f i n i t i o n

J f*(r)6(r)f(?)dr= |f(ï)|2
space

f o r any a r b i t r a r y function f ( r )

(d) E l e m e n t a r y d e s c r i p t i o n of the a t o m i c wave f u n c t i o n

H m r e p r e s e n t s an i n t e r a c t i o n between n u c l e u s and e l e c t r o n s . T h e r e f o r e
it a c t s in a s p a c e of wave f u n c t i o n s d e s c r i b i n g both t h e s t a t e s of the n u c l e u s
and of t h e e l e c t r o n s . As we a r e i n t e r e s t e d g e n e r a l l y in one n u c l e a r l e v e l
(the g r o u n d l e v e l , m o s t o f t e n ) , we r e p r e s e n t it by k e t s of t h e type | I M j ) ,
w h e r e only I and M, (the p r o j e c t i o n of T on the z - a x i s ) a r e s p e c i f i e d . As in
t h e c a s e of the a t o m , we m a y often be i n t e r e s t e d in s e v e r a l a t o m i c l e v e l s .
M o r e o v e r we know [1] t h a t , in the a b s e n c e of e x t e r n a l f i e l d s 2 , e a c h a t o m i c
s t a t e is an e i g e n s t a t e of t h e o p e r a t o r [ j | f o r t h e eigenvalue J ( J + 1). We
w r i t e s u c h a s t a t e a s |a J M j ) , w h e r e a s p e c i f i e s the coupling (possibly i n t e r -
m e d i a t e [1] ), i. e. t h e way e l e c t r o n i c o r b i t a l and s p i n a n g u l a r m o m e n t a a r e
coupled to y i e l d J .
F i n a l l y , the wave f u n c t i o n of the c o m p l e t e s y s t e m ( e l e c t r o n s + n u c l e u s )
c a n be expanded on t h e b a s i s of the ket p r o d u c t s 3

\a J M )| I M , ) = I a J I Mj M,)

(e) Application of the p e r t u r b a t i o n m e t h o d

In the s p a c e of wave f u n c t i o n s just d e s c r i b e d , we m u s t c o n s i d e r t h e t o t a l


H a m i l t o n i a n H 0 + H m , w h e r e H0 is the e l e c t r o n i c H a m i l t o n i a n [ 1 ] . H 0 i s
d i a g o n a l , with e i g e n s t a t e s | a J I M j M j ) , c o r r e s p o n d i n g to t h e e n e r g i e s E a J ,
i n d e p e n d e n t of M j , I, and M j , d i f f e r i n g one f r o m the o t h e r by g e n e r a l l y at
l e a s t one h u n d r e d K a y s e r s in t h e i n t e r e s t i n g p a r t s of the a t o m i c s p e c t r a . So
the " s m a l l " H a m i l t o n i a n H m c a n be c o n s i d e r e d a s a p e r t u r b a t i o n . In the
f i r s t o r d e r of p e r t u r b a t i o n , we have t o d i a g o n a l i ž e t h e m a t r i x of H m on t h e
s u b s p a c e c o r r e s p o n d i n g to a given a j - l e v e l .

(f) Application of t h e W i g n e r - E c k a r t t h e o r e m

T h e f i r s t thing to do is to build up t h i s m a t r i x . Using t h e c o n d e n s e d


n o t a t i o n ( w i j M j ) = (a J I M . M j ) , we c a n w r i t e

2
In fact, the hfs phenomenon itself can be considered as the effect of a field "external" to the "atom" so
that, in principle, J is only an "almost good" quantum number.
3
If several nuclear levels are of interest and if their wave functions are known, one may label them as
iBIMj).
IAEA-SMR-12/7 219

(MJ M J | H ^ I M J ' M J ' ) = £ (MJMJIX^I^M; M-)


q = x,y,z

= (Mj M Xq Mj M } (Mj M iq Mji m j>


Xq MJ*XM}* ' ' ' " " " "' ' '
= Y (M J Mj |X q |MJ' MJ ) (M,' MJ |l q I M j MJ' )

Now, b e c a u s e the o p e r a t o r X i s a v e c t o r a c t i n g in the e l e c t r o n i c s p a c e


like J , we c a n apply the W i g n e r - E c k a r t t h e o r e m and w r i t e

(Mj MJ I X q |Mj' Mj ) = A ^ (Mj Mj | J^ М/ Mj )

w h e r e A a J is i n d e p e n d e n t of M j , M j and Mj, and w h e r e J q (q = x , y , z ) is a


p r o j e c t i o n of J . C a l c u l a t i n g in the s a m e way a s above but b a c k w a r d s , we
d e r i v e the c l a s s i c a l Hamiltonian

H .M. = A a j I - J

Note : t h e r i g o r o u s d e r i v a t i o n j u s t given is o f t e n r e p l a c e d by the s h o r t e r


s e n t e n c e : " d u e to the p r e c e s s i o n of the a t o m a r o u n d J , the e x p e c t a t i o n v a l u e
of any v e c t o r in the s y s t e m is p r o p o r t i o n a l to J " .
If applied to the n u c l e u s , which is a s y s t e m of n u c l é o n s , it p r o v e s t h a t
i t s m a g n e t i c m o m e n t /JN i s p r o p o r t i o n a l to Г. A a J is c a l l e d the h y p e r f i n e
s t r u c t u r e c o n s t a n t of t h e l e v e l a J .

(g) Hfs s u b l e v e l s

With the new e x p r e s s i o n f o r H M (valid only in t h e s u b s p a c e of the


j a J I M j Mj ) s t a t e s ) we c a n i m m e d i a t e l y find the e n e r g i e s . We f i r s t go f r o m
t h e u n c o u p l e d s t a t e s | a J I M j M j ) t o the coupled s t a t e s | a J I F M p ) , by i n t r o -
d u c i n g the t o t a l a n g u l a r m o m e n t u m F = 3+1 T h e n we note that

2
H - ÄA (I^I - M - |JF)
"M aJ о

T h e r e f o r e H M is d i a g o n a l on the b a s i s of the coupled s t a t e s , and i t s e i g e n -


values a r e

AW m t, J I F) = AaJ F(F+1)-I(I + D- J ( J + 1)

We s e e that e a c h a J - l e v e l of t h e e l e c t r o n i c s y s t e m is s p l i t up into a
n u m b e r of s u b l e v e l s c h a r a c t e r i z e d by the q u a n t u m n u m b e r F . T h i s n u m b e r
i s t h e s m a l l e r one of the n u m b e r s ( 2 J 4 1) and (21 + 1). M o r e o v e r a kind of
220 BAUCHE

L a n d é i n t e r v a l r u l e , w e l l known f o r t h e fine s t r u c t u r e e n e r g i e s [1]


a p p l i e s s o that

AWm(a J I F ) - A W m ( a J I F - l ) = AaJF

2.1.3. E l e m e n t a r y t h e o r y of the m a g n e t i c - d i p o l e h f s : t h e t r a n s i t i o n s

Having found the h f s s t r u c t u r e s of the l e v e l s , we c a n d e r i v e the s t r u c -


t u r e s of t h e l i n e s .

(a) S e l e c t i o n r u l e s f o r e l e c t r i c dipole t r a n s i t i o n s

Let u s c o n s i d e r an a t o m i c t r a n s i t i o n b e t w e e n two l e v e l s , a J and a ' J ' ,


which is " a l l o w e d " in the a b s e n c e of h f s . T h i s m e a n s that the line obeys t h e
s e l e c t i o n r u l e s f o r the type of r a d i a t i v e t r a n s i t i o n c a l l e d " e l e c t r i c dipole
t r a n s i t i o n " [ 1 ] , which s a y that t h e p a r i t i e s of the l e v e l s a r e d i f f e r e n t and
I J - J'| i 1 g j +ji.
Since the e l e c t r i c dipole t r a n s i t i o n o p e r a t o r E r . a c t s only in the e l e c t r o n i c
s p a c e , which is not i n f l u e n c e d by the p r e s e n c e of W s , t h e t r a n s i t i o n r e m a i n s
allowed a s a whole. T h e s e l e c t i o n r u l e on F is e x a c t l y analogous to that on
J : | F - F ' | S 1 Š F + F ' . It c a n b e kept in m i n d e a s i l y (and e v e n d e m o n s t r a t e d ,
in a way) by noting that an e l e c t r i c dipole photon c a r r i e s an a n g u l a r m o m e n -
t u m h., which i s t a k e n away f r o m the a t o m t h r o u g h the t r a n s i t i o n . T h e
p r i n c i p l e of c o n s e r v a t i o n of t o t a l angular m o m e n t u m f o r the s y s t e m (atom in
s u b l e v e l or J I F , a t o m in s u b l e v e l a 1 J 1 1 F ' + photon) i m m e d i a t e l y y i e l d s the
d e s i r e d t r i a n g u l a r condition.

— f • F =0

J = - J'= 1

F =1

• F . J . * -F = 1 J = 0 •
4 : - F=0
-F.J-* •F=J-1
IAEA-SMR-12/7 221

(b) Examples

(a) I s o t o p e with I = f

A l i n e s p l i t s into

3 components if J f J 1 (J and J ' f 0)


4 components if J = J' f j
3 components if J =J' = \
2 components if J or J ' = 0

(ß) One l e v e l with J = 0

N e c e s s a r i l y J ' = 1, and t h e l i n e

d o e s not s p l i t if I = 0
s p l i t s into 2 c o m p o n e n t s if I = \
s p l i t s i n t o 3 c o m p o n e n t s if I s 1

(с) Line intensities

The c o m p o n e n t i n t e n s i t i e s c a n b e c a l c u l a t e d in the s a m e way a s t h o s e


without h f s [ 1 ] , u s i n g the t e n s o r o p e r a t o r f o r m a l i s m . F o r a g i v e n a J - > a ' J '
t r a n s i t i o n , t h e y a r e a l l n u m e r i c a l m u l t i p l e s of one r e d u c e d m a t r i x e l e m e n t
s q u a r e d , n a m e l y | (q-jU? r t | | a ' J ' ) | 2 . T h e n u m e r i c a l c o e f f i c i e n t s h a v e b e e n
t a b u l a t e d f o r m a n y v a l u e s of J and I [ 4 , 5 ] .

2.1.4. T h e o r y of the e l e c t r i c - q u a d r u p o l e h f s

T h e m a g n e t i c - d i p o l e h f s w a s s t u d i e d above without t h e u s e of t e n s o r
o p e r a t o r m e t h o d s with t h e only a i m of an e x p l i c i t c o m p u t a t i o n of t h e c o m p o n e n t
i n t e n s i t i e s . F o r the e l e c t r i c - q u a d r u p o l e p a r t of t h e h f s , t h e r e s u l t s w e r e
o b t a i n e d by C a s i m i r (1936) at t h e end of a long w o r k . T h e y c a n now b e
r e p r o d u c e d v e r y e a s i l y by u s e of R a c a h ' s m e t h o d s .

(a) The H a m i l t o n i a n

In t e n s o r - o p e r a t o r f o r m , t h e m a g n e t i c - d i p o l e H a m i l t o n i a n i s w r i t t e n a s
a scalar product

Hm = (X(1)-I(1))

To obtain t h e e l e c t r i c - q u a d r u p o l e H a m i l t o n i a n , t h e t o t a l i n t e r a c t i o n e n e r g y
b e t w e e n t h e e l e c t r o n s (with t h e i r p o s i t i o n s d e f i n e d by v e c t o r s l i k e r ; ) and t h e

в
p r o t o n s ( p o s i t i o n s : Rj) i s w r i t t e n a s

» • Zт^ ii.i j кi , - R-
222 BAUCHE

T h e f r a c t i o n c a n b e expanded a s

w h e r e the o p e r a t o r C(k)
c o r r e s p o n d s to e l e c t r o n a n g u l a r c o - o r d i n a t e s and
to n u c l é o n a n g u l a r c o - o r d i n a t e s . S e l e c t i n g t h e p a r t of the e x p a n s i o n
with k= 2, and applying the W i g n e r - E c k a r t t h e o r e m to the n u c l e a r p a r t , we
obtain t h e e l e c t r i c - q u a d r u p o l e h f s H a m i l t o n i a n
Hq = ( Y ( 2 ) . K t 2 ) )

where
(2) e 2 Q Y Cj(2>
(electronic operator)
1(21-1) Л г »

and

K (2) = J l (I(Dl(l)}W (nuclear operator)

Q i s t h e e l e c t r i c q u a d r u p o l e m o m e n t of the n u c l e u s . Hq is not d e f i n e d
f o r 1 = 0 and i , in which c a s e t h e r e is no h f s q u a d r u p o l e i n t e r a c t i o n .

Note on k ' 2 ^ : in the e x p r e s s i o n f o r K^ 2 ', n/ 3 / 2 is a t r a d i t i o n a l f a c t o r ; the


operator (I^'l ^ is the s i m p l e s t t e n s o r o p e r a t o r of r a n k 2 built up f r o m
j(i) (j(l) b e i n g t h e only n u c l e a r o p e r a t o r w h o s e e i g e n v a l u e s a r e known in our
s i m p l e q u a n t u m d e s c r i p t i o n of t h e n u c l e u s ) .

(b) Energies

We e a s i l y c a l c u l a t e the d i a g o n a l m a t r i x e l e m e n t s of H q [1]:

(a J I F M p I (Y f2> "K ( 2 ) )\a J I F ' M ^ )

= (-1) , + I + F б (F, F ' ) 6(Мр, Мр ) (« J||Y ( 2 ' M ( I II К ( 2 ) | | I)

T h i s r e s u l t p r o v e s t h a t the coupled s t a t e s |a J I F M f ) , which a r e t h e


e i g e n s t a t e s of H m in t h e s u b s p a c e c o r r e s p o n d i n g t o t h e l e v e l a J , a r e a l s o
t h e e i g e n s t a t e s of Hq in the s a m e s u b s p a c e . T h e d e p e n d e n c e of the e n e r g y
A W q ( a J I F ) on F i s given by the f a c t o r

T h e f o r m a l e x p r e s s i o n of t h e 6 i - s y m b o l c a n b e found in the l i t e r a t u r e ([6] p. 132).


The reduced m a t r i x
e l e m e n t (I||K ( 2 ) ||I) c a n be c a l c u l a t e d by m e a n s of a f o r m u l a
f o r two coupled t e n s o r o p e r a t o r s acting on the s a m e s y s t e m ([6] p. 109).
IAEA-SMR-12/7 223

(с) The C a s i m i r f o r m u l a

F i n a l l y , t h e h f s e n e r g y f o r a s u b l e v e l a J I F in the p r e s e n c e of both
m a g n e t i c - d i p o l e and e l e c t r i c - q u a d r u p o l e e f f e c t s i s given by t h e t r a d i t i o n a l
Casimir formula

3K(K + 1) - 41(1 + 1) J ( J + 1 )
A Wa J I F j A a j K + B aJ
81 (21 - 1) J (2 J - 1)

w h e r e К = F<F + 1 ) - 1(1 + 1 ) - J{ J + 1 ) and the h y p e r f i n e c o n s t a n t s of the l e v e l


a J are

A a J = ( a j II X(1)||or J) [J ( J + 1) ( 2 J + 1)]~* (I, J ž •§)

and

B a J = ( o j | | y ' 2 ' I I a j ) 21(21-1 ) [ J ( 2 J - 1 ) / ( J + l ) ( 2 J + l ) ( 2 J + 3 ( I , J ž l )

T h i s f o r m u l a s h o w s c l e a r l y t h a t , in the f i r s t o r d e r of p e r t u r b a t i o n , two
" p a r a m e t e r s " , A and B, a r e s u f f i c i e n t to i n t e r p r e t t h e h f s s t r u c t u r e of a
l e v e l , l i m i t e d to the m a g n e t i c - d i p o l e and e l e c t r i c - q u a d r u p o l e c o n t r i b u t i o n s .
M o r e i m p r e s s i v e is the c o n c l u s i o n that f o u r p a r a m e t e r s a r e s u f f i c i e n t to
i n t e r p r e t t h e h f s s t r u c t u r e of a l i n e , w h a t e v e r the n u m b e r of c o m p o n e n t s .
T h i s c o n c l u s i o n and the C a s i m i r f o r m u l a can b e u s e d to " r e s o l v e " n u m e r i c a l l y
a h f s s t r u c t u r e with u n r e s o l v e d c o m p o n e n t s , if t h e p r o f i l e of an i s o l a t e d
c o m p o n e n t is a c c e s s i b l e .
When t h e C a s i m i r f o r m u l a f a i l s to i n t e r p r e t t h e p o s i t i o n s of t h e h f s
c o m p o n e n t s , this m a y b e due to

(a) e r r o r s in the i d e n t i f i c a t i o n of the c o m p o n e n t s ; f o r t h i s i d e n t i f i c a t i o n , t h e


i n t e n s i t y r a t i o s ( s e e 2.1.3. c) a r e an e s s e n t i a l help;
(b) e n e r g y c o n t r i b u t i o n s due to the s e c o n d o r d e r of p e r t u r b a t i o n of t h e
H a m i l t o n i a n H m + H q , in the c a s e w h e r e n e i g h b o u r i n g J - l e v e l s a r e r e l a -
tively c l o s e to one a n o t h e r ;
(c) e n e r g y c o n t r i b u t i o n s due to m u l t i p o l a r h f s e f f e c t s of h i g h e r r a n k .

2.2. I n t e r p r e t a t i o n of t h e h f s c o n s t a n t s of t h e l e v e l s

A f t e r h a v i n g d e t e r m i n e d t h e c o n s t a n t s AaJ and B a J f o r one o r s e v e r a l


l e v e l s , an e x p e r i m e n t a l i s t is i n t e r e s t e d in t h e i r i n t e r p r e t a t i o n .

2.2,1. Hfs c o n s t a n t s of the e l e c t r o n s

(a) M o r e d e t a i l e d d e s c r i p t i o n of the a t o m i c wave f u n c t i o n

Now we h a v e to g a t h e r m o r e i n f o r m a t i o n on an i n t e r e s t i n g l e v e l t h a n
j u s t i t s e n e r g y and J - v a l u e . M o r e p r e c i s e l y , we a r e i n t e r e s t e d to know both
t h e e l e c t r o n i c c o n f i g u r a t i o n t o which the l e v e l e s s e n t i a l l y b e l o n g s and the
coupling c o r r e s p o n d i n g to this l e v e l [ 1 ] .
224 BAUCHE

In g e n e r a l , t h i s i n f o r m a t i o n i s o b t a i n e d t h r o u g h a c o n s i d e r a t i o n of t h e
l e v e l e n e r g i e s , w h i c h i s t h e e a s i e r t h e m o r e l e v e l s of t h e c o n s i d e r e d p a r t of
the e n e r g y s p e c t r u m a r e known. I n p r i n c i p l e , coupling i s a l w a y s i n t e r m e d i a t e [1],
but s o m e t i m e s a p u r e and s i m p l e c o u p l i n g (LS, j j , etc. ) m a y be
considered a satisfactory approximation.

(b) T h e p r i n c i p l e of the c o m p u t a t i o n f o r an a l k a l i

T h e s p e c t r a of t h e a l k a l i s m a y b e c o n s i d e r e d , in a n e x c e l l e n t a p p r o x i -
m a t i o n , as o n e - e l e c t r o n s p e c t r a . This m e a n s that all atomic configurations
w h e r e one e l e c t r o n of the c o m p l e t e s u b s h e l l s (the " c o r e " ) h a s b e e n e x c i t e d ,
l i e v e r y h i g h a b o v e t h e c o n f i g u r a t i o n s [ c o r e + one n í e l e c t r o n ] . Consequently
a low l e v e l of an a l k a l i c a n b e d e n o t e d a s [ c o r e + n i j ] .
W e now c a l c u l a t e the h f s c o n s t a n t A f o r t h i s l e v e l , f r o m

i i
with
Г; (Sj T j )
N.1 = 1I. -1 s. + 3 • 1 ^2 11

F i r s t , r e c o u p l i n g of t h e t e n s o r o p e r a t o r s s h o w s t h a t

. ^+3 M ç i i ^ , - ^ïï{S;i,c;2)}(1) (show it -, )

O b v i o u s l y t h e a t o m i c c o r e ( c o u p l e d to J = 0) d o e s not c o n t r i b u t e to the
h f s s i n c e t h e r e d u c e d m a t r i x e l e m e n t of X ( 1 ) ( s e e 2 . 1 . 4 . c) i s z e r o f o r J = 0
s y s t e m s . T h e r e f o r e we j u s t c a l c u l a t e the q u a n t i t y

(níej|| Д ( * ( 1 ) - Л о { 3 № с ^ j ^ + fLôfr^llnisj)

H e r e w e u s e t h e c l a s s i c a l f o r m u l a s f o r t h e m a t r i x e l e m e n t s of c o u p l e d
t e n s o r o p e r a t o r s a n d / o r coupled s y s t e m s [1].

(c) Hfs c o n s t a n t s of the e l e c t r o n s

It i s e v i d e n t t h a t , at the end of t h i s c a l c u l a t i o n , we a r e l e f t w i t h t h e
r e d u c e d m a t r i x e l e m e n t s of ( l / r 3 ) i ( 1 ) , ( l / r 3 ) C ( 2 ) and 6 ( r ) s ( 1 ) . By m e a n s of
t h e W i g n e r - E c k a r t t h e o r e m , t h e y a r e e a s i l y r e l a t e d t o the m a t r i x e l e m e n t s
t h e m s e l v e s of, s a y , the q= 0 c o m p o n e n t s of the t e n s o r o p e r a t o r s . In t h e s e
e l e m e n t s a p p e a r the i n t e g r a l s

DO

< Г = |u
' \ I n*(r)|2 ^ r 2 d r and
/ 1 Ф П*Т/ ? >| 2 ё (?><1т
0 space
IAEA-SMR-12/7 225

1
where m ^(r) is the s p a t i a l p a r t of t h e o n e - e l e c t r o n wave f u n c t i o n ï^ tsm m
1 s
and u,^ (r) is the r a d i a l p a r t .
The f i r s t i n t e g r a l , h o w e v e r , is u s e f u l only if the r e d u c e d m a t r i x e l e m e n t s
of Je*1) and C ( 2 )
a r e n o n - z e r o , which is the c a s e only f o r l фО. M o r e o v e r , the
s e c o n d i n t e g r a l h a s the v a l u e of lu^ ( 0 ) | 2 , which is n o n - z e r o only if i = 0 .
We c o n c l u d e that the o r b i t a l p a r t ( i ( 1 ) ) and t h e s p i n - d i p o l e p a r t ({s (1 'c (2) } (1) )
of H m c o n t r i b u t e to the h f s of a l l e l e c t r o n s e x c e p t the s - e l e c t i o n s (11=0), and
t h a t the F e r m i - c o n t a c t p a r t (s (1) ) c o n t r i b u t e s only to the h f s of s - e l e c t r o n s .
T h e h f s c o n s t a n t s A f o r a l k a l i l e v e l s (and m o r e g e n e r a l l y f o r e a c h l e v e l of an
a r b i t r a r y p u r e c o n f i g u r a t i o n of an a r b i t r a r y s p e c t r u m ) can be e x p r e s s e d in
t e r m s of the h f s - c o n s t a n t s of the e l e c t r o n s

and
2
ans = 3 I
| nsv(0)|
1u
'1

Note: f o r e x p l i c i t c a l c u l a t i o n s , a t i m e - s a v i n g n u m e r i c a l help is the following:


if the v a l u e of a ^ is to be obtained in m K , and the v a l u e of ^ r " 3 ^ is given in
a t o m i c u n i t s (the a t o m i c unit f o r this quantity is 1 / a 3 ) , then 2ß ßN - 3 . 1 8 2
(check t h i s r e s u l t ! ).
In the s a m e way a s above, h f s e l e c t r o n i c c o n s t a n t s c a n be defined f o r
the e l e c t r i c - q u a d r u p o l e e f f e c t :

bni = e 2 Q < r - 3 > n { (£?0)

(d) E x a m p l e s of r e s u l t s

(a) L e v e l ni j in an a l k a l i

A nsi,

R - Ед-1) b a 41)
nij (2 j + 2 ) n£ 4 rz)

(ß) C o n f i g u r a t i o n sp

M a t r i x of a.
Ü.

C o e f f i c i e n t 4 of a s = ( % P » S L j j l ^ H , l P a S ' L ' J )
( f f j | | j II a J)
4
Taking into account the fact that, for one-particle operators and matrix elements between states of one
and the same configuration, the antisymmetry problem, when solved (see [1]) yields this simple result.
226 BAUCHE

T h e n u m e r a t o r of this f r a c t i o n c a n b e w r i t t e n [1] as

(-ds+l+j+1[J; l ^ K b ,
щ © »

and the new r e d u c e d m a t r i x e l e m e n t r e a d s

Moreover
( a j | | J ( 1 ) I <*J) = -J J ( J + 1 ) ( 2 J + 1)
So we have obtained the g e n e r a l f o r m u l a s which give u s a l l e l e m e n t s of
the m a t r i x of the c o e f f i c i e n t s of a s . A f t e r having applied it n u m e r i c a l l y
(do i t ! ) , we can c h e c k the v a l u e s of t h e d i a g o n a l e l e m e n t s in the following way:
We f i r s t note that

( s p S L j | | S s ( 1 ) | | s p S L J ) = (s p S L j | | Sp 1 '||s p SLJ)

b e c a u s e both e l e c t r o n s p i n s e n t e r the coupling in the s a m e way.


T h e n we know t h a t , in t h e study of t h e Z e e m a n e f f e c t in LS coupling [ 1 ] ,
the L a n d é f a c t o r is given by

( a S L j | | S (1) IIa S L J ) = J (J + 1 ) + S(S + 1 ) - L(L + 1 )


g SU = + (1) = + 2J
* (.SLJ||J ||.SLJ) <J+1>

Since S (1) = S ^ ' + S p 4 , we deduce i m m e d i a t e l y

(s p S L J H Ss 1 '|]sp S L J ) _ 1 - J ( J + 1 ) + S(S + 1 ) - L ( L + 1)
(*J||J(1)|M 4 J (J + 1 )

// 3
P, 'p. g ^ g t ^ f
1 1 g(4 )= 1
и 2Í2

1
0
2УУ

1
Д
IAEA-SMR-12/7 227

M a t r i x of a p

In the m a t r i x of a p e a c h e l e m e n t is the s u m of two q u a n t i t i e s , one


c o r r e s p o n d i n g to the o r b i t a l p a r t and the o t h e r to t h e s p i n - d i p o l e p a r t .
T o obtain the o r b i t a l p a r t we m u s t c a l c u l a t e

( s p S L J [I L ( 1 ) | | s p S ' L ' J )
( « J II J ( 1 ) | | A J )

b e c a u s e the s - e l e c t r o n g i v e s no c o n t r i b u t i o n to the t o t a l IL.


We obtain

( - l ) S ' + L ' + , + 1 t J ] - j ^ g ^ . j - 6(S,S')(ßL|| L(1)||ß'L')


However,

(ßL II L ||ß ' L ' ) = 5 (ß,ß ')ô(L, L') N/L(L + 1 ) ( 2 L + 1)

The m a t r i x is d i a g o n a l . T h e r e is a g a i n an e a s i e r way to c a l c u l a t e it in the


s a m e way a s above.
C o e f f i c i e n t of a p = 2 - g a J

3p
, 'P,

1
2 0

'p, 0 1

1
2

Spin-dipole part 4

'P| 'p,

1 (compute the o t h e r
10 elements ! )
(compute a l s o the
P
2 c o e f f i c i e n t s of bp ! )
228 BAUCHE

(e) D e t e r m i n a t i o n of t h e hfs c o n s t a n t s

T h e work we have done f o r t h e s e few c a s e s c a n b e done f o r any l e v e l of


any c o n f i g u r a t i o n in any coupling. Of c o u r s e , in a l a r g e c o n f i g u r a t i o n in
i n t e r m e d i a t e coupling, t h e r e a r e lots of m a t r i x e l e m e n t s to c o m p u t e , g e n e r a l l y
on an L S - c o u p l i n g b a s i s ; i n d e e d , if

|aJ)=
X lßSLJ)
BSL

then

(a j | | Op II a J) = Y (ßSLj||Op|| ß'S'L'J)x«su x « ^
BSL
ß'S'L'
f o r any a r b i t r a r y o p e r a t o r O p . 5
When we h a v e obtained the e x p r e s s i o n of A (or B) f o r the i n t e r e s t i n g
l e v e l ( s ) , in t e r m s of the h f s c o n s t a n t s f o r t h e e l e c t r o n s , the work m a y
p r o c e e d in two d i f f e r e n t w a y s :
(a) If s e v e r a l m e a s u r e m e n t s a r e a v a i l a b l e f o r l e v e l s of the s a m e
c o n f i g u r a t i o n , they m a y be n u m e r o u s enough to allow the d e t e r m i n a t i o n of
the e l e c t r o n i c h f s c o n s t a n t s , with the help of t h e " p a r a m e t r i c " m e t h o d : one
s o l v e s , by l e a s t - s q u a r e s , the s e t of e q u a t i o n s

n i
A , = Y x a „
oíjJí i nC

w h e r e the A a . j a r e e x p e r i m e n t a l v a l u e s (the e q u a t i o n s a r e not c o m p a t i b l e ,


but m u s t be a l m o s t c o m p a t i b l e ; s e e [1] ).'
(b) An a b - i n i t i o m e t h o d m a y be u s e d to c o m p u t e d i r e c t l y the v a l u e s of
the electronic hfs constants ( H a r t r e e - F o c k method, L a y z e r method, etc. ;
s e e [1]), and then the l e v e l h f s c o n s t a n t s , with m o r e o r l e s s (but e s s e n t i a l l y
unknownj) a c c u r a c y . E x c e p t f o r s o m e r e c e n t , e f f e c t i v e but c u m b e r s o m e ,
m e t h o d s (those of t h e B r u e c k n e r - G o l d s t o n e t y p e , f o r e x a m p l e ) , t h e s e
a b - i n i t i o m e t h o d s give often no b e t t e r r e s u l t s than t h e old, f a m o u s s e m i -
c l a s s i c a l f o r m u l a s like the G o u d s m i t - F e r m i - S e g r é f o r m u l a [ 5 ] .

2.3. Results — Refinements

2.3.1. Results

So f a r we have d e f i n e d the g e n e r a l p r o c e d u r e f o r studying t h e o r e t i c a l l y


the h f s l e v e l c o n s t a n t s m e a s u r e d ; now let u s c o n s i d e r the types of r e s u l t s
obtained in t h i s way.
We obtained t h e ( m o r e o r l e s s a c c u r a t e ) v a l u e s of m a n y n u c l e a r m a g n e t i c -
dipole and e l e c t r i c - q u a d r u p o l e m o m e n t s ; t h e p r e s e n t s i t u a t i o n , h o w e v e r , is
s o m e w h a t d i f f e r e n t (for m a g n e t i c m o m e n t s only), b e c a u s e m a n y m a g n e t i c

5
There exist computer programs to compute such large numbers of matrix elements!
IAEA-SMR-12/7 229

m o m e n t s h a v e b e e n d e t e r m i n e d d i r e c t l y ( f o r e x a m p l e t h r o u g h t h e s t u d y of t h e
Z e e m a n e f f e c t in s t r o n g f i e l d s ) .
We a l s o found an " i n t e r p r e t a t i o n " of m a n y m e a s u r e m e n t s , i . e . m a n y
A - v a l u e s of l e v e l s in t h e s a m e c o n f i g u r a t i o n m a y b e " i n t e r p r e t e d " by a v e r y
s m a l l n u m b e r of p a r a m e t e r s , w h i c h p r o v e s t h e c o h e r e n c e of a l l t h e s e
measurements.
F i n a l l y , new p r o b l e m s of a t o m i c s t r u c t u r e a r o s e , i. e. c a s e s w h e r e t h e
m e t h o d s o u t l i n e d a b o v e h a v e f a i l e d . We now s t u d y s u c h c a s e s .

2.3.2. Configuration interaction

So f a r we h a v e s u p p o s e d t h a t t h e l e v e l s s t u d i e d b e l o n g to a p u r e c o n f i g u -
r a t i o n . But it f r e q u e n t l y h a p p e n s t h a t the f i r s t o r d e r of p e r t u r b a t i o n t h e o r y ,
applied to the " p e r t u r b i n g Hamiltonian" [1].

( e s s e n t i a l l y V) — e2 + V
in _ OTbit ), is not a s a t i s f a c t o r y a p p r o x i m a t i o n .
•T1- r i j
i>]

(a) M i x i n g of n e i g h b o u r i n g c o n f i g u r a t i o n s

In s o m e c a s e s two c o n f i g u r a t i o n s a p p e a r in the s p e c t r u m a l m o s t at the


same energy; o f t e n t h e y s i m p l y e x t e n d o v e r s u c h a l a r g e r a n g e of e n e r g y
t h a t t h e y o v e r l a p s t r o n g l y . U s u a l l y , t h e two c o n f i g u r a t i o n s a r e t h e r e f o r e
taken together as a b a s i s for diagonalizing the p e r t u r b i n g Hamiltonian. T h e
e i g e n s t a t e s b e c o m e a m i x t u r e of k e t s b e l o n g i n g to two c o n f i g u r a t i o n s . It i s
e a s y t o p r o v e t h a t the e x p r e s s i o n s f o r the c o r r e s p o n d i n g A - f a c t o r s c o n t a i n
s u p p l e m e n t a r y ( o f f - d i a g o n a l ) e l e c t r o n i c h f s c o n s t a n t s , with i n t e g r a l s of t h e t y p e

OO

(b) Other difficulties

In a s e r i e s of o t h e r c a s e s , a s a t i s f a c t o r y i n t e r p r e t a t i o n of A - c o n s t a n t s
c a n n o t b e o b t a i n e d b y t h e a p p l i c a t i o n of t h e m e t h o d o u t l i n e d a b o v e , a l t h o u g h
n o n e a r b y c o n f i g u r a t i o n c a n be s e e n w h i c h would c a u s e t h i s t r o u b l e . D i f f i c u l -
t i e s m a y i n d e e d a p p e a r at two d i f f e r e n t s t a g e s .

(a) T h e f o r m a l e x p r e s s i o n s of t h e c o n s t a n t s A m a y b e s e e n to d i s a g r e e
w i t h e x p e r i m e n t , s u c h a s in t h e c a s e of L i I l s 2 2 p :

A ( 2 P i / 2 ) = 46.17 ± 0.35 MHz


2 (experimental values for 7Li)
A( P ) = - 3 . 0 7 ± 0 . 1 3 MHz

But o u r f o r m u l a ( 2 . 2 . 1 . (d)) p r e d i c t s A ( P 1 / 2 ) / A ( P 3 / 2 ) = + 5! H e r e we s p e a k of a
" p a r a m e t r i c " difficulty.
230 BAUCHE

2 (energy in К)
L i - I low l e v e l s : I s 2s
О
l s 2 2 p J = 1 /2 14 903.66

J = 3/2 14 904.00

ls23s 27 206

ls23p J = 1 /2, 30 925


3/2

Obviously no o t h e r c o n f i g u r a t i o n is " c l o s e " to the i n t e r e s t i n g l e v e l s .

(ß) T h e " e x p e r i m e n t a l " v a l u e s f o r the e l e c t r o n i c h f s c o n s t a n t s m a y be


of the w r o n g o r d e r of m a g n i t u d e , c o m p a r e d to the a b - i n i t i o e v a l u a t i o n s ,
e. g. in the c a s e of Mn III 3 d 5 6 S 5 / 2 .
E P R m e a s u r e m e n t s with Mn s a l t s y i e l d e d a r a t h e r l a r g e h y p e r f i n e
c o n s t a n t A f o r the g r o u n d - s t a t e l e v e l 3d 5 6 S 5 ^ 2 . Now t h i s l e v e l , c o r r e s p o n d i n g
to L = 0 and c o n t a i n i n g no u n p a i r e d s - e l e c t r o n , should have the hfs c o n s t a n t s
A= B= 0. A c t u a l l y , LS coupling is not e x a c t l y f u l f i l l e d , but t h e v e r y s m a l l
m i x i n g of t h i s l e v e l with t h e o t h e r 3d s J = 5 / 2 l e v e l s (through i n t e r m e d i a t e
coupling) cannot e x p l a i n the A - v a l u e m e a s u r e d , u n l e s s t h e a d - c o n s t a n t is
given an u n r e a s o n a b l y l a r g e v a l u e ( s o t h i s c a n b e c a l l e d an " a b - i n i t i o " difficulty).

(c) Spin-core-polarization

T h e p r o b l e m of M n " and o t h e r 3d N c o n f i g u r a t i o n s is c o n s i d e r e d a s
solved by A b r a g a m , Horowitz and P r y c e [7] in 1955, who i n t r o d u c e d the
notion of " c o r e p o l a r i z a t i o n " . T h i s p h e n o m e n o n , a c o r r e c t i o n to the s i n g l e -
c o n f i g u r a t i o n m o d e l , c a n be d e s c r i b e d in t h r e e w a y s :

( a ) it c a n be s e e n a s t h e r e s u l t of the m i x i n g of the c o n f i g u r a t i o n u n d e r
study with e x c i t e d c o n f i g u r a t i o n s c o n t a i n i n g u n p a i r e d s - e l e c t r o n s . E x a m p l e :
m i x i n g of l s 2 2 s 2 . . . 3d 5 ®S with ( I s n s ) 3 S 2 s 2 . . 3d 5 indeed the F e r m i c o n t a c t
H a m i l t o n i a n g i v e s an o f f - d i a g o n a l e l e m e n t b e t w e e n t h e s e two t e r m s , and a l s o
a d i a g o n a l e l e m e n t f o r t h e e x c i t e d t e r m . Of c o u r s e m i x i n g is v e r y s m a l l
( b e c a u s e t h e e x c i t e d t e r m i s s o high), but this is c o m p e n s a t e d by the e x t r e m e l y
high v a l u e of Uj s (0) s o that an a p p r e c i a b l e e f f e c t r e s u l t s . Note that t h e
e x c i t a t i o n of a n o n - s - e l e c t r o n would give no e f f e c t , b e c a u s e L= 0.

(ß) It c a n b e r e g a r d e d a l s o in a n o t h e r way which we s h a l l d e s c r i b e with


the h e l p of the s i m p l e r e x a m p l e of L i I 1 ^ 2 p . C o n s i d e r t h e s t a t e M L = 1,
M s = + •§•. T h e c o r r e s p o n d i n g wave f u n c t i o n c o n t a i n s two l s - e l e c t r o n s with
the spin projections and - i and one 2 p - e l e c t r o n with spin p r o j e c t i o n + §.
If we i n d i v i d u a l i z e the e l e c t r o n s (although t h e t o t a l f u n c t i o n m u s t b e a n t i -
s y m m e t r i c ! ), we c a n s a y that t h e r e p u l s i o n b e t w e e n the I s and the 2p is
s m a l l e r than b e t w e e n I s and 2p; indeed, in the f i r s t c a s e t h e r e a p p e a r s in
t h e i n t e r a c t i o n e n e r g y an e x c h a n g e S l a t e r i n t e g r a l ( G 1 ( l s , 2 p ) ) with a n e g a t i v e
s i g n , u n l i k e the s e c o n d c a s e . So if we allow the two l s - e l e c t r o n s to c o r r e s -
pond to d i f f e r e n t r a d i a l f u n c t i o n s , a wave f u n c t i o n c a n b e found which is
IAEA-SMR-12/7 231

c e r t a i n l y c l o s e r to the t r u e wave f u n c t i o n than the c e n t r a l - m o d e l wave


function. The s p i n - u n r e s t r i c t e d H a r t r e e - F o c k method has been derived
along t h e s e l i n e s .
C o n s i d e r e d in the s a m e way a s L i I l s ? 2 p (M L = 1 M g = + i ) , the s t a t e
Mn + + I s 2 . . . 3d 5 6 S (ML =0 M s = 5 / 2 ) p o s s e s s e s five 3 d - e l e c t r o n s with m s = +
which i n t e r a c t in a d i f f e r e n t m a n n e r with a l l the and - \ s - e l e c t r o n s .

(7) If we want to s t i c k to the p a r a m e t r i c m e t h o d , we can u s e a r e s u l t of


Judd [9] f o r t h e n i N c o n f i g u r a t i o n s : t h e A ^ - c o n s t a n t of any l e v e l of a c o n -
f i g u r a t i o n i N can b e c o r r e c t e d f o r t h e c o r e - p o l a r i z a t i o n e f f e c t by j u s t adding
to it t h e quantity c f g ^ j - l ) , w h e r e с is a new p a r a m e t e r to b e o p t i m i z e d .

(d) Far-configuration interaction; general case

R e c e n t l y (1965) t h e f a r - c o n f i g u r a t i o n i n t e r a c t i o n p h e n o m e n o n w a s c l e a r l y
put into e v i d e n c e a l s o f o r the SL - d e p e n d e n t m a g n e t i c h f s ( t e r m s in and
{s ( 1 ) C (2) }), f r o m e x p e r i m e n t s by H a r v e y [8] on t h e oxygen ( O) ground t e r m
2 p 4 3 P . V e r y a c c u r a t e m e a s u r e m e n t s allowed H a r v e y to d e t e r m i n e f o u r h f s
A - v a l u e s (A( 3 Pj), A( 3 P 2 ) and two o f f - d i a g o n a l A - c o n s t a n t s ) . T h e n he t r i e d to
i n t e r p r e t t h e m with t h e p a r a m e t e r s a 2 p and с (see the above p a r a g r a p h ) ; t h i s
t w o - p a r a m e t e r fit showed l a r g e d i s c r e p a n c i e s with the e x p e r i m e n t a l v a l u e s .
He then s u p p o s e d that the a ç p - p a r a m e t e r s m a y be d i f f e r e n t f o r t h e i d ) and t h e
2
{S(1)C< >}(1) h f s p a r t s . F o r this t h r e e - p a r a m e t e r fit a 2 p (sC), and
a 2 p (s) - a new notation f o r c), the i n t e r p r e t a t i o n of the f o u r e x p e r i m e n t a l
values becomes excellent.
Judd [9] g a v e a t h e o r e t i c a l s u p p o r t to t h i s new p a r a m e t r i c p r o c e d u r e .
He showed t h a t , in an L S - t e r m of , t h e s e c o n d - o r d e r c r o s s e d e f f e c t s of the
e l e c t r o s t a t i c C o u l o m b r e p u l s i o n and of t h e h f s m a g n e t i c (and e l e c t r i c )
H a m i l t o n i a n can be t a k e n into a c c o u n t , k e e p i n g t h e LS wave f u n c t i o n s c h e m e ,
u n d e r the a s s u m p t i o n that the v a l u e s of ^ r " 3 ) ^ m a y b e d i f f e r e n t f o r the
and t h e {s ( 1 ) C ( 2 '} ( 1 ) (and t h e C (2) ) p a r t s . T h i s is an a p p l i c a t i o n of t h e s o -
c a l l e d m e t h o d of e f f e c t i v e o p e r a t o r s , which i s widely u s e d in o t h e r f i e l d s of
atomic physics.

Note: J r ^ f a c t , we h a v e e n c o u n t e r e d above o t h e r e f f e c t i v e o p e r a t o r s : A a j l - J
and с S-1, the o p e r a t o r which b r i n g s the a d d i t i v e c o n t r i b u t i o n c f g ^ - l ) to
A ^ i n JP n . A g e n e r a l p r o p e r t y of e f f e c t i v e o p e r a t o r s is t h a t t h e v a l i d i t y of
e a c h one is r e s t r i c t e d to a l i m i t e d wave f u n c t i o n s p a c e .

(e) The S t e r n h e i m e r effect

The famous "Sternheimer effect" or "Sternheimer correction" (traditional


t e r m s ) i s a p a r t i c u l a r type of a f a r - c o n f i g u r a t i o n i n t e r a c t i o n e f f e c t . It is t h e
e f f e c t on the e l e c t r i c - q u a d r u p o l e h f s e l e c t r o n i c p a r a m e t e r of t h e m i x i n g
b e w e e n t h e c o n f i g u r a t i o n c o n s i d e r e d . . . . (n'i ') 4f 4 2 . . . . ( n i ) N and c o n f i g u r a t i o n s
of the type (n4L ' ) 4 i ' + 1 (ní )N (n"i ").
F r o m a p a r a m e t r i c point of v i e w , this s e c o n d - o r d e r e f f e c t i s t r i v i a l :
it m u l t i p l i e s t h e h f s c o n s t a n t b n i by (1+Ç) ( f « l ) , w h e r e Ç is i n d e p e n d e n t of
the l e v e l in t h e s t u d i e d c o n f i g u r a t i o n . A m a j o r w o r k of S t e r n h e i m e r s i n c e
1950 h a s b e e n to c o m p u t e ab initio v a l u e s of ? f o r m a n y c o n f i g u r a t i o n s in a
g r e a t n u m b e r of e l e m e n t s . E x e r c i s e : C o m p i l e l i s t of t h e r e l e v a n t Jl'-*SL "
e x c i t a t i o n s , f o r SL ' going f r o m 0 to 3.
232 BAUCHE

2.3.3. Relativity

We a l l b e l i e v e in r e l a t i v i t y , and we e v e n know that the D i r a c e q u a t i o n


a l l o w s u s to handle it in q u a n t u m m e c h a n i c s (at l e a s t f o r h y d r o g e n ; c o m p l i -
c a t i o n s a p p e a r a l r e a d y when we go to h e l i u m , w h e r e the B r e i t a p p r o x i m a t e
H a m i l t o n i a n m u s t be u s e d [1] ).
S a n d a r s and B e c k showed how to t a k e r e l a t i v i t y into account f o r h f s [10],
with the h e l p of e f f e c t i v e o p e r a t o r s . To be s h o r t , in , r e l a t i v i t y is a
s e c o n d r e a s o n f o r the a nJ! (i) and a n i ( s C ) to b e d i f f e r e n t and f o r t h e a n i ( s ) to b e
n o n - z e r o w h e n i = 0. F o r the e l e c t r i c p a r t , r e l a t i v i t y c o n t r i b u t e s to fcy , but
a l s o i n t r o d u c e s new e f f e c t i v e o p e r a t o r s with a n g u l a r p a r t s w ( n ) 2 and w

2.3.4. H y p e r f i n e - s t r u c t u r e anomaly

In our m o d e l , when the f i r s t - o r d e r p e r t u r b a t i o n m e t h o d is a s a t i s f a c t o r y


a p p r o x i m a t i o n to h f s c o m p u t a t i o n s (i. e. a l m o s t a l w a y s ) , the m a g n e t i c hfs
e n e r g y AW is the p r o d u c t of / I by a p u r e l y e l e c t r o n i c f a c t o r . So, when the
h f s c o n s t a n t s A of a given l e v e l can be m e a s u r e d f o r two d i f f e r e n t i s o t o p e s
1 and 2, they should a g r e e with the r e l a t i o n A-^j/Mj = ^ is Possible
to t r y to c h e c k t h i s r e l a t i o n , b e c a u s e ju c a n be m e a s u r e d d i r e c t l y (by NMR,
f o r e x a m p l e ) . Owing to the g r e a t a c c u r a c y of a l l t h e s e m e a s u r e m e n t s , the
r e l a t i o n is s o m e t i m e s found not to hold true. 1 The quantity

is c a l l e d the h y p e r f i n e - s t r u c t u r e a n o m a l y f o r a l e v e l if isotope 2 is h e a v i e r
than i s o t o p e 1. We m a y a s k why Д 1 2 can s o m e t i m e s d i f f e r f r o m 0.
F u n d a m e n t a l l y we find h e r e a p r o b l e m w h e r e t h e s e c o n d o r d e r of p e r t u r -
b a t i o n c o n t r i b u t e s , but m o r e p r e c i s e l y the s e c o n d o r d e r of the s u m of the
h y p e r f i n e s t r u c t u r e and i s o t o p e shift e f f e c t s ; to s p e a k m o r e s i m p l y , the
e l e c t r o n i c wave f u n c t i o n c h a n g e s a l i t t l e from one i s o t o p e to the other,
b e c a u s e the s p a t i a l e x t e n s i o n and d i s t r i b u t i o n of c h a r g e and m a g n e t i s m
c h a n g e . T h i s c h a n g e in the wave f u n c t i o n is a l m o s t l i m i t e d to the s - e l e c t r o n s ,
which " s p e n d s o m e t i m e " in the n u c l e u s . So the h y p e r f i n e - s t r u c t u r e a n o m a l y
c a n b e u s e d a s a t e s t f o r the p r e s e n c e of s p i n c o r e - p o l a r i z a t i o n .

E x e r c i s e s : (a) P r o v e that e v e r y s p e c t r a l line of e v e r y n a t u r a l c h e m i c a l


e l e m e n t is a g r o u p of s e v e r a l c o m p o n e n t s (only t h e v a r i o u s c a u s e s f o r line
b r o a d e n i n g often p r e v e n t the o b s e r v a t i o n of t h i s s t r u c t u r e ) ;
(b) Find out which two n a t u r a l c h e m i c a l e l e m e n t s p o s s e s no
h y p e r f i n e s t r u c t u r e in t h e i r s p e c t r a l l i n e s .

P A R T II: ISOTOPE SHIFT

3. ISOTOPE S H I F T : GENERAL

In the following we s h a l l c o n s i d e r two i s o t o p e s of the s a m e e l e m e n t , with


m a s s n u m b e r s A1 and A j and z e r o n u c l e a r s p i n s .
IAEA-SMR-12/7 233

Although t h e r e is h e r e no h f s , t h e r e r e m a i n two d i f f e r e n c e s b e t w e e n the


t r u e n u c l e u s and the v e r y s i m p l e d e s c r i p t i o n u s e d f o r s t u d y i n g e l e c t r o n i c
s t r u c t u r e [1 ] :

very simple description true nucleus


infinite n u c l e a r m a s s finite nuclear m a s s
point n u c l e u s finite nuclear volume

T h e f i r s t d i f f e r e n c e l e a d s to the m a s s i s o t o p e s h i f t , due to the f a c t that


the n u c l e u s is not the c e n t r e of g r a v i t y of the a t o m ; the s e c o n d d i f f e r e n c e
l e a d s to the f i e l d isotope s h i f t (or v o l u m e i s o t o p e s h i f t ) , owing to the f a c t
that the e l e c t r i c n u c l e a r p o t e n t i a l " s e e n " by the e l e c t r o n s is not Z e / r f r o m
r = 0 t o г = ю. Both t y p e s of i s o t o p e s h i f t a l w a y s c o - e x i s t .

3.1. C o - e x i s t e n c e of m a s s and field i s o t o p e s h i f t s

3.1.1. Mass shift

(a) The Hamiltonian

An obvious a r g u m e n t is the following: as the n u c l e u s m o v e s , i t s k i n e t i c


e n e r g y (p N ) 2 /2M m u s t b e added to the H a m i l t o n i a n . In a c o - o r d i n a t e s y s t e m ,
h o w e v e r , w h e r e the t o t a l m o m e n t u m is z e r o ( c e n t r e - o f - m a s s s y s t e m ) ,
p N = - Çp w h e r e pi is t h e m o m e n t u m of e l e c t r o n i. So we have i m m e d i a t e l y
t h e m a s s - s h i f t H a m i l t o n i a n in t e r m s of e l e c t r o n i c o p e r a t o r s : H =(1/2M)(£ Pj)'
T h i s H a m i l t o n i a n is the s u m of H ^ g = ( 1 / 2 M ) Ç ( p ^ C n o r m a l " o r " B o h r "
m a s s s h i f t ) and H SMS = ( l / M ) E (pj • pj ) ( " s p e c i f i c " m a s s s h i f t ) .

(b) N o r m a l m a s s s h i f t (NMS)

If we add H to the m a i n e l e c t r o n i c H a m i l t o n i a n [1]

we s e e t h a t the n o r m a l m a s s - s h i f t p a r t is e a s i l y c o m b i n e d with the e l e c t r o n i c


k i n e t i c e n e r g y and y i e l d s

w h e r e ц is t h e r e d u c e d m a s s , s u c h that 1/м = l / m + 1 / M . So, in the s a m e


way a s m e 4 / i l 2 is the only e n e r g y - d i m e n s i o n e d c o n s t a n t of the p r o b l e m when
i s o t o p e s h i f t i s a b s e n t , now ß e 4 / h 2 i s the only e n e r g y - d i m e n s i o n e d c o n s t a n t .
A p a r t f r o m t h i s d i f f e r e n c e , the two e q u a t i o n s (with and without H NMS ) a r e
e x a c t l y the s a m e . So E w i t h N M S = (ß/m) E w i t h o u t N M S .
Now, what is known e x p e r i m e n t a l l y (if we s u p p o s e N M S » S M S , which is
the c a s e ) is p r a c t i c a l l y E w i t h N M S . So we c a n d e t e r m i n e the c o n t r i b u t i o n of
NMS, which i s
234 BAUCHE

ДР = F F = p (1 S3L) = P
NMS with NMS without NMS with NMS \ p / M with NMS

AF ~ - Fe x
" ^ M S - M P

A c t u a l l y A E N M S ( e n e r g y d i f f e r e n c e b e t w e e n the c a s e s M =oo and M ^oo) i s


of no i n t e r e s t ; we a r e r a t h e r i n t e r e s t e d in
M -M.
ДЕ (M = M ) - ДЕ
v x (M = M ) = — - m E
NMS 2 ^NMS Y M M exp.
1 2

o r even b e t t e r , in a t r a n s i t i o n a = or'J'-» aj, with

^ N M S (M 2 .E ' J ' ) - A E n m s (MJ,<*'J')j - [ДЕ ЫМЗ ( M 2 . a J ) - AE N M S ( M ^ J )

( isotope shift for level a'JM


and i s o t o p e s M j and M2 J
/isotope shift for level a J \
l and i s o t o p e s M j and IV^ J

with the f i n a l v a l u e

Ло =
19 W ^ 1 "
MjlVIg
1
^ w h e r e ста=
E(a'J') - E(aJ)

T h i s s h o w s t h a t the NMS in an a t o m i c l i n e d e p e n d s only on t h e w a v e


n u m b e r of t h e l i n e . T h e s i g n we have c h o s e n f o r it i s t h e u s u a l one: it i s
p o s i t i v e in a l l t r a n s i t i o n s , i . e . t h e c o m p o n e n t f o r t h e h e a v i e r i s o t o p e h a s t h e
l a r g e r w a v e n u m b e r . We c a n d r a w t h e e n e r g y s c h e m e a s shown in the
following:

a'j'

0, = 0(M| l<n) a2- o(ii2lm)

a J •
M =oo M = M. M = м 2 >м,

On t h i s s t u d y of the n o r m a l m a s s s h i f t we a l r e a d y s e e t h a t any i s o t o p e
s h i f t AO12 in a l i n e i s a " d i f f e r e n c e of d i f f e r e n c e s " : it c a n b e s e e n e i t h e r a s
t h e d i f f e r e n c e b e t w e e n Oj and <j2 o r a s t h e d i f f e r e n c e b e t w e e n the i s o t o p e
s h i f t s of two l e v e l s .
IAEA-SMR-12/7 235

3.1.2. Field shift

T h e p o t e n t i a l e n e r g y of one e l e c t r o n in the n u c l e a r e l e c t r i c f i e l d i s
V = - Z e 2 / r only f o r r > R , R b e i n g the r a d i u s of a s p h e r i c a l n u c l e u s . T h e
c u r v e s obtained f o r V a r e shown in the following.

Applying the f i r s t o r d e r of p e r t u r b a t i o n to t h e c a s e of one e l e c t r o n rü., we


obtain f o r the d i f f e r e n c e b e t w e e n the c a s e s R ^ O and R = 0

Ze2
ДЕ, V(r) + I V r ) | 2 r 2 dr

which is a p o s i t i v e quantity.

3.1.3. O r d e r s of m a g n i t u d e

(a) Mass shift

F o r m a s s s h i f t , the only l i n e quantity which is not e l e c t r o n i c is


(M 2 -M 1 )/M 1 M 2 ; it i s of the o r d e r of m a g n i t u d e of 1 / A M (A b e i n g the m a s s
n u m b e r ) . So t h e o r d e r of m a g n i t u d e of t h e m a s s s h i f t in an o p t i c a l line is

Hartree X ^ or H a r t r e e X ^ X - i—£2 m K

w h e r e A2 is a f a c t o r which can v a r y f r o m a few u n i t s (for h y d r o g e n ) to


60 000 ( f o r p l u t o n i u m ) .
T h e o r d e r of m a g n i t u d e of the m a s s s h i f t d e c r e a s e s r a p i d l y (°c 1 /А 2 ) a s
A i n c r e a s e s in t h e p e r i o d i c t a b l e .

(b) Field shift

F o r an a p p r o x i m a t e e v a l u a t i o n of field s h i f t we a s s u m e that the whole


n u c l e a r c h a r g e is l o c a t e d on the s p h e r e of r a d i u s R. T h e n V ( r ) = - Z e 2 / R f o r
0 < r < R . T h e field s h i f t is i m p o r t a n t only f o r s - e l e c t r o n s , whose wave
f u n c t i o n is n o n - z e r o f o r r = 0. We s u p p o s e that t h i s wave f u n c t i o n i s a l m o s t
c o n s t a n t in t h e n u c l e a r v o l u m e (a v e r y good a p p r o x i m a t i o n , a s R i s so s m a l l ) .
236 BAUCHE

We obtain

Z(;2r2
AF -
V°>l 2

H e r e e2 and |u n j ! (0)| 2 a r e t h e only e l e c t r o n i c q u a n t i t i e s . So we could conclude


that the o r d e r of m a g n i t u d e of AE fs i s s i m p l y H a r t r e e X R 2 / a 2 . H o w e v e r , as
in the c a s e of t h e m a s s s h i f t , we a r e i n t e r e s t e d in the g r o s s d e p e n d e n c e of
the f i e l d s h i f t on A. So we c o n s i d e r the quantity

R2
H a r t r e e X ^ X Z X a 3 | u „(0)| 2

f o r an o r d e r - o f - m a g n i t u d e e s t i m a t e ;

(a3| U n { (0)| 2 is d i m e n s i o n l e s s )

We now u s e the f o r m u l a R = r 0 A1^3, with r 0 ~ 1 f e r m i , a s w e l l as t h e f a c t that


| u n i ( 0 ) | d e p e n d s m a r k e d l y upon Z; u s i n g the f o r m u l a s f o r h y d r o g e n i c a t o m s [11],
we t a k e a d e p e n d e n c e in Z 3 .
The o r d e r of m a g n i t u d e of AE fs b e c o m e s

H a r t r e e X 4 - X Z4A2/3
a

and, b e t w e e n two i s o t o p e s w h o s e m a s s n u m b e r s d i f f e r by ДА = 2,

H a r t r e e X ^ - X Z 4 А" 1 / 3 , i . e . | X 10" 2 А п / 3 mK ( b e c a u s e Z ^ A / 2 )

T h e f i e l d s h i f t i n c r e a s e s r a p i d l y (« A 11 / 3 ) along the p e r i o d i c t a b l e .

Note: the f a c t o r A11^3 is r e l a t i v e l y c o r r e c t , but the c o n s t a n t f a c t o r is m u c h


too l a r g e a s we s h a l l show l a t e r (3.2. c. ).

3.1.4. T h e King g r a p h s

(a) Historical background. R e l a t i v e i s o t o p e s h i f t (RIS)

F o r m a n y y e a r s only t h e g e n e r a l t r e n d s of t h e two p a r t s of isotope s h i f t


w e r e t a k e n into a c c o u n t , t o g e t h e r with t h e i d e a that f o r Z < 3 0 (Zn)
( r e s p . > 54 (Xe)) only the m a s s ( r e s p . field) s h i f t w a s p r e s e n t , and that b e t w e e n
Z = 30 and Z = 54 the i s o t o p e s h i f t is v e r y s m a l l . C o n s e q u e n t l y , a s no a p p r e -
c i a b l e m i x i n g b e t w e e n the two e f f e c t s a p p e a r e d , the r e l a t i v e i s o t o p e s h i f t
(RIS) w a s the s a m e in a l l l i n e s of a given e l e m e n t :

RIS f o r A ^ A 2 , А 3 = Д а у Д а а 2
IAEA-SMR-12/44,46,48 237

Indeed we s e e t h a t , f o r e v e r y line,

RIS
= Щ Ч ^ Щ (only m a s s ehlft)

RIS = (only f i e l d s h i f t )
c 2 -q
where
Ze2 2,
C. = v( (r) + r dr

At high m a s s n u m b e r s the RIS f o r m a s s s h i f t is v e r y c l o s e to u n i t y , f o r


A j , A 2 and A 3 in a r i t h m e t i c p r o g r e s s i o n . T h e RIS f o r f i e l d s h i f t d e p e n d s on
t h e f o r m of t h e n u c l e u s .
With the i m p r o v e m e n t in e x p e r i m e n t a l a c c u r a c y ( e s p e c i a l l y t h r o u g h the
u s e of e n r i c h e d i s o t o p e s ) , S t r i g a n o v and c o - w o r k e r s [12] could m e a s u r e in
1962 a lot of l i n e s of Sm I f o r a s e r i e s of i s o t o p e s , p r o v i n g that the RIS
c h a n g e s m a r k e d l y f r o m s o m e l i n e s to o t h e r s .
Soon t h e r e a f t e r King [13] i n t e r p r e t e d t h i s v a r i a t i o n by the m i x i n g of
m a s s and f i e l d s h i f t s . Indeed, if both a r e of c o m p a r a b l e m a g n i t u d e , we
can w r i t e
М
з-М2 , .
A
°*23 1 Д Л + (С3 C 2 ) E a
RIS. =
M 2 - M]L±K (C2-Cl)Ea
MjM2 a+

f o r the RIS in line a, K a and E a b e i n g p u r e l y e l e c t r o n i c m a s s (SMS included)


and field f a c t o r s , d e p e n d i n g only on the line a. E v i d e n t l y RIS d e p e n d s on a.

(b) The King g r a p h

King p r o p o s e d to r e p r e s e n t g r a p h i c a l l y t h i s s i t u a t i o n . If one d e f i n e s

and
A A
? = До15 • »• •>• • (line b)
l] A. - A .
] i
then

E / E
s 5 К
=ЁГ Ч .- Ér15*
b b

f o r e v e r y p a i r (i, j) of i s o t o p e s . So, in c o - o r d i n a t e s , e a c h p a i r of l i n e s
( a , b ) m u s t c o r r e s p o n d to a s t r a i g h t l i n e (see f i g u r e ) , independent of the
i s o t o p e s c o n s i d e r e d ( s e e a l s o [14] f o r s u c h a g r a p h ) .
238 BAUCHE

E a_
Slope

I n t e r c e p t ОМ

g (line b)

T h e i n t e r c e p t and the s l o p e of t h e line a r e p u r e l y e l e c t r o n i c q u a n t i t i e s .


Since 1963 e x p e r i m e n t a l i s t s have d e t e r m i n e d m a n y King l i n e s with good
a c c u r a c y (the m e a s u r e m e n t s m u s t be v e r y a c c u r a t e f o r t h e t e s t on w h e t h e r
the p o i n t s a r e aligned to be s i g n i f i c a n t ) .
One i m p o r t a n t r e s u l t is the following. F o r odd i s o t o p e s , whose l i n e s
a r e a f f e c t e d by t h e h y p e r f i n e - s t r u c t u r e p h e n o m e n o n , it is e a s i l y shown that
the c e n t r e of g r a v i t y of the s t r u c t u r e is at the p l a c e w h e r e the line would b e
in the a b s e n c e of h f s . ( E x e r c i s e : p r o v e t h a t , f o r h f s of a r b i t r a r y m u l t i p o l a r
t y p e , the c e n t r e of g r a v i t y of any l e v e l s t r u c t u r e is at t h e e n e r g y t h e l e v e l
would have in t h e a b s e n c e of h f s , if the f i r s t o r d e r of p e r t u r b a t i o n t h e o r y is
s u f f i c i e n t ( g e n e r a l c a s e ) . ) H o w e v e r , we c a n plot in t h e King g r a p h t h e p o i n t s
f o r even and odd i s o t o p e s s e p a r a t e l y . It will b e a l m o s t c e r t a i n t h a t , in
s o m e c a s e s , s u c h p o i n t s " f o r odd i s o t o p e s " d e f i n i t e l y do not lie on the line
obtained f o r t h e e v e n i s o t o p e s .
A n o t h e r way of c o n s i d e r i n g the King line i s the following. Denote by
y = K a and x = K b t h e unknown q u a n t i t i e s K a and Kfe. T h e s e q u a n t i t i e s a r e
r e l a t e d by the l i n e a r e q u a t i o n y = a x + ß , w h e r e a= E a / E b a n d ß = K a - ( E a / E b ) K b
a r e given e x p e r i m e n t a l q u a n t i t i e s . T h i s e q u a t i o n is e x a c t l y the equation of
the King line. Suppose now that s e v e r a l King l i n e s a r e d r a w n with a c o m m o n
line " a " . It would then b e enough to know (by an a - p r i o r i t h e o r e t i c a l c o m -
p u t a t i o n ? ) t h e v a l u e of K j to d e d u c e i m m e d i a t e l y t h e K^, - v a l u e s .

x : l i n e s "b'tt
у : line "a"
IAEA-StoR-12/7 239

3.2. Theoretical approaches

(a) P a r a m e t r i c study of s p e c i f i c m a s s shift plus field s h i f t

S u b t r a c t i n g the NMS f r o m t h e e x p e r i m e n t a l r e l a t i v e v a l u e s of t h e s h i f t s
(between i s o t o p e s 1 and 2) of l e v e l s of a given c o n f i g u r a t i o n , we c a n t r y and
" i n t e r p r e t " the r e s i d u a l s h i f t s by m e a n s of the p a r a m e t r i c m e t h o d [15].

(b) Mass shift

( a ) V a r i o u s a u t h o r s have t r i e d t o e v a l u a t e t h e s p e c i f i c m a s s s h i f t by
" a b - i n i t i o " m e t h o d s , but the r e s u l t s achieved s o f a r [16] w e r e r e l a t i v e l y poor.
(j3) F o r m a l e x p r e s s i o n s f o r r e l a t i v i t y c o r r e c t i o n s to the m a s s s h i f t w e r e
given by Stone [17]; the c o r r e s p o n d i n g o p e r a t o r s act in the n o n - r e l a t i v i s t i c
s p a c e . No c o m p l e t e l y r e l a t i v i s t i c e x p r e s s i o n f o r t h e m a s s s h i f t is yet known.
T h e i n t e r p r e t a t i o n of s h i f t s in Ne I p r o v e s t h e e x i s t e n c e of e f f e c t s of
r e l a t i v i t y [18].

(c) Field shift

( а ) T h e f i r s t a t t e m p t to e v a l u a t e field s h i f t t h e o r e t i c a l l y w a s m a d e by
B a r t l e t t [ 1 9 ] , who u s e d n o n - r e l a t i v i s t i c e l e c t r o n i c f u n c t i o n s . H o w e v e r , the
e l e c t r o n h a s a m a r k e d r e l a t i v i s t i c c h a r a c t e r when it is v e r y c l o s e to o r
i n s i d e t h e n u c l e u s ( e x e r c i s e : c o m p u t e the n o n - r e l a t i v i s t i c k i n e t i c e n e r g y of a
I s - e l e c t r o n , in t h e h y d r o g e n a t o m i c s p e c t r u m , when it is located at r = 1 f e r m i ,
which is a l m o s t t h e r a d i u s of the p r o t o n ) . F o r a c o r r e c t e v a l u a t i o n we m u s t
c o n s i d e r t h e D i r a c equation f o r one e l e c t r o n at v e r y s m a l l v a l u e s of r [20].
(ß) In the c a s e of s e v e r a l e l e c t r o n s the s c r e e n i n g f a c t o r s a r e i n t r o d u c e d
p h e n o m e n o l o g i c a l l y . T h e y c a n b e computed a p p r o x i m a t e l y by a b - i n i t i o
m e t h o d s [21].
(7) T h e study of i s o t o p e s h i f t in a t o m i c t r a n s i t i o n s of m u o n i c a t o m s
( a t o m s w h e r e one of t h e e l e c t r o n s is r e p l a c e d by a m u o n ) and in the X - r a y
t r a n s i t i o n s of o r d i n a r y a t o m s y i e l d s e a s i l y the f i e l d s h i f t s , b e c a u s e t h e r e the
SMS is n e g l i g i b l e .
(б) As c o n c e r n s t h e n u c l e u s , the isotope s h i f t g i v e s an i n f o r m a t i o n on a
quantity c l o s e to the r o o t - m e a n - s q u a r e value of i t s c h a r g e d i s t r i b u t i o n . Is
t h i s quantity of any i n t e r e s t to the n u c l e a r p h y s i c i s t ?

REFERENCES

[1] FENEUILLE, S . , t h e s e P r o c e e d i n g s .
[2] S C H W A R T Z , C . , P h y s . R e v . 9 7 (1955) 3 8 0 a n d 105 (1957) 1 7 3 .
MALLI, G . , FRAGA, S . , C a n . J . P h y s . 4 5 ( 1 9 6 7 ) 219.
[3] RAMSEY, N . F . , N u c l e a r M o m e n t s , John W i l e y a n d Sons, N e w York ( 1 9 5 3 ) .
[4] KOPFERMANN, H . , N u c l e a r M o m e n t s ( t r a n s l a t i o n ) . A c a d e m i c Press, N e w York ( 1 9 5 8 ) .
[5] KUHN, H . G . , A t o m i c s p e c t r a , L o n g m a n s , London ( 1 9 6 9 ) .
[6] EDMONDS, A . R . , A n g u l a r M o m e n t u m i n Q u a n t u m M e c h a n i c s , P r i n c e t o n U n i v e r s i t y Press ( 1 9 6 0 ) .
[7] AGRAGAM, A . , H O R O W I T Z , J . , PRYCE, M . H . L . , P r o c . R . S o c . , A230 ( 1 9 5 5 ) 1 6 9 .
[8] HARVEY, J . S . M . , P r o c . R . S o c . 2 8 5 (1965) 5 8 1 .
[9] JUDD, B . R . , H y p e r f i n e S t r u c t u r e s in t h e A t o m i c 2 p - S h e l l , in "La S t r u c t u r e H y p e r f i n e M a g n é t i q u e des
A t o m e s e t des M o l é c u l e s " , Editions du C . N . R . S . , Paris ( 1 9 6 7 ) .
[10] SANDARS, P . G . H . , BECK, J . . P r o c . R . S o c . A 2 8 9 ( 1 9 6 5 ) 1 0 8 .
2 4 0 BAUCHE

[11] CONDON, E . U . , SHORTLEY, G . H . , T h e T h e o r y of A t o m i c S p e c t r a , C a m b r i d g e U n i v e r s i t y Press ( 1 9 5 1 ) .


[12] STRIGANOV, A . R . , KATULIN, V . A . , ELISEEV, V . V . , O p t . S p e c t r o s c . 12 (1962) 9 1 .
[13] KING, W . H . , J . O p t . S o c . A m . 5 3 (1963) 6 3 8 .
[14] KING, W . H . , J . P h y s . В ( A t o m . M o l e c . P h y s . ) 4 (1971) 2 8 8 .
[15] STONE, A . P . , P r o c . P h y s . S o c . 74 (1959) 4 2 4 Г
BAUCHE, J . , P h y s i c a 4 4 ( 1 9 6 9 ) 2 9 1 .
[16] BAUCHE, J . , CRUBELLIER, A . , J . P h y s . (1969) c o l l o q u e C l .
[17] S T O N E , A . P . , P r o c . P h y s . S o c . 77 (1961) 786 a n d 81 (1963) 8 6 8 .
[18] BAUCHE, J . . KELLER, J . C . , P h y s . L e t t . 36A (1971) 2 1 1 .
[19] BARTLETT, J . H . , N a t u r e 128 (1932) 4 0 8 .
[20] RA С А Н , G - , N a t u r e 1 2 9 (1932) 7 2 3 .
ROSENTHAL, J . E . . BREIT, G . , P h y s . R e v . 4 1 (1932) 4 5 9 .
HUMBACH, W . , Z . P h y s . 1 4 1 (1955) 5 9 .
[21] WILSON, M . , P h y s . R e v . Г76 (1968) 5 8 .
IAEA-S M R - 1 2 / 4 5

HIGHLY EXCITED ATOMS

I . C . PERCIVAL
University of Stirling,
Stirling,

Scotland, United Kingdom

Abstract
HIGHLY EXCITED A T O M S .
1. I n t r o d u c t i o n ; 2 . E l e m e n t a r y p r o p e r t i e s ; 3. T h e c o r r e s p o n d e n c e p r i n c i p l e for i n t e n s i t y of r a d i a t i o n ;
4. Classical collisions; 5. C l a s s i c a l c r o s s - s e c t i o n s ; 6. D i s c r e t e s t a t e s a n d c o r r e s p o n d e n c e p r i n c i p l e s ;
7 . Discussion of l i t e r a t u r e . Appendix.

1. INTRODUCTION

By highly excited we m e a n an a t o m o r ion which h a s an e l e c t r o n whose


b i n d i n g e n e r g y i s v e r y s m a l l c o m p a r e d with i t s b i n d i n g e n e r g y in t h e g r o u n d
s t a t e . P r o p e r t i e s of s u c h a t o m s d i f f e r c o n s i d e r a b l y f r o m t h o s e of o t h e r
atoms or ions.
H i g h l y e x c i t e d a t o m s a r e found in p l a s m a s , w h e r e t h e y p l a y a n i m p o r t a n t
r o l e in r e c o m b i n a t i o n . T h e s e p l a s m a s m a y b e f o u n d in t h e l a b o r a t o r y , in
s t e l l a r a t m o s p h e r e s o r i n i n t e r s t e l l a r s p a c e . T h e y m a y not a l w a y s b e
o b s e r v e d in a l l t h e s e r e g i o n s but t h e y a r e d i r e c t l y o b s e r v e d in h i g h l y i o n i z e d
r e g i o n s (HII r e g i o n s ) of s p a c e , in t h e n e i g h b o u r h o o d of hot s t a r s a n d a l s o i n
t h e HI r e g i o n s w h i c h a r e c o o l e r a n d h a v e a r e l a t i v e l y low d e g r e e of
i o n i z a t i o n . In e a c h c a s e , r a d i o f r e q u e n c y t r a n s i t i o n s a r e o b s e r v e d b e t w e e n
close-lying states using r a d i o - t e l e s c o p e s .
F o r e x a m p l e , t h e t r a n s i t i o n H(109a), w h i c h i s

H(n = 110) - H(n = 109) + hv

w h e r e v i s in t h e r a d i o f r e q u e n c y r a n g e .
S t a t e s of a r a t h e r l o w e r l e v e l of e x c i t a t i o n m a y b e of p r a c t i c a l i m p o r t a n c e
i n t h e p r o d u c t i o n of hot l a b o r a t o r y p l a s m a s . T h e s e p l a s m a s a r e r e q u i r e d if
we w a n t to p r o d u c e c o n t r o l l e d t h e r m o n u c l e a r r e a c t i o n s , n e e d e d t o e a s e t h e
W o r l d ' s energy p r o b l e m s in the coming d e c a d e s .
T h e r e i s m o r e t h a n one p o s s i b l e m e a n s to t h i s end: t h a t w h i c h i n v o l v e s
h i g h l y e x c i t e d a t o m s i s t h e p r o d u c t i o n of p l a s m a s in a m a g n e t i c f i e l d by
i n j e c t i o n of a f a s t (10 keV o r m o r e ) b e a m of d e u t e r i u m a t o m s . In the e a r l y
s t a g e s of p l a s m a p r o d u c t i o n , g r o u n d - s t a t e a t o m s a r e not s i g n i f i c a n t l y
i o n i z e d b y t h e p l a s m a , and a t o m s in a low s t a t e of e x c i t a t i o n (n <, 7) d e c a y
r a p i d l y to the I s o r 2s s t a t e s . However, highly excited s t a t e s have a v e r y
weakly bound o r b i t a l e l e c t r o n which is r e l a t i v e l y easily s t r i p p e d f r o m the
d e u t e r i u m n u c l e u s to c o n t r i b u t e a n e w ion to t h e p l a s m a . T y p i c a l l y , a t o m s
w i t h p r i n c i p a l q u a n t u m n u m b e r n l e s s t h a n 16 a r e i n v o l v e d .
So w e s e e t h a t t h e a r e a s of i n t e r e s t in h i g h l y e x c i t e d a t o m s a r e l a r g e .
H i g h l y e x c i t e d s t a t e s a r e c o m m o n l y o b s e r v e d in t h e u . v . a n d in
t h e v i s i b l e . T h e h i g h e s t i s t h e o b s e r v a t i o n of a s t a t e of B a with n = 105 by

2 4 1
2 4 2 PERCIVAL

m e a n s of a 3 0 - f t (9 m) u . v . s p e c t r o g r a p h at t h e A r g o n n e N a t i o n a l L a b o r a t o r y
in U . S . A . [ G a r t o n a n d T o m k i n s (unpublished)] . T h i s work c o n c e r n s
t r a n s i t i o n s f r o m a highly e x c i t e d state t o a low s t a t e .
T h e o b s e r v a t i o n s we c a n m a k e in t h e l a b o r a t o r y a r e c o m p l e m e n t a r y to
t h o s e m a d e by a s t r o n o m e r s . T h e f o r m e r involve t r a n s i t i o n s f r o m a highly
e x c i t e d s t a t e to a l o w - l y i n g s t a t e ; t h e l a t t e r t r a n s i t i o n s b e t w e e n highly
e x c i t e d s t a t e s w h e r e o b s e r v a t i o n s a r e m a d e of the " r a d i o - r e c o m b i n a t i o n
l i n e s " . T h e d i s t i n c t i o n b e t w e e n the above o b s e r v a t i o n s i s an i m p o r t a n t one.
A highly e x c i t e d s t a t e i s c h a r a c t e r i z e d by q u a n t u m n u m b e r s (Í, m) in
a d d i t i o n to t h e p r i n c i p a l q u a n t u m n u m b e r n, and t h e i m p o r t a n t (Í, m) s t a t e s
in t h e two c a s e s d i f f e r :
for radio-recombination i , m < , n
in t h e l a b o r a t o r y I , m ~ 0 , 1 , 2, 3.
B e c a u s e t h e p r o p e r t i e s of highly e x c i t e d s t a t e s d i f f e r so m u c h f r o m
t h o s e of l o w - s t a t e a t o m s , t h e a p p r o p r i a t e t h e o r y a l s o d i f f e r s . In p a r t i c u l a r ,
f o r highly e x c i t e d a t o m s the c l a s s i c a l m o d e l of t h e a t o m can b e t a k e n
s e r i o u s l y . M e t h o d s can b e used which a r e at b e s t doubtful f o r low s t a t e s
of e x c i t a t i o n .

2. ELEMENTARY PROPERTIES

C o n s i d e r t h e B o h r m o d e l of a c l a s s i c a l e l e c t r o n moving in a c i r c u l a r
o r b i t a r o u n d a p r o t o n to r e p r e s e n t t h e g r o u n d s t a t e (n = 1 ) of t h e h y d r o g e n
a t o m , w h e r e t h e m o d e l i s evidently v e r y c r u d e .

T A B L E I. E L E M E N T A R Y P R O P E R T I E S O F HIGHLY E X C I T E D S T A T E S

I II III IV

Property n = 1 Arbitrary n n = 110

Binding e n e r g y U n 1 Ry = 1 3 . 6 eV Ry/n 2 1 . 1 X 10"3 eV

Radius a R of a 0 = aL n2a0 6 . 4 X 10"5 c m


Bohr o r b i t = 5 . 3 X 1СГ9 c m

G e o m e t r i c cross - 8. 8 X 1 0 " " cm2 n4iraj 1 . 3 X 10"" c m


s e c t i o n ira^j

rms velocity c a = v j = 2 . 2 X 10 s vj/n 2 . 0 X 10 6 c m / s


of e l e c t r o n v n cm/s

3„
Period T n 1 . 5 X 10"1S s n T! 2. 0 X 10" 1 0 s

Fundamental Vi - n"3!^ 4 . 9 4 1 X 10 9 Hz
classical frequency vc 6 . 5 7 6 X 10 1 5 Hz [(n - [ 5 . 0 0 9 X 10® H z ]

Classical wave >4 1 = 2 R H 2n"3RH 0.1648 cm"1


n u m b e r X."1 = 2 . 1 9 4 X 10 5 c m " 1 [2(n - £)"3 R H ] [0.1671 cm"1 ]

Ouantal na None n - i 5 . 009 M H z


frequency [n(n - l)]2
IAEA-SMR-12/44,46,48 243

T h e g e o m e t r i c c r o s s - s e c t i o n g i v e s a good i d e a of the e f f e c t i v e s i z e of
t h e a t o m , t h e r m s v e l o c i t y is e x a c t l y r i g h t , but the c l a s s i c a l f r e q u e n c y h a s
no m e a n i n g . T h e c l a s s i c a l p r o p e r t i e s of a highly e x c i t e d s t a t e can b e
o b t a i n e d f r o m t h o s e of t h e g r o u n d s t a t e by c e r t a i n s c a l i n g l a w s , a s s e e n in
c o l u m n s III and IV of T a b l e I.
S t a r t i n g with t h e q u a n t a l e x p r e s s i o n f o r t h e e n e r g y we find t h e H(110)
a t o m s a r e so v e r y weakly bound ( 1 . 1 X 10" 3 eV) that p a r t i c l e s at r o o m
t e m p e r a t u r e (1/40 eV) h a v e enough e n e r g y to d e s t r o y t h e m . Only low d e n s i t y
can s a v e t h e m .
A c c o r d i n g to C o u l o m b ' s l a w t h e o r b i t a l r a d i u s of a c h a r g e d p a r t i c l e
bound to a n o t h e r one t y p i c a l l y v a r i e s i n v e r s e l y with t h e e n e r g y , so t h e m e a n
B o h r r a d i u s f o r an H a t o m v a r i e s a s n 2 . T h e s i z e of an H(110) a t o m i s
t y p i c a l of a s m a l l b i o l o g i c a l o r g a n i s m . If it w e r e s o l i d it could b e s e e n
e a s i l y with an o p t i c a l m i c r o s c o p e . It is a s big when c o m p a r e d to a t y p i c a l
g r o u n d - s t a t e a t o m as a g r o u n d - s t a t e a t o m i s c o m p a r e d to i t s n u c l e u s . By
analogy, t h e s t r u c t u r e of t h e i o n i c c o r e of a highly e x c i t e d a t o m c a n usually
b e n e g l e c t e d . T h e c o r e is d i s t i n g u i s h e d only by i t s c h a r g e and m a s s , except
f o r r e l a t i v e l y v e r y s m a l l e f f e c t s a n a l o g o u s to t h e h y p e r f i n e s t r u c t u r e of
o r d i n a r y a t o m s . To t h i s e x t e n t , all highly e x c i t e d a t o m s a r e t h e s a m e , t h e i r
p r o p e r t i e s depending p r i m a r i l y on t h e c h a r g e of the c o r e and t h e q u a n t u m
n u m b e r s of the highly e x c i t e d e l e c t r o n s . E v e n a m o l e c u l a r ion c o r e m a k e s
little d i f f e r e n c e .
F r o m K e p l e r ' s l a w s of p l a n e t a r y m o t i o n , t h e p e r i o d of the e l e c t r o n in
i t s o r b i t s c a l e s a s the 3 / 2 p o w e r of the m e a n r a d i u s . F r o m t h i s we obtain
the f u n d a m e n t a l c l a s s i c a l f r e q u e n c y f o r a highly e x c i t e d a t o m , v i z .

v c = n" 3 vc (2.1)
n l \ • )

w h e r e v^ i s the " f r e q u e n c y " of the c l a s s i c a l a t o m i c m o d e l f o r t h e g r o u n d


s t a t e . F o r c i r c u l a r o r b i t s with m a x i m u m a n g u l a r . m o m e n t u m f o r fixed
e n e r g y U n , only t h e f u n d a m e n t a l f r e q u e n c y i s e m i t t e d (this c o r r e s p o n d s to
t h e q u a n t u m m e c h a n i c a l r u l e t h a t if I = jf m a x , a t r a n s i t i o n with A t = + 1 i s
i m p o s s i b l e ) . F o r e l l i p t i c o r b i t s with s m a l l e r a n g u l a r m o m e n t u m , t h e r e a r e
F o u r i e r c o m p o n e n t s of the m o t i o n at t h e h a r m o n i c f r e q u e n c i e s 2vc, 3v°, e t c . ,
which c o r r e s p o n d to q u a n t a l t r a n s i t i o n s with change Д п in t h e p r i n c i p a l
q u a n t u m n u m b e r of Д п = 2 , 3 , . . . e t c . F o r t h e q u a n t a l a t o m , t h e s e t r a n s i t i o n s
h a v e f r e q u e n c i e s which a r e not e x a c t m u l t i p l e s of t h e f u n d a m e n t a l f r e q u e n c y ,
but it i s hot too bad an a p p r o x i m a t i o n when Д п « п.
F r o m c l a s s i c a l f r e q u e n c i e s , following B o h r , we can obtain an e s t i m a t e
of t h e e n e r g y d i f f e r e n c e b e t w e e n i n i t i a l and f i n a l s t a t e s of an o p t i c a l t r a n s i t i o n
by u s i n g t h e P l a n c k r e l a t i o n

Д Е = \w = (2.2)

T h i s i s a d i r e c t a p p l i c a t i o n of B o h r ' s c o r r e s p o n d e n c e p r i n c i p l e f o r
frequencies.
T h e c o r r e s p o n d e n c e p r i n c i p l e i s v a l i d in t h e l i m i t of high q u a n t u m
n u m b e r s , and f r o m T a b l e I we s e e that it i s c l e a r l y m u c h b e t t e r f o r n = 110
t h a n f o r n = 1, a s we would e x p e c t .
In q u a n t u m o r wave m e c h a n i c s , the wave f u n c t i o n s of highly e x c i t e d
s t a t e s have v e r y m a n y o s c i l l a t i o n s (nodes), about 10 6 f o r n = 110. T r a d i t i o n a l
q u a n t a l m e t h o d s , s u c h a s c l o s e - c o u p l i n g , f o r t r e a t i n g the c o l l i s i o n s with
244 PERCIVAL

s u c h a t o m s r e q u i r e the n u m e r i c a l r e p r e s e n t a t i o n of t h e wave f u n c t i o n s in a
c o m p u t e r , and the n u m b e r of r e a l n u m b e r s r e q u i r e d to r e p r e s e n t s u c h a
wave f u n c t i o n i s at l e a s t a s l a r g e as the n u m b e r of o s c i l l a t i o n s . F u r t h e r m o r e
one n e e d s to c o n s i d e r a p p r o x i m a t e l y 10 6 d i f f e r e n t wave f u n c t i o n s (n in e a c h
of the t h r e e d i m e n s i o n s ) in o r d e r to s o l v e t h e c o l l i s i o n p r o b l e m . Obviously
when we a r e d e a l i n g with a n o n - s e p a r a b l e s y s t e m t h i s is a v e r y g r e a t
h a n d i c a p . T h e r e a r e m e t h o d s of s i m p l i f y i n g the q u a n t a l p r o b l e m by taking
a d v a n t a g e of the l a r g e n u m b e r of o s c i l l a t i o n s . T h e s e m e t h o d s a r e e i t h e r
r e l a t i v e l y r o u g h , o r they r e s u l t in e x p r e s s i o n s which can o f t e n be obtained
m o r e s i m p l y by c l a s s i c a l m e t h o d s o r m e t h o d s b a s e d on the c o r r e s p o n d e n c e
principle.
T h e c o r r e s p o n d e n c e p r i n c i p l e s that we s h a l l u s e can a l l be d e r i v e d f r o m
the S c h r ö d i n g e r o r H e i s e n b e r g f o r m s of q u a n t u m m e c h a n i c s . When t h i s i s
done they can b e applied d i r e c t l y to a wide v a r i e t y of p h y s i c a l p r o b l e m s .
C l a s s i c a l and c o r r e s p o n d e n c e p r i n c i p l e m e t h o d s should not be r e g a r d e d a s
an a l t e r n a t i v e m e t h o d to q u a n t u m m e c h a n i c s , but a s a m e t h o d of applying
q u a n t u m m e c h a n i c s which i s a p p r o p r i a t e to highly e x c i t e d s t a t e s .

3. C O R R E S P O N D E N C E P R I N C I P L E F O R INTENSITY O F RADIATION

B o h r w a s able to p r e d i c t the a p p r o x i m a t e i n t e n s i t y of s p o n t a n e o u s l y
e m i t t e d r a d i a t i o n b e t w e e n highly e x c i t e d s t a t e s by s u p p o s i n g that the m e a n
p o w e r W e m i t t e d in t h e t r a n s i t i o n n n1 t e n d s to c o i n c i d e with t h e m e a n
p o w e r W c e m i t t e d at the c o r r e s p o n d i n g c l a s s i c a l f r e q u e n c y :
If ДЕ i s the e n e r g y d i f f e r e n c e , and A is the quantal t r a n s i t i o n p r o b a b i l i t y ,
then

AAE^WC (3.1)

C o n s i d e r a c l a s s i c a l h y d r o g e n a t o m , and f o r s i m p l i c i t y s u p p o s e that
the n u c l e u s h a s infinite m a s s and is at r e s t at t h e o r i g i n of o u r c o - o r d i n a t e
s y s t e m . Let (g ,rj) b e t h e c o - o r d i n a t e s of t h e e l e c t r o n in the p l a n e of i t s
e l l i p t i c m o t i o n . Suppose that t h e unit v e c t o r f points in t h e d i r e c t i o n of the
p e r i h e l i o n (the c l o s e s t point of t h e e l e c t r o n to t h e n u c l e u s ) , a s in F i g . l .
T h e e l e c t r o n m o v e s in a p o s i t i v e , a n t i - c l o c k w i s e s e n s e in t h e (Ç,r?)
p l a n e . F r o m t h e s t a n d a r d t h e o r y of p l a n e t a r y m o t i o n , a s given by Landau
and L i f s h i t s (1969), in t e r m s of a p a r a m e t e r u which i s c a l l e d t h e ' e c c e n t r i c
a n o m a l y ' , we h a v e

f = a ( c o s u - e) r) = a(l - e 2 ) ^ s i n u (3.2)

w h e r e e i s t h e e c c e n t r i c i t y of t h e orbit a n d 2a i s t h e l e n g t h of t h e m a j o r
a x i s of t h e e l l i p s e .
T h e t i m e т i s given e x p l i c i t l y in t e r m s of u by

шт = u - e s i n u (3. 3)

T h e s e e q u a t i o n s m a y be v e r i f i e d by s u b s t i t u t i o n into N e w t o n ' s l a w s of m o t i o n .
S e m i - m a j o r a x i s a a n d f u n d a m e n t a l a n g u l a r f r e q u e n c y u a r e given in t e r m s
of the i o n i z a t i o n e n e r g y U by
IAEA-SMR-12/44,46,48 245

e2 2
- П ^

w h e r e e i s t h e c h a r g e of the e l e c t r o n and m e i s i t s m a s s . Note t h a t both a


and w a r e i n d e p e n d e n t of t h e e c c e n t r i c i t y e f o r a given U.
N T h e e c c e n t r i c i t y e i s r e l a t e d to the c l a s s i c a l a n g u l a r m o m e n t u m I e
through the equation

1 = (3.5)
m e4
e
C i r c u l a r o r b i t s with e = 0 a r e t h e c l a s s i c a l o r b i t s of m a x i m u m a n g u l a r
momentum
i

f o r a g i v e n U. T h e y c o r r e s p o n d t o q u a n t a l s t a t e s of m a x i m u m a n g u l a r
m o m e n t u m q u a n t u m n u m b e r i m a x = n - 1. T h e s t r a i g h t - l i n e o r b i t s of l e n g t h
2a, with e = 1 c o r r e s p o n d t o q u a n t a l s - s t a t e s .

FIG. 1. C o - o r d i n a t e s y s t e m for e l e c t r o n o r b i t a l m o t i o n .

In o r d e r t o apply t h e c o r r e s p o n d e n c e p r i n c i p l e we h a v e t o o b t a i n t h e
F o u r i e r c o m p o n e n t s of t h e m o t i o n with r e s p e c t to t h e t i m e r , a s w a s done
f o r p l a n e t a r y m o t i o n by L a g r a n g e in 1790:

f ( T ) = Y €s e x p ( - i s i o r ) (3.7)
S = - CO

w h i c h g i v e s us by t h e F o u r i e r t h e o r e m
T = 271 /ш

€S f С (т)exp(ISCOT)dr (3.8)
0
2тг
= J ? (u) (1 - e c o s u) exp {is(u - e sinu)}du (3.9)
о
246 PERCIVAL

therefore

sg s = a JJ (se), (s Ф 0) (3.10)

u s i n g t h e s t a n d a r d i n t e g r a l f o r m f o r t h e B e s s e l f u n c t i o n J s (x).
Of g r e a t e r i n t e r e s t f o r r a d i a t i o n a n d c o l l i s i o n t h e o r y i s t h e v e l o c i t y ,
whose and r j - c o m p o n e n t s a r e

v ,ts = - i u a j 's 4( s e )'


(3.11)
v, = ш a (e - 1)* J (se)

N o t e t h a t f o r c i r c u l a r o r b i t s (e = 0) t h e only n o n - z e r o c o e f f i c i e n t s a r e f o r
s = ± 1 , a n d it i s t h i s w h i c h r e s t r i c t s e m i s s i o n t o t h e f u n d a m e n t a l f r e q u e n c y .
F r o m L a n d a u a n d L i f s h i t s ( C l a s s i c a l T h e o r y of F i e l d s (1971) § 67) the
i n t e n s i t y o r p o w e r r a d i a t e d into the (s - 1 )th h a r m o n i c of f r e q u e n c y su i s

4 s 4 u 2 e 2 i-> i 2
: =
s " T T - К I (3.12)

v V +
s = SS 5 \ s "

therefore
= 4 s W a 2 ( J , 2 ( s e ) + (e-2 . 1)J (se)) (3.13)
s
3c

B y a v e r a g i n g o v e r the d i s t r i b u t i o n in e c c e n t r i c i t y , w h i c h in m o s t
c i r c u m s t a n c e s i s u n i f o r m i n e 2 , b e t w e e n 0 a n d 1, w e o b t a i n a c o r r e s p o n d e n c e
p r i n c i p l e f o r t h e o s c i l l a t o r s t r e n g t h f ( n ' , n ) , a f t e r M e z g e r (1969).

f(n =
8 J , ( s ) J , ' ( s ) n .2
'"> 3 g2 ^ T (n'<n) (3.14)

Here
s = n - n' (3.15)

F o r s = 2, n = 5 ( i . e . 5 3 t r a n s i t i o n ) t h e e r r o r i s 10%
s = l , n = 1 0 ( i : e . 10 9 t r a n s i t i o n ) t h e e r r o r i s 0 . 5 %
a n d f o r t h e r a d i o - r e c o m b i n a t i o n l i n e s it i s n e g l i g i b l e .
E n c o u r a g e d b y t h i s a g r e e m e n t w e c a n c o n t i n u e in t h e s p i r i t of C o p e n h a g e n
and G ö t t i n g e n of t h e 1 9 2 0 s a n d a p p l y t h e c o r r e s p o n d e n c e p r i n c i p l e to
collisions.

4. CLASSICAL COLLISIONS

In t h e c a s e of t h e t h e o r y of r a d i a t i o n , we w e r e a b l e t o a p p e a l to a
s t a n d a r d text f o r the c o r r e s p o n d i n g c l a s s i c a l t h e o r y . F o r collisions this is
not s o , a n d b e f o r e c o n s i d e r i n g t h e c o r r e s p o n d e n c e p r i n c i p l e w e m u s t
d e v e l o p t h e c l a s s i c a l t h e o r y of c o l l i s i o n s . F i r s t c o n s i d e r t h e t h e o r y of
c o l l i s i o n s of c h a r g e d p a r t i c l e s with h i g h l y e x c i t e d a t o m s .
Suppose a c l a s s i c a l e l e c t r o n collides with a c l a s s i c a l H - a t o m with a
n u c l e u s of i n f i n i t e m a s s . U i s t h e b i n d i n g e n e r g y of t h e a t o m w h i c h in t h i s
c l a s s i c a l m o d e l i s not q u a n t i z e d ( i . e . w e h a v e a c o n t i n u u m of b o u n d s t a t e s ) .
IAEA-SMR-12/44, 46 , 48 247

L e t E b e t h e i n i t i a l e n e r g y of t h e i n c i d e n t e l e c t r o n a n d s u p p o s e that

E > U (4.1)

F o r i o n i z a t i o n to t a k e p l a c e , t h e bound e l e c t r o n m u s t gain enough e n e r g y


to l e a v e t h e p r o t o n , but the incident e l e c t r o n m u s t not l o s e so m u c h e n e r g y
t h a t it b e c o m e s bound to the p r o t o n .
We c a n c l a s s i f y c l a s s i c a l c o l l i s i o n s of e l e c t r o n s with H a t o m s a c c o r d i n g
to the r a n g e of v a l u e s of the e n e r g y t r a n s f e r

ДЕ = E - E ' (4.2)

f r o m t h e incident e l e c t r o n to the i n i t i a l l y bound e l e c t r o n . Here E1 is the


f i n a l e n e r g y of t h e incident e l e c t r o n .
We h a v e t h e p o s s i b i l i t i e s :
Direct scattering;
ДЕ < U i n c l u d e s both e x c i t a t i o n (4.3a)
and d e - e x c i t a t i o n
U < ДЕ < E Ionization (4.3b)
E < ДЕ Exchange (4.3c)

T h e exchange p r o c e s s i s m o r e v i o l e n t t h a n the i o n i z a t i o n , but i s v e r y


r a r e when E U.
T h e c l a s s i c a l i o n i z a t i o n c r o s s - s e c t i o n i s given by

<j c = cr c (U < Д Е < E ) (4.4)

T h e q u a n t a l c r o s s - s e c t i o n f o r highly e x c i t e d s t a t e s is given to a good


a p p r o x i m a t i o n by t h e s a m e f o r m u l a

CTq~crc v( 4 . 5 )
i l '

(The e r r o r i s v e r y s m a l l . )
S y s t e m s of p a r t i c l e s i n t e r a c t i n g t h r o u g h Coulomb f o r c e s s a t i s f y s i m p l e
s c a l i n g l a w s . If old t r a j e c t o r i e s R ; (t) f o r 3 - p a r t i c l e s i = 1, 2, 3 s a t i s f y t h e
e q u a t i o n s of m o t i o n , t h e n new t r a j e c t o r i e s RJ(t') a l s o s a t i s f y t h e e q u a t i o n s
of m o t i o n , p r o v i d e d t h a t

R.(t)=6R!(ť) (4.6a)

t = e3/2ť (4.6b)

F o r e x a m p l e , in t h e K e p l e r m o t i o n of a p l a n e t , the p e r i o d v a r i e s a s t h e
3 / 2 p o w e r of t h e r a d i u s of o r b i t . H o w e v e r t h e s c a l i n g law a p p l i e s f o r any
n u m b e r of c h a r g e d p a r t i c l e s . T h i s m a y b e v e r i f i e d by s u b s t i t u t i o n in
N e w t o n ' s e q u a t i o n s of m o t i o n . F o r the s c a l i n g of a c o m p l e x d y n a m i c a l
p r o b l e m , a l l p o s i t i o n s and l e n g t h s m u s t b e s c a l e d a s in (4. 6a) and a l l t i m e s
a s in ( 4 . 6 b ) . V e l o c i t i e s v , e n e r g i e s E a n d c r o s s - s e c t i o n s a r e s c a l e d
a c c o r d i n g to t h e t r a n s f o r m a t i o n s

v = 6"*v' (4.7a)
248 PERCIVAL

E = e"1E' (4.7b)

a (4.7c)

C o n s e q u e n t l y , if our H a t o m h a s the b i n d i n g e n e r g y U, t h e quantity

CT( E/U)/<yg (4.8)

i s a u n i v e r s a l f u n c t i o n of t h e d i m e n s i o n l e s s quantity E / U , w h e r e the g e o -
m e t r i c c r o s s - s e c t i o n is

a S = 7га2 = — g (independent of t h e i n c i d e n t p a r t i c l e ) (4.9)

T h e s c a l i n g l a w s e n a b l e u s to o b t a i n c r o s s - s e c t i o n s f o r a t o m s of a l l
b i n d i n g e n e r g i e s f r o m t h o s e of a given binding e n e r g y , s a y U = \ in s o m e
units.
T h e i n i t i a l c o n d i t i o n s f o r a c l a s s i c a l c o l l i s i o n depend on t h e n a t u r e of
the q u a n t a l c o l l i s i o n that it is hoped to m o d e l . F o r a highly e x c i t e d l e v e l n,
t h e r e a r e m a n y d i f f e r e n t p o s s i b l e c o l l i s i o n s , depending on the d i s t r i b u t i o n
a m o n g the ( n í m ) s t a t e s o f t h a t l e v e l . We n e g l e c t s p i n .
In a s t r o p h y s i c a l s i t u a t i o n s and in l a b o r a t o r y p l a s m a s t h e individual
s t a t e s f o r a given n a r e i n i t i a l l y equally p o p u l a t e d to a v e r y good a p p r o x i -
m a t i o n . T h e d i s t r i b u t i o n with t h e s e p r o p e r t i e s with e n e r g y U n fixed and
( i m ) s t a t e s equally p o p u l a t e d i s known in s t a t i s t i c a l m e c h a n i c s a s a q u a n t a l
microcanonical distribution.
Highly e x c i t e d s t a t e s p r o d u c e d by c o l l i s i o n s e x c i t i n g f r o m the g r o u n d
s t a t e and a l s o by c h a r g e t r a n s f e r have a d i f f e r e n t d i s t r i b u t i o n which i s
u s u a l l y unknown in d e t a i l . F o r this r e a s o n we c o n s i d e r only t h e m i c r o -
canonical distribution.
A c l a s s i c a l m i c r o c a n o n i c a l d i s t r i b u t i o n c o n s i s t s of h y d r o g e n a t o m s with
f i x e d b i n d i n g e n e r g y U, and e l l i p t i c a l e l e c t r o n o r b i t s which a r e d i s t r i b u t e d
i s o t r o p i c a l l y with all o r i e n t a t i o n s , and with a d i s t r i b u t i o n in e c c e n t r i c i t y
which i s u n i f o r m in e 2 b e t w e e n 0 and 1. T h e c l a s s i c a l d i s t r i b u t i o n
c o r r e s p o n d i n g to the q u a n t a l m i c r o c a n o n i c a l d i s t r i b u t i o n at l e v e l n i s

Binding e n e r g y . U = Ry/n2 (4.10a)


2
e u n i f o r m l y d i s t r i b u t e d in (0, 1 ) (4.10b)
A r b i t r a r y orientation, isotropic
(spherically symmetric) distribution (4.10c)

C l a s s i c a l l y one can s p e c i f y position and m o m e n t u m s i m u l t a n e o u s l y ;


q u a n t a l l y , by t h e u n c e r t a i n t y p r i n c i p l e , one c a n n o t . T h u s in m a k i n g a
c l a s s i c a l m o d e l of a q u a n t a l a t o m one cannot at the s a m e t i m e obtain t h e
c o r r e c t d i s t r i b u t i o n in p o s i t i o n and m o m e n t u m of t h e o r b i t i n g e l e c t r o n .
F o r a collision the momentum distribution is much m o r e important
t h a n t h e d i s t r i b u t i o n in p o s i t i o n .
T h e m i c r o c a n o n i c a l q u a n t a l d i s t r i b u t i o n in m o m e n t u m w a s given by
F o c k (1935) a s

(4.11)
IAEA-SMR-12/44,46,48 249

where
pť n = m e vn = 4(2m e Un ' 4 ( 4 . 1 2 )'

By good f o r t u n e t h i s d i s t r i b u t i o n in m o m e n t u m is i d e n t i c a l to the c l a s -
s i c a l m i с r o c ano ni c a l d i s t r i b u t i o n in m o m e n t u m f o r b i n d i n g e n e r g y U n and
f o r a l l n. ( T h i s i s a p r o p e r t y which c o m e s f r o m a c o n s i d e r a t i o n of g r o u p
s y m m e t r i e s . ) T h i s r e m o v e s all doubt as to what i n i t i a l c o n d i t i o n s should
be chosen for the atom - a classical microcanonical distribution over
elliptical orbits.
F o r s i m p l i c i t y of c a l c u l a t i o n , s o m e a u t h o r s e x p l i c i t l y o r i m p l i c i t l y
c o n s i d e r an i n i t i a l i s o t r o p i c d i s t r i b u t i o n of c i r c u l a r o r b i t s (e = 0) f o r which
t h e m o m e n t u m p i s f i x e d in m a g n i t u d e at p n . P a r t i c u l a r l y f o r h i g h - e n e r g y
c o l l i s i o n s t h i s i s in p r a c t i c e a f a i r l y good a p p r o x i m a t i o n f o r t r a n s i t i o n s
between different levels.

5. CLASSICAL CROSS-SECTIONS

T h e r e a r e t h r e e m a i n m e t h o d s which h a v e b e e n u s e d to obtain c l a s s i c a l
c r o s s - s e c t i o n s f o r c o l l i s i o n s b e t w e e n c h a r g e d p a r t i c l e s of m a s s m j and
atoms.

Classical-impulse or binary-encounter approximation (5.1a)


Classical perturbation theory (5.1b)
O r b i t i n t e g r a t i o n o r Monte C a r l o m e t h o d (5.1c)

E a c h of t h e s e m e t h o d s is a p p r o p r i a t e in p a r t i c u l a r c i r c u m s t a n c e s
d e f i n e d by t h e n o r m a l i z e d i n c i d e n t e n e r g y E / U = m e E / m 1 U and t h e n o r m a l i z e d
energy t r a n s f e r Д Е / U . The appropriate ranges a r e

B i n a r y e n c o u n t e r Ë ' » U, ЁДЕ » U2 (5.2a)


Classical perturbation theory ДЕ « U (5.2b)
Monte C a r l o Ë ~ U (5.2c)

T h e a p p r o x i m a t i o n s a r e given in i n c r e a s i n g o r d e r of d i f f i c u l t y . F o r incident
e l e c t r o n s Ê = E a n d f o r incident i o n s , including p r o t o n s , E i s t h e e n e r g y of
a n e l e c t r o n with t h e s a m e v e l o c i t y a s the i n c i d e n t i o n .
T h e b i n a r y - e n c o u n t e r o r c l a s s i c a l - i m p u l s e a p p r o x i m a t i o n h a s a long and
t o r t u o u s h i s t o r y . T h e e x c e l l e n t but v e r y t e r s e l y w r i t t e n e a r l y p a p e r s of
T h o m a s ( 1 9 2 7 a , b ) , W i l l i a m s (1931) and o t h e r s in t h e 1930s w e r e l a r g e l y
f o r g o t t e n d u r i n g t h e b u r s t of e n t h u s i a s m following the p u b l i c a t i o n of
G r y z i n s k i (1959). D e t a i l s can be found in r e v i e w a r t i c l e s ( B u r g e s s and
P e r c i v a l 1968, V r i e n s 1967). T h i s a p p r o x i m a t i o n i s b a s e d on the a s s u m p t i o n
t h a t t h e p r o b a b i l i t y of a given e n e r g y t r a n s f e r Д Е i s the s a m e a s if t h e
i n c i d e n t p a r t i c l e w e r e p a s s i n g t h r o u g h a g a s of f r e e e l e c t r o n s with t h e s a m e
v e l o c i t y d i s t r i b u t i o n a s that of the e l e c t r o n s in the c l a s s i c a l m o d e l a t o m .
S i n c e t h e e n e r g y of a c l a s s i c a l bound s y s t e m i s c o n t i n u o u s , l i k e e v e r y
d y n a m i c a l v a r i a b l e of c l a s s i c a l m e c h a n i c s , t h e c l a s s i c a l c r o s s - s e c t i o n f o r
an e n e r g y t r a n s f e r Д Е i s a d i f f e r e n t i a l c r o s s - s e c t i o n
250 PERCIVAL

эЙз <5-3)
C l a s s i c a l l y , the t o t a l c r o s s - s e c t i o n f o r e n e r g y t r a n s f e r b e t w e e n two l i m i t s
AE mm . a n d A E max i s
AE
max
' ( A E m i l < A E < AEmax) = J ^ dAE (5.4)
AEm .in

The b i n a r y - e n c o u n t e r d i f f e r e n t i a l c r o s s - s e c t i o n is obtained f r o m t h e
R u t h e r f o r d f o r m u l a through the important, deceptively simple, T h o m a s
e x p r e s s i o n f o r the double d i f f e r e n t i a l c r o s s - s e c t i o n 9 2 a / ( 3 q 9 A E ) ,
w h e r e q i s t h e m a g n i t u d e of t h e m o m e n t u m t r a n s f e r . It i s given by

тг 32P _ 4тге2 1

X i s a f u n c t i o n of v 0 , V, q and ЛЕ which i s 1 when t h e s e q u a n t i t i e s a r e


c o n s i s t e n t with c o n s e r v a t i o n conditions and 0 o t h e r w i s e . In t h e T h o m a s
f o r m u l a it i s s u p p o s e d ~J 2E/m1 = V i s t h e velocity of the incident p a r t i c l e
and that t h e bound e l e c t r o n h a s an i s o t r o p i c v e l o c i t y d i s t r i b u t i o n with fixed
m a g n i t u d e v 0 . T h i s would be the c a s e f o r c i r c u l a r o r b i t s .
I n t e g r a t i n g t h i s e x p r e s s i o n o v e r m o m e n t u m t r a n s f e r we o b t a i n f o r t h e
b i n a r y - e n c o u n t e r (BE) i o n i z a t i o n c r o s s - s e c t i o n

i / £ I . 1 _L ^ ( B E ЬУ e l e c t r o n s ) (5.6)
g V 3 " g " 3 g 2 ; (g=E/U)

4 f 5 1 • N, (BE by p r o t o n s )
(5
E V3 4 ( 2 - 1) (Ê = m e E / m U) "7)

A d d i t i o n a l f a c t o r s a r e s o m e t i m e s i n t r o d u c e d to t a k e account of a c c e l e r a t i o n
of the incident p a r t i c l e by the n u c l e u s , n e g l e c t e d in t h e o r i g i n a l a p p r o x i m a -
tion, a n d / o r f o c u s s i n g of i n c i d e n t e l e c t r o n s .
F o r a given i n c i d e n t e n e r g y E , t h i s a p p r o x i m a t i o n i s only v a l i d f o r
s u f f i c i e n t l y l a r g e e n e r g y t r a n s f e r s , by condition ( 5 . 2 a ) .
When t h e c o l l i s i o n i s w e a k e r , the b i n a r y - e n c o u n t e r a p p r o x i m a t i o n
b r e a k s down, but it i s p o s s i b l e to u s e c l a s s i c a l p e r t u r b a t i o n t h e o r y in a
s i m i l a r f a s h i o n to L a g r a n g e ' s t r e a t m e n t of t h e p e r t u r b a t i o n of the p l a n e t s .
T h e w o r k done by t h e p a s s i n g p a r t i c l e , s u p p o s e d to b e u n p e r t u r b e d , on
t h e o r b i t i n g e l e c t r o n i s c a l c u l a t e d by t h e f o r m u l a
CO

ДЕ W = J F 1 2 • d? 2 (5. 8)

Using L a g r a n g e ' s e x p a n s i o n ( 3 . 7 - 3 . 1 0 ) we can obtain a s e r i e s f o r m f o r


AE in t e r m s of t h e F o u r i e r c o m p o n e n t s of t h e m o t i o n and t h e a n g l e s of
o r i e n t a t i o n of t h e e l l i p t i c o r b i t . By a v e r a g i n g o v e r t h e s e o r i e n t a t i o n s and
making some fairly satisfactory simplifying assumptions, the differential
c r o s s - s e c t i o n c a n be obtained in the " a d i a b a t i c " r e g i o n of d i r e c t c o l l i s i o n s
( e x c i t a t i o n and d e - e x c i t a t i o n ) w h e r e t h e b i n a r y - e n c o u n t e r t h e o r y b r e a k s down.
IAEA-SMR-12/44,46,48 251

By c a r e f u l c o n s i d e r a t i o n of d i s t r i b u t i o n s in e n e r g y t r a n s f e r , i m p a c t
p a r a m e t e r and m o m e n t u m t r a n s f e r , it i s p o s s i b l e to obtain a c o m b i n e d
t h e o r y which i s j u s t i f i e d by b i n a r y - e n c o u n t e r and c l a s s i c a l p e r t u r b a t i o n
t h e o r y in t h e i r r e s p e c t i v e r e g i o n s of v a l i d i t y ( P e r c i v a l , 1973b). T h e
r e s u l t a n t c r o s s - s e c t i o n s a r e o b t a i n e d n u m e r i c a l l y but m a y b e a p p r o x i m a t e d
by t h e s i m p l e a n a l y t i c f o r m :

Эст
C(q_) - C(q + ) (AE > 0) (5.9)
ЭДЕ

where
ДЕ
«Û = l § 1 + ± 1 (5.10a)
U

and

Cfx" 1 ) : In 1 + (5.10b)

Unlike both t h e b i n a r y - e n c o u n t e r and c o m b i n e d t h e o r y i s the c l a s s i c a l -


t r a j e c t o r y o r Monte C a r l o m e t h o d which m u s t b e u s e d when the a n a l y t i c
m e t h o d s b r e a k down, p a r t i c u l a r l y when t h e v e l o c i t y of t h e incident p a r t i c l e
i s c o m p a r a b l e to that of the bound e l e c t r o n ( P e r c i v a l , 1973c).
In t h i s m e t h o d the c l a s s i c a l p r o b l e m i s solved d i r e c t l y by r e p e a t e d
n u m e r i c a l i n t e g r a t i o n of the c l a s s i c a l e q u a t i o n s of m o t i o n f o r i n i t i a l s t a t e s
which a r e c h o s e n by a p p r o p r i a t e r a n d o m s a m p l i n g in the s p a c e of p o s i t i o n s
and v e l o c i t i e s of a l l t h r e e c o l l i d i n g p a r t i c l e s . T h i s f o r m s in e f f e c t a
c o m p u t e r m o d e l of t h e p h y s i c a l s c a t t e r i n g p r o c e s s .

о 50 100 150 200 250 300


INCIDENT PROTON ENERGY ( keV)

FIG. 2 . p - H i o n i z a t i o n c r o s s - s e c t i o n for i n i t i a l n = l . Full c u r v e : Bates a n d G r i f f i n g ( 1 9 5 3 ) using Born


approximation; open circles: Gilbody and Ireland (1963); full circles: Fite et a l . ( i 9 6 0 ) ; squares:
Monte Carlo results.
2 5 2 PERCIVAL

T h e c r o s s - s e c t i o n s , both total and d i f f e r e n t i a l , a r e obtained by counting


t h e n u m b e r of f i n a l s t a t e s with p a r a m e t e r s s u c h a s e n e r g y t r a n s f e r , in a
given r a n g e . T h e e r r o r s a r e both s y s t e m a t i c a n d s t a t i s t i c a l . The s y s t e m a t i c
e r r o r s c o m e f r o m the f i n i t e s t e p length of n u m e r i c a l i n t e g r a t i o n and c u t - o f f s
due to f i n i t e t i m e s at which i n t e g r a t i o n m u s t n e c e s s a r i l y s t a r t and f i n i s h and
to t h e finite m a x i m u m i m p a c t p a r a m e t e r . Unlike t h e e x p e r i m e n t a l s i t u a t i o n
" e r r o r p a r a m e t e r s " c a n be c h o s e n w h i c h r e d u c e t h e s y s t e m a t i c e r r o r s to
v a l u e s below t h e s t a t i s t i c a l e r r o r s due to t h e finite s a m p l e . T h e l a t t e r can
b e r e p r e s e n t e d by s t a n d a r d deviation a s in a l a b o r a t o r y e x p e r i m e n t , as f o r
the p - H ionization c u r v e of A b r i n e s a n d P e r c i v a l (1966b), shown in F i g . 2 .
T h e c o m p u t i n g t i m e is long, but not p r o h i b i t i v e , f o r s t a n d a r d e r r o r s
~5% f o r t o t a l c r o s s - s e c t i o n s and ~ 15% f o r s i n g l e d i f f e r e n t i a l c r o s s - s e c t i o n s .
Many of the c l a s s i c a l r e s u l t s w e r e o b t a i n e d f o r a t o m s of low q u a n t u m
n u m b e r w h e r e t h e v a l i d i t y i s in g r e a t e r doubt t h a n f o r highly e x c i t e d a t o m s .
N e v e r t h e l e s s , p a r t i c u l a r l y f o r i o n i z a t i o n and f o r c r o s s - s e c t i o n s n e a r t h e i r
m a x i m u m v a l u e , t h e c l a s s i c a l t h e o r y i s not too b a d , even f o r H with n = 1.

6. D I S C R E T E STATES AND CORRESPONDENCE P R I N C I P L E S

We now c o n s i d e r t h e a p p l i c a t i o n of c l a s s i c a l t h e o r i e s to q u a n t a l s y s t e m s ,
the f i e l d of c o r r e s p o n d e n c e p r i n c i p l e s . F o r bound s t a t e s the c l a s s i c a l
e n e r g y " s p e c t r u m " i s continuous w h e r e a s the q u a n t a l s p e c t r u m i s d i s c r e t e .
T h e c l a s s i c a l d i f f e r e n t i a l c r o s s s e c t i o n Эст/ЭДЕ with r e s p e c t to e n e r g y
t r a n s f e r m u s t b e r e l a t e d to t h e t o t a l q u a n t a l c r o s s - s e c t i o n ст(п - n') f r o m
l e v e l n to l e v e l n' of t h e q u a n t i z e d bound s y s t e m .
If Эст/ЭДЕ v a r i e s by only a s m a l l f r a c t i o n o v e r v a l u e s of ДЕ c o r r e s p o n d i n g
to s e v e r a l n e i g h b o u r i n g f i n a l excited s t a t e s n ' , t h e n t h e r e i s l i t t l e difficulty
in o b t a i n i n g f r o m it u n a m b i g u o u s a p p r o x i m a t e e x c i t a t i o n c r o s s - s e c t i o n s ,
b y a s s u m i n g a s m o o t h d i s t r i b u t i o n a m o n g the f i n a l s t a t e s n 1 , a s shown in
F i g , 3 and a s follows

da i da i ЭДЕ
o(n n' ) : 1 (6.1)
9n' 'эДЕ 6n'

ДЕ

3tr
ЛЕ = 0
ЭДЕ

FIG. 3. E x c i t a t i o n c r o s s - s e c t i o n s a s a f u n c t i o n of e n e r g y d i f f e r e n c e .
IAEA-SMR-12/44,46,48 253

H e r e n i s s u p p o s e d to be fixed, ДЕ i s t h e e n e r g y t r a n s f e r

Д Е = Ry (n" 2 - n ' - 2 ) (6.2)

r e q u i r e d to excite the a t o m f r o m l e v e l n to l e v e l n ' , and

(6.3)

i s t h e m e a n e n e r g y r a n g e b e t w e e n s t a t e s l a b e l l e d by n 1 , o r the i n v e r s e m e a n
d e n s i t y of l e v e l s in t h e n e i g h b o u r h o o d of n ' .
T h e t h e o r e t i c a l condition f o r the v a l i d i t y of t h i s d e n s i t y - o f - s t a t e s
c o r r e s p o n d e n c e p r i n c i p l e i n v o l v e s c l a s s i c a l a c t i o n f u n c t i o n s . In p r a c t i c e
it i s v a l i d when

all n , n \ An » 1 (6.4)

and i s s o m e t i m e s v a l i d even when Д п i s c o m p a r a b l e with unity.


T h e c l a s s i c a l t h e o r y with the d e n s i t y - o f - s t a t e s c o r r e s p o n d e n c e p r i n c i p l e
i s s o m e t i m e s i n a d e q u a t e f o r s m a l l Дп. B e c a u s e of t h e s t r o n g s i n g u l a r i t y in
I Эст/ЭДЕ I at ДЕ = 0, t h e a s s i g n m e n t of the e n e r g y r a n g e i s a m b i g u o u s ; and
e v e n t h e f o r m of t h e c r o s s - s e c t i o n c a n be w r o n g .
F o r s u f f i c i e n t l y high i n c i d e n t - p a r t i c l e e n e r g i e s , t h e B e t h e - B o r n
a p p r o x i m a t i o n i s v a l i d and p r o v i d e s a quantal c r o s s - s e c t i o n which h a s the
form
AlnE + В
cr q (n - n ' ) ЯК (E l a r g e ) (6.5)
E
F o r l a r g e n and Дп t h e l o g a r i t h m i c t e r m i s i n s i g n i f i c a n t , but f o r s m a l l Дп
it m a y be dominant f o r v a l u e s of E of p h y s i c a l i n t e r e s t . H o w e v e r the
c l a s s i c a l r e s u l t s ( 5 . 6 , 5 . 7 ) h a v e no l o g a r i t h m i c t e r m .
T h e a d d i t i o n a l l o g a r i t h m i c t e r m c o m e s f r o m weak c o l l i s i o n s with l a r g e
i m p a c t p a r a m e t e r s , w h e r e the c l a s s i c a l e n e r g y t r a n s f e r r e d to t h e bound
e l e c t r o n i s l e s s than the e n e r g y s p l i t t i n g b e t w e e n t h e s t a t e s . T h e n e i g h -
b o u r i n g e n e r g y s t a t e s a r e t h u s c l a s s i c a l l y i n a c c e s s i b l e . Two c l u e s enable
u s to o v e r c o m e t h i s p r o b l e m : W i l l i a m s (1931) pointed out that c l a s s i c a l
t h e o r y can give a c o r r e c t v a l u e f o r t h e e n e r g y l o s s of c h a r g e d p a r t i c l e s ,
e v e n f o r t h e s e weak c o l l i s i o n s , s o t h a t the m e a n c l a s s i c a l e n e r g y t r a n s f e r
b e h a v e s a s if it w e r e s h a r e d out a m o n g the q u a n t u m - m e c h a n i c a l s t a t e s .
B o h r ' s c o r r e s p o n d e n c e p r i n c i p l e f o r r a d i a t i o n d e a l s with a s i m i l a r
s i t u a t i o n , f o r t h e m e a n e n e r g y l o s s of a c l a s s i c a l r a d i a t i n g e l e c t r o n i s
s h a r e d out a m o n g the q u a n t u m - m e c h a n i c a l s t a t e s . In t h i s c a s e the e n e r g y
t r a n s f e r to e a c h q u a n t a l s t a t e i s d e t e r m i n e d by the F o u r i e r c o m p o n e n t s
of t h e i n t e r a c t i o n with t h e r a d i a t i o n f i e l d . T h u s we should e x p e c t t h e
(n -» n 1 ) - t r a n s i t i o n p r o b a b i l i t y P(b) a s a function of the i m p a c t p a r a m e t e r b to
b e r e l a t e d to t h e F o u r i e r c o m p o n e n t s (3.7) of o r d e r s and - s , w h e r e s = n ' - n.
T h i s i s c o r r e c t ( P e r c i v a l and R i c h a r d s , 1 9 7 0 a , b ) p r o v i d e d that t h e i n t e r a c t i o n
i s s u f f i c i e n t l y weak f o r t h e s u m o v e r a l l p r o b a b i l i t i e s f r o m an i n i t i a l s t a t e n
i s s m a l l c o m p a r e d to 1 and p r o v i d e d that j s J <iC n. T h e s e c o n d i t i o n s m e a n
that f i r s t - o r d e r q u a n t a l p e r t u r b a t i o n t h e o r y m u s t b e v a l i d f o r the q u a n t a l
i n t e r a c t i o n and a l s o t h a t c l a s s i c a l p e r t u r b a t i o n t h e o r y m u s t be v a l i d f o r the
classical interaction. Unfortunately this is very r e s t r i c t i v e .
254 PERCIVAL

H e i s e n b e r g (1949) o b t a i n e d a f o r m of t h e c o r r e s p o n d e n c e p r i n c i p l e
which i s m o r e p o w e r f u l and convenient t h a n t h a t of B o h r , and r e l a t e s
c l a s s i c a l F o u r i e r c o e f f i c i e n t s to quantal m a t r i x e l e m e n t s . Suppose

(6.6)

i s t h e p o s i t i o n of a p a r t i c l e moving p e r i o d i c a l l y in one d i m e n s i o n . T h e n
any f u n c t i o n F c (x) m a y a l s o b e e x p r e s s e d a s a F o u r i e r s e r i e s in t i m e :

(6.7)

T h e n H e i s e n b e r g 1 s f o r m of t h e c o r r e s p o n d e n c e p r i n c i p l e s t a t e s that the
q u a n t a l m a t r i x e l e m e n t s b e t w e e n s t a t e s n and n 1 of the d y n a m i c a l v a r i a b l e F
t e n d s to c o i n c i d e with t h e c l a s s i c a l F o u r i e r c o m p o n e n t s

<n' | F | n > «=F°, (s = n - n ' , s « n, n ' ) (6.8)

w h e r e the c l a s s i c a l o r b i t i s t a k e n n e a r the m e a n e n e r g y of t h e i n i t i a l and


f i n a l s t a t e s . The t h e o r y c a n b e g e n e r a l i z e d to s e p a r a b l e s y s t e m s of many
d i m e n s i o n s by u s i n g the t h e o r y of a c t i o n - a n g l e v a r i a b l e s .
T h u s , if a c o l l i s i o n p r o b l e m can b e f o r m u l a t e d in t e r m s of m a t r i x
e l e m e n t s of o p e r a t o r s which a r e known f u n c t i o n s of p o s i t i o n , H e i s e n b e r g ' s
f o r m of t h e c o r r e s p o n d e n c e p r i n c i p l e can b e u s e d .
T h i s t h e o r y , when a p p l i e d to a c l a s s i c a l - p a t h f i r s t - o r d e r q u a n t a l
p e r t u r b a t i o n t h e o r y of c o l l i s i o n s , gives the s a m e r e s u l t a s the a p p l i c a t i o n
of B o h r ' s c o r r e s p o n d e n c e p r i n c i p l e . It h a s a l s o b e e n a p p l i e d to t h e p l a n e -
wave B o r n a p p r o x i m a t i o n by R i c h a r d s (1973) and t o t h e s u d d e n a p p r o x i m a t i o n
( A l d e r , W i n t h e r , 1960; K r a m e r , B e r n s t e i n , 1964) by P e r c i v a l a n d
R i c h a r d s (1970b). T h e l a s t a u t h o r s a l s o d e r i v e d a m o r e g e n e r a l s t r o n g -
c o u p l i n g c o r r e s p o n d e n c e p r i n c i p l e f o r t h e S - m a t r i x v a l i d wherfever f i r s t -
o r d e r c l a s s i c a l perturbation theory is valid for the c l a s s i c a l model. This
l a s t r e s u l t h a s b e e n shown t o a g r e e with t h e d e n s i t y - o f - s t a t e s c o r r e s p o n d e n c e
p r i n c i p l e in the r a n g e 1 « | n - n' | < n, n ' .
T h e t r a n s i t i o n a m p l i t u d e s f o r a o n e - d i m e n s i o n a l s y s t e m f o r weak
coupling, sudden and s t r o n g coupling t h e o r i e s a r e given by

2тг/ш

(6.9)
n'
27Г/ÜJ

( s I « n , n ' ; íú X ( t i m e of c o l l i s i o n ) « 1
) (6.10)
IAEA-SMR-12/44,46,48 255

2тг/ш
S. (n',n)=^~ / dT exp isuT - - / dtV (x(t + t ) , t)
strong v ' 2тг J
о

s с n, n (6.11)

T h e f u n c t i o n V c (x(t + T ) , t ) is the v a l u e of the c l a s s i c a l i n t e r a c t i o n


p o t e n t i a l at t i m e t , w h e r e it i s s u p p o s e d that at t i m e t = 0 t h e bound p a r t i c l e
h a s r e a c h e d the point on i t s o r b i t which i s a t t a i n e d a f t e r a t i m e т f r o m a
given f i x e d i n i t i a l p o i n t . T h e m a n y - d i m e n s i o n a l t h e o r y i s m o r e c o m p l i c a t e d ,
but d i f f e r s in no e s s e n t i a l s .
T h e s e m e t h o d s h a v e b e e n u s e d in a s e r i e s of p a p e r s (the l a s t b e i n g
P e r c i v a l and R i c h a r d s , 1971) to obtain an a n a l y t i c f o r m u l a f o r c o l l i s i o n
c r o s s - s e c t i o n s b e t w e e n e l e c t r o n s and highly e x c i t e d h y d r o g e n a t o m s f o r
i n c i d e n t e l e c t r o n e n e r g i e s E in t h e r a n g e

R
y < E < 1 Ry (6.12)

Above E = 1 Ry t h e B o r n a p p r o x i m a t i o n i s v a l i d , and f o r E in the r a n g e

(6.13)
n2 n

t h e c o r r e s p o n d e n c e - p r i n c i p l e m e t h o d s h a v e b e e n u s e d m o r e r e c e n t l y by
Richards.
B e l o w t h e l o w e r l i m i t of 4 R y / n 2 of E it i s n e c e s s a r y to u s e c l a s s i c a l
Monte C a r l o m e t h o d s .
A n a l y t i c f o r m u l a s a r e a l s o p r o v i d e d f o r incident p o s i t i v e ions and a l s o
f o r t a r g e t s which a r e h y d r o g e n - l i k e i o n s .

7. DISCUSSION O F L I T E R A T U R E

T h e l i t e r a t u r e on highly e x c i t e d s t a t e s i s e x t e n s i v e and h a s not to m y


knowledge b e e n s u m m a r i z e d in a single r e v i e w . H e r e I n a m e a few p a p e r s
c l o s e l y r e l a t e d to t h e t h e m e of c l a s s i c a l and c o r r e s p o n d e n c e m e t h o d s
p r e s e n t e d in t h e s e l e c t u r e s . P u r e l y c l a s s i c a l m e t h o d s and in p a r t i c u l a r
b i n a r y - e n c o u n t e r m e t h o d s h a v e b e e n r e v i e w e d by B u r g e s s and P e r c i v a l
(1968) by V r i e n s (1969) and by B a t e s a n d K i n g s t o n (1970). T h e a u t h o r s w e r e
m a i n l y c o n c e r n e d with t h e a p p l i c a t i o n of t h e t h e o r y to low s t a t e s of a t o m s .
Monte C a r l o m e t h o d s h a v e b e e n a p p l i e d to e l e c t r o n - h y d r o g e n c o l l i s i o n s
by A b r i n e s , P e r c i v a l and V a l e n t i n e (1966), B r a t t s e v and O c h k u r (1967),
M a n s b a c h a n d Keck (1969), P e r c i v a l (1973a) and G r u j i č (1973).
T h e c l a s s i c a l - m e c h a n i c s b a c k g r o u n d to t h e c l a s s i c a l p e r t u r b a t i o n
t h e o r y and t h e c o r r e s p o n d e n c e - p r i n c i p l e m e t h o d s i s b e t t e r p r e s e n t e d by
B o r n (196 0) than in m o s t m o d e r n t e x t s .
A s e m i - c l a s s i c a l t h e o r y of B e i g m a n et a l . (1970), and a s i m p l i f i c a t i o n
of an a p p r o x i m a t e q u a n t a l t h e o r y of P r e s n y a k o v and Urnov (1970) have
both b e e n shown by R i c h a r d s (1972) t o b e equivalent to t h e s t r o n g coupling
correspondence principle f o r one-dimensional motion.
256 PERCIVAL

S a r a p h (1969) h a s a p p l i e d S e a t o n ' s (1962) c l a s s i c a l - p a t h dipole t h e o r y ,


in w h i c h the i n t e r a c t i o n i s t r e a t e d by q u a n t a l p e r t u r b a t i o n t h e o r y o r the
c o n s e r v a t i o n l i m i t , to e l e c t r o n - h y d r o g e n n ^ n + 1 t r a n s i t i o n s . T h e
c o r r e s p o n d e n c e - p r i n c i p l e r e s u l t s a r e in r e a s o n a b l e a g r e e m e n t with t h i s
t h e o r y except f o r the l o w e r incident e n e r g i e s E ,
B o r n o r B e t h e - B o r n c a l c u l a t i o n s h a v e b e e n p e r f o r m e d by McCoyd and
M i l f o r d (1963) by O m i d v a r (1965) and by O m i d v a r and K h a t e e b (1973).
F u r t h e r t h e o r y h a s b e e n p r e s e n t e d by M i n a e v a , S o b e l ' m a n and Sorochenko
(1967). A g e n e r a l r e v i e w of c o l l i s i o n s of c h a r g e of p a r t i c l e s with highly
e x c i t e d s t a t e s i s to a p p e a r ( P e r c i v a l a n d R i c h a r d s , 1975).
A 1971 S u m m e r School P r o c e e d i n g s ( C a r s o n and R o b e r t s , 1972) c o n t a i n s
a r t i c l e s by C h u r c h w e l l , P e r c i v a l and Seaton on the a s t r o p h y s i c a l a s p e c t s
of highly e x c i t e d s t a t e s , and B e r k n e r , King and R i v i e r e (1967) w r i t e on t h e i r
r e l e v a n c e to c o n t r o l l e d t h e r m o n u c l e a r r e a c t i o n s .
T h e r e i s an A p p e n d i x on p h a s e - s p a c e c o n s i d e r a t i o n s a t t a c h e d to t h i s
paper.

ACKNOWLEDGEMENTS

I a m g r a t e f u l to N. P o m p h r e y f o r a s s i s t a n c e in w r i t i n g t h e s e l e c t u r e
n o t e s and to D. R i c h a r d s f o r sending m e h i s p a p e r s b e f o r e p u b l i c a t i o n .

APPENDIX

PHASE SPACE CONSIDERATIONS

T h e p r o p e r t i e s of a q u a n t a l e n e r g y s p e c t r u m in t h e s e m i - c l a s s i c a l l i m i t
of high q u a n t u m n u m b e r s m a y be obtained by t h e m e t h o d s of t h e old q u a n t u m
theory.
A c o n s e r v a t i v e c l a s s i c a l d y n a m i c a l s y s t e m of N d e g r e e s of f r e e d o m i s
i n t e g r a b l e if t h e r e a r e N independent c o n s t a n t s of m o t i o n . A s y s t e m with
e q u a t i o n s of m o t i o n w h i c h a r e c o m p l e t e l y s e p a r a b l e i s a s p e c i a l c a s e .
A c c o r d i n g to a w e l l - k n o w n t h e o r e m of K o l m o g o r o v , A r n o l d and M o z e r ,
bounded s y s t e m s which have an a n a l y t i c H a m i l t o n i a n , and which a r e
s u f f i c i e n t l y c l o s e to b e i n g s e p a r a b l e , have a s i g n i f i c a n t f r a c t i o n of t h e i r
p h a s e s p a c e f u l l of t r a j e c t o r i e s which b e h a v e v e r y m u c h like t h o s e of
s e p a r a b l e s y s t e m s . We s h a l l c a l l the r e g i o n s containing t h e s e t r a j e c t o r i e s
the r e g u l a r r e g i o n s of p h a s e s p a c e .
In r e g u l a r r e g i o n s the t r a j e c t o r i e s lie on N - d i m e n s i o n a l i n v a r i a n t
t o r o i d s . On e a c h t o r o i d t h e r e is defined a v e c t o r a c t i o n c o n s t a n t

I = (I. I * . . . . I N ) (1)

where

I = £ p.dq (2)
bk

and w h e r e q and p a r e a c a n o n i c a l l y c o n j u g a t e v e c t o r c o - o r d i n a t e and


momentum
IAEA-SMR-12/44,46,48 257

q = ( q r q 2 , • . . , q N ); p = (pr p 2 , • • -, p N ) (3)

f o r t h e s y s t e m . T h e b k a r e N independent c l o s e d c u r v e s on the t o r o i d .
E a c h t o r o i d m a y be p a r a m e t r i z e d by the v e c t o r angle v a r i a b l e в, so t h a t

q =QI(0), P = PÏ (0) (4)

E a c h component 0 k of в i s p e r i o d i c of p e r i o d 2u and i s l i n e a r l y
dependent on t h e t i m e t with an ( a n g u l a r ) f r e q u e n c y c o e f f i c i e n t u k

ek = u k t + el (5)

uk = u k ( I ) (6)

T h e c l a s s i c a l m o t i o n r e s o n a t e s in N f u n d a m e n t a l m o d e s of f r e q u e n c i e s u k ,
and a l s o in i n t e g e r c o m b i n a t i o n s of t h e s e f u n d a m e n t a l f r e q u e n c i e s . T h e
m o t i o n i s a l m o s t p e r i o d i c , with an i n f i n i t e n u m b e r of d i s c r e t e F o u r i e r
c o m p o n e n t s . With a r e a s o n a b l e choice of 6 k the a m p l i t u d e s of the o v e r t o n e s
and i n t e r c o m b i n a t i o n m o d e s d e c r e a s e r a p i d l y with t h e i r o r d e r . T h e
s y s t e m r e s o n a t e s s t r o n g l y at r e l a t i v e l y few d i s c r e t e f r e q u e n c i e s .
N u m e r i c a l e x p e r i m e n t s on n o n - i n t e g r a b l e s y s t e m s c l e a r l y show r e g u l a r
r e g i o n s of p h a s e s p a c e . In the 2 - d i m e n s i o n a l cubic p o t e n t i a l w e l l of Hénon
and H e i l e s t h e s y s t e m i s c l o s e to b e i n g i n t e g r a b l e n e a r t h e b o t t o m of t h e
well at E = 0, and t h e r e is an e n e r g y of e s c a p e at E = 1 / 6 . R e g u l a r r e g i o n s
d o m i n a t e t h e p h a s e s p a c e up to E = 1 / 1 2 , w h e r e " i r r e g u l a r " r e g i o n s b e c o m e
s i g n i f i c a n t . T h e i r r e g u l a r r e g i o n s d o m i n a t e n e a r the e s c a p e e n e r g y .
T h e t r a j e c t o r i e s in an i r r e g u l a r r e g i o n a p p e a r to b e h a v e e r g o d i c a l l y
in that r e g i o n . A c c o r d i n g to Contopoulos the i r r e g u l a r r e g i o n s a r e
a s s o c i a t e d with u n s t a b l e o r b i t s . A c c o r d i n g to Sinai, who p r o v e d e r g o d i c i t y
f o r h a r d s p h e r e s , e r g o d i c i t y follows f r o m i n s t a b i l i t y , and so we s h a l l
a s s u m e , in the a b s e n c e of a p r o o f , t h a t t h e t r a j e c t o r i e s in the i r r e g u l a r
r e g i o n s a r e e r g o d i c . A l m o s t e v e r y t r a j e c t o r y q(t), p(t) in an i r r e g u l a r
r e g i o n then h a s a continuous f r e q u e n c y s p e c t r u m and r e a c h e s a r b i t r a r i l y
c l o s e to e v e r y p h a s e point of the s a m e e n e r g y in that i r r e g u l a r r e g i o n . An
i r r e g u l a r r e g i o n h a s t h e d i m e n s i o n 2N.
T h e r e g u l a r and i r r e g u l a r r e g i o n s t h e m s e l v e s have a v e r y c o m p l i c a t e d
g e o m e t r i c a l fine s t r u c t u r e , which we i g n o r e , a s no s t r u c t u r e in a v o l u m e
of p h a s e s p a c e s m a l l e r than (27rh) i s of g r e a t i m p o r t a n c e f o r the q u a n t i z e d
system.
On a p p l y i n g weak t i m e - d e p e n d e n t p e r t u r b a t i o n s to a s y s t e m with a p h a s e
point in a r e g u l a r r e g i o n , the s y s t e m r e s p o n d s at i t s r e s o n a n t m o d a l
f r e q u e n c i e s , with d e c r e a s i n g e f f e c t as t h e o r d e r of the r e s o n a n c e i n c r e a s e s .
A f t e r a weak s h o r t - l i v e d p e r t u r b a t i o n h a s c e a s e d , the new t r a j e c t o r y
a l m o s t a l w a y s s t a y s in the n e i g h b o u r h o o d of the old o n e .
If the s y s t e m w e r e on an i r r e g u l a r t r a j e c t o r y , it would r e s p o n d o v e r a
continuous r a n g e of f r e q u e n c i e s and r a p i d l y d i v e r g e f r o m i t s o r i g i n a l
trajectory.
F r o m the c o r r e s p o n d e n c e p r i n c i p l e it f o l l o w s that a high q u a n t u m l e v e l
of the d i s c r e t e e n e r g y s p e c t r u m of a b o u n d q u a n t a l s y s t e m b e l o n g s to
e i t h e r R, a r e g u l a r e n e r g y s p e c t r u m ,
o r I, a n i r r e g u l a r e n e r g y s p e c t r u m .
258 PÉROVAL

T h e r e g u l a r e n e r g y s p e c t r u m and i t s a s s o c i a t e d s t a t e s h a v e t h e
following p r o p e r t i e s :
( R I ) A s t a t e m a y be l a b e l l e d by the v e c t o r q u a n t u m n u m b e r
n = (n a , n 2 , . . . , n N ) .
(R2) A q u a n t a l s t a t e with quantum n u m b e r n c o r r e s p o n d s to t h o s e p h a s e
s p a c e t r a j e c t o r i e s of t h e c o r r e s p o n d i n g c l a s s i c a l s y s t e m which lie in an
N - d i m e n s i o n a l i n v a r i a n t t o r o i d with a c t i o n c o n s t a n t s I k given by q u a n t u m
c o n d i t i o n s of t h e B o h r - S o m m e r f e l d - W i l s o n t y p e :

I k = (n k + c o n s t a n t ) h

A p a r t f r o m the p h a s e s p a c e f o r m u l a t i o n and the p o s s i b i l i t y of a n o n - z e r o


c o n s t a n t ( K e l l e r ) t h i s r e s u l t i s due to E i n s t e i n .
(R3) T h e q u a n t a l s t a t e m u s t r e s o n a t e at f r e q u e n c i e s c l o s e to t h o s e of t h e
c o r r e s p o n d i n g c l a s s i c a l m o t i o n . Given two q u a n t a l s t a t e s with one n k
d i f f e r i n g by unity and the o t h e r s the s a m e , t h e P l a n c k r e l a t i o n f o r t h e i r
energy difference is

ДЕк = îiuk (7)

w h e r e u k is a f u n d a m e n t a l f r e q u e n c y on t h e c o r r e s p o n d i n g t o r o i d .
(R4) A " n e i g h b o u r i n g s t a t e " t o a state n° with e n e r g y E ° i s a s t a t e with
v e c t o r q u a n t u m n u m b e r n c l o s e to n . N e i g h b o u r i n g s t a t e s a r e c l o s e in
e n e r g y t o E°, with e n e r g y d i f f e r e n c e no m o r e than a s m a l l m u l t i p l e of t h e
maximum | д Е к | .
(R5) We now u s e t h e c o r r e s p o n d e n c e p r i n c i p l e f o r weak p e r t u r b a t i o n s , whose
m o s t w e l l - k n o w n f o r m i s t h e c o r r e s p o n d e n c e p r i n c i p l e f o r i n t e n s i t y of
r a d i a t i o n . Under weak e x t e r n a l p e r t u r b a t i o n s t h e s t a t e n° i s m u c h m o r e
s t r o n g l y coupled to n e i g h b o u r i n g s t a t e s t h a n to o t h e r s t a t e s , with the
coupling tending to d e c r e a s e r a p i d l y with | n - n°| .
Not a l l s t a t e s c l o s e in e n e r g y to a given s t a t e a r e n e i g h b o u r i n g s t a t e s ,
not e v e n all t h o s e belonging to t h e s a m e r e g u l a r s p e c t r u m . H o w e v e r ,
e x p e r i m e n t s which a r e a b l e to select a few h i g h - n s t a t e s of a r e g u l a r
s p e c t r u m have a high p r o b a b i l i t y of s e l e c t i n g n e i g h b o u r i n g s t a t e s , so it
would be p o s s i b l e t o o b s e r v e t h e r e g u l a r i t y . If t r a n s i t i o n s with e n e r g y
d i f f e r e n c e s Д Е 1 a n d Д Е 2 a r e o b s e r v e d , a p p r o x i m a t e m u l t i p l e s and i n t e g e r
c o m b i n a t i o n s of t h e m would a l s o be o b s e r v a b l e . Bound i n t e g r a b l e s y s t e m s
have a regular s p e c t r u m .
T h e c o r r e s p o n d e n c e p r i n c i p l e p r e d i c t s p r o p e r t i e s of an i r r e g u l a r
s p e c t r u m in s t r i k i n g c o n t r a s t to t h o s e of a r e g u l a r s p e c t r u m :
(11) T h e r e i s no u n a m b i g u o u s a s s i g n m e n t of a v e c t o r q u a n t u m n u m b e r to a
s t a t e фQ.
(12) T h e d i s c r e t e bound s t a t e quantal s p e c t r u m m u s t tend to a continuous
c l a s s i c a l s p e c t r u m in t h e c l a s s i c a l l i m i t . T h e e n e r g y d i f f e r e n c e s

Е(ф) - E((//0) = (8)

f o r fixed s t a t i o n a r y s t a t e ф0 a n d v a r y i n g ф f o r m a d i s c r e t e d i s t r i b u t i o n which
t e n d s to t h e continuous d i s t r i b u t i o n i n t i ú .
(13) T h e e n e r g y d i f f e r e n c e s c a n have l i t t l e s t r u c t u r e — t h e d i s t r i b u t i o n of
l e v e l s at t h e i r r e g u l a r s p e c t r u m would a p p e a r to b e a r a n d o m d i s t r i b u t i o n
c o n s i s t e n t with (12).
IAEA-SMR-12/44,46,48 2 5 9

(14) B y a p p l y i n g t h e c o r r e s p o n d e n c e p r i n c i p l e f o r weak p e r t u r b a t i o n s , t h e r e
a r e no n e i g h b o u r i n g s t a t e s in the s e n s e of (R4) and (R5). E x c e p t f o r
s e l e c t i o n r u l e s and a c c i d e n t s , a s t a t e of an i r r e g u l a r s p e c t r u m i s coupled by
a weak p e r t u r b a t i o n with i n t e n s i t i e s of s i m i l a r m a g n i t u d e to all t h o s e
s t a t e s of a s i m i l a r e n e r g y which c o r r e s p o n d to the s a m e i r r e g u l a r r e g i o n of
c l a s s i c a l p h a s e s p a c e . The n u m b e r of s u c h s t a t e s i s v e r y l a r g e , of o r d e r

where nj is a typical quantum number,


(15) T h e e n e r g i e s of t h e i r r e g u l a r s p e c t r u m a r e m o r e s e n s i t i v e to a slowly
changing o r f i x e d p e r t u r b a t i o n t h a n t h o s e of the r e g u l a r s p e c t r u m .
In t h e B o h r - O p p e n h e i m e r a p p r o x i m a t i o n , t h e v i b r a t i o n a l e n e r g y
s p e c t r u m of a p o l y a t o m i c m o l e c u l e i s o b s e r v e d to b e r e g u l a r n e a r e q u i l i -
b r i u m , except f o r F e r m i r e s o n a n c e s , which a r e a r e s i d u a l f o r m of i r r e g u l a r
s p e c t r u m . N e a r the d i s s o c i a t i o n l i m i t the s p e c t r u m should be m a i n l y
i r r e g u l a r , with a l a r g e n u m b e r of w e a k e m i s s i o n l i n e s in p l a c e of a s m a l l
n u m b e r of s t r o n g o n e s . A r e g u l a r p r o g r e s s i o n should b e o b s e r v e d to
t e r m i n a t e a b r u p t l y at a m a x i m u m e n e r g y below the d i s s o c i a t i o n l i m i t . An
i r r e g u l a r s p e c t r u m could e a s i l y b e c o n f u s e d with a c o n t i n u u m u n d e r poor
c o n d i t i o n s of o b s e r v a t i o n .
P r e c i s e c a l c u l a t i o n s on a n i r r e g u l a r s p e c t r u m would b e difficult to
c a r r y out, e v e n with a c o m p l e t e knowledge of the i n t e r a c t i o n . If s t r o n g
i n t e r a c t i o n s a r e b a s i c a l l y n o n - l i n e a r t h e s a m e would apply to t h e h i g h e r
r e s o n a n c e s of p a r t i c l e p h y s i c s .
I should like to thank t h e U . K . S c i e n c e R e s e a r c h C o u n c i l f o r a g r a n t ,
the I n t e r n a t i o n a l C e n t r e f o r T h e o r e t i c a l P h y s i c s f o r t h e i r h o s p i t a l i t y and
Neil P o m p h r e y for a helpful discussion.

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l A E A - S M R - 1 2 / 4 4 , 4 6 , 48

ASTROPHYSICAL APPLICATIONS
OF ATOMIC PHYSICS

M.J. SEATON
Department of Physics and Astronomy,
University College, London,
United Kingdom

Abstract

ASTROPHYSICAL APPLICATION OF A T O M I C PHYSICS.


In t h r e e s e c t i o n s t h e a u t h o r discusses t h e i n f o r m a t i o n w h i c h c a n b e d e d u c e d f r o m t h e r a d i a t i o n e m i t t e d by:
1. Stellar atmospheres; 2. T h e solar c o r o n a ; 3. Gaseous n e b u l a e .

INTRODUCTION

The s t e l l a r a t m o s p h e r e s , the s o l a r c o r o n a , and the g a s e o u s nebulae,


a r e c o n s i d e r e d in t h r e e s e c t i o n s .
In o r d e r t o a p p r e c i a t e t h e p r o b l e m s in a t o m i c p h y s i c s w h i c h a r e of
i m p o r t a n c e f o r a s t r o p h y s i c s , it i s n e c e s s a r y to h a v e s o m e k n o w l e d g e of
the g e n e r a l n a t u r e of the a s t r o n o m i c a l p h e n o m e n a c o n c e r n e d . In p r e p a r i n g
w r i t t e n n o t e s t h e a u t h o r h a s c o n c e n t r a t e d a t t e n t i o n on the g e n e r a l n a t u r e
of t h e a s t r o n o m i c a l p r o b l e m s .
A s b a c k g r o u n d m a t e r i a l t h e f o l l o w i n g g e n e r a l r e f e r e n c e s s h o u l d be
m e n t i o n e d . F o r a n i n t r o d u c t i o n to a s t r o n o m y , " D e r n e u e K o s m o s " by
A. Unsold, H e i d e l b e r g e r T a s c h e n b ü c h e r , Band 16/17 (English T r a n s l a t i o n ,
" T h e New C o s m o s " , L o n g m a n s , 1969), c a n be r e c o m m e n d e d . A S u m m e r
S c h o o l a t S t i r l i n g i n 1971 w a s c o n c e r n e d w i t h " A t o m s and M o l e c u l e s i n
A s t r o p h y s i c s " (edited b y T . R . C a r s o n and M . J . R o b e r t s and p u b l i s h e d
by A c a d e m i c P r e s s , 1972). A v a l u a b l e r e c e n t r e v i e w a r t i c l e i s :
V . M . M y e r s c o u g h and G . P e a c h , " A t o m i c P r o c e s s e s i n A s t r o p h y s i c a l
P l a s m a s " , ( C a s e S t u d i e s i n A t o m i c C o l l i s i o n P h y s i c s , V o l . 2 , 1972; "
E d s M . R . C . M c D o w e l l and E . W . M c D a n i e l , N o r t h - H o l l a n d P u b l . )
T h e a u t h o r h i m s e l f a l s o g a v e s o m e l e c t u r e s on " P r o b l e m s in A s t r o -
p h y s i c s " — w i t h e m p h a s i s o n a t o m i c p r o c e s s e s — at t h e B o u l d e r I n s t i t u t e
f o r T h e o r e t i c a l P h y s i c s , 1961 ( e d i t e d b y W . E . B r i t t i n , B . W . D o w n s and
J . D o w n s , a n d p u b l i s h e d by I n t e r s c i e n c e , 1962).
M a n y t o p i c s i n a t o m i c p h y s i c s r e l e v a n t to a s t r o p h y s i c s a r e d i s c u s s e d
in " P l a s m a S p e c t r o s c o p y " by H . R . G r i e m , M c G r a w H i l l , 1964.

1. STELLAR ATMOSPHERES

A p h o t o n p r o d u c e d i n t h e i n t e r i o r of a s t a r h a s only a v e r y s m a l l
p r o b a b i l i t y of e s c a p i n g f r o m t h e s t a r . P u t a n o t h e r w a y , t h e r a d i a t i o n
w h i c h we o b s e r v e f r o m a s t a r c o m e s f r o m a t h i n o u t e r l a y e r . T h i s o b s e r v a -
b l e r e g i o n i s known a s t h e s t e l l a r a t m o s p h e r e . L e t t h e a t m o s p h e r e h a v e
a t h i c k n e s s A r and t h e s t a r a r a d i u s R s . We u s u a l l y h a v e A r « R s , in
w h i c h c a s e w e can n e g l e c t e f f e c t s of c u r v a t u r e , a n d d i s c u s s t h e a t m o s p h e r e

2 6 1
262 SEATON

in a p l a n e p a r a l l e l a p p r o x i m a t i o n . L e t the s t a r have a m a s s M*s. T h e


g r a v i t a t i o n a l f o r c e , p e r unit m a s s , in the a t m o s p h e r e i s g = G M S / R 2 . TO
a v e r y good a p p r o x i m a t i o n , t h e g r a v i t a t i o n a l f o r c e m u s t b a l a n c e t h e p r e s s u r e
gradient, i . e .

^ = - P < Dg (1.1)

w h e r e : r i s a d i s t a n c e m e a s u r e d o u t w a r d s in a d i r e c t i o n at r i g h t a n g l e s
to t h e p l a n e p a r a l l e l l a y e r s of the a t m o s p h e r e ; p ( r ) i s the p r e s s u r e ; p(r)
i s the density.
C o l l i s i o n s a r e a l w a y s v e r y e f f e c t i v e in r e - d i s t r i b u t i n g k i n e t i c e n e r g y
and in s e t t i n g up a Maxwell d i s t r i b u t i o n of p a r t i c l e v e l o c i t i e s . We m a y
t h e r e f o r e a s s u m e t h a t t h e c o n c e p t of a l o c a l kinetic t e m p e r t u r e , T ( r ) , i s
w e l l d e f i n e d . We m a y a l s o a s s u m e the p e r f e c t g a s law, p = NkT w h e r e
N i s t h e t o t a l n u m b e r of p a r t i c l e s p e r unit v o l u m e . We m a y put p = Npi
w h e r e ß i s t h e m e a n m o l e c u l a r w e i g h t . T h e equation of s t a t e i s t h e n

P = ркТ/м (1.2)

T h e c o n d i t i o n s in the a t m o s p h e r e a r e f u r t h e r d e t e r m i n e d by t h e f a c t
t h a t e n e r g y i s p r o d u c e d in t h e i n t e r i o r of t h e s t a r , p a s s e s t h r o u g h t h e
a t m o s p h e r e , and i s r a d i a t e d into s p a c e . L e t I„ dy du ds_^be the r a d i a n t
e n e r g y p e r unit t i m e c r o s s i n g an a r e a d s in a d i r e c t i o n t n o r m a l to d s ,
and within a solid angle du and f r e q u e n c y r a n g e dy. In going a d i s t a n c e àî.,
e n e r g y c a n be both a b s o r b e d and e m i t t e d . T h e e q u a t i o n of r a d i a t i v e t r a n s f e r
is

^ f = - p * u l v +PÍV (1.3a)

w h e r e kv i s the a b s o r p t i o n c o e f f i c i e n t p e r unit m a s s , and j ^ t h e e m i s s i v i t y


p e r unit m a s s , and p e r unit solid a n g l e . L e t the d i r e c t i o n SL m a k e an angle
0 with t h e d i r e c t i o n ? . We t h e n have d r = c o s 9 di and t h e t r a n s f e r equation

= - p »c„ I„ +piv (1.3b)

It m a y be a s s u m e d t h a t kv and depend only on r ; I v , h o w e v e r , d e p e n d s


on both r and 0. T h e t r a n s f e r equation m u s t be solved s u b j e c t to t h e b o u n d a r y
condition t h a t , at t h e top of t h e a t m o s p h e r e , all r a d i a t i o n i s in the o u t w a r d
d i r e c t i o n (we m a y n e g l e c t r a d i a t i o n c o m i n g f r o m s p a c e to the s t a r ) .
T h e o u t w a r d d i r e c t i o n i s 0 < тг/2, the i n w a r d d i r e c t i o n 0 > 7t/2. T h e
b o u n d a r y condition i s I ( r , 0)-> 0 a s r-> » f o r 0 > 7T/2.
T h e i n t e n s i t y I ( r , 6 ) h a s a c o m p o n e n t lv(r,9) cos 6 in the upward direction.
T h e net u p w a r d flux at f r e q u e n c y v i s

F ( r ) = J J lv(r, в) c o s 0 du dv = 2тгJ J I„(r, 0) c o s 0 s i n 0 d6 dv (1.4a)


v=0 6=0

If o t h e r f o r m s of e n e r g y t r a n s f e r , such a s conduction and c o n v e c t i o n , c a n


b e n e g l e c t e d , e n e r g y c o n s e r v a t i o n r e q u i r e s that
I A E A - S M R - 1 2 / 4 4 , 46 , 4 8 263

F = c o n s t a n t i n d e p e n d e n t of r (1.4b)

T h e e q u a t i o n s which we have g i v e n d e f i n e the c l a s s i c s t e l l a r a t m o s p h e r e


p r o b l e m . Suppose t h a t the following a r e s p e c i f i e d : (i) t h e c h e m i c a l c o m p o -
sition of t h e a t m o s p h e r e ; (ii) t h e g r a v i t y , g; (iii) the flux c o n s t a n t F . We
c a n then solve the e q u a t i o n s (1. 1), (1.2) and ( 1 . 3 b ) , s u b j e c t to the b o u n d a r y
c o n d i t i o n s and t h e c o n s t r a i n t ( 1 . 4 b ) , to d e t e r m i n e all p r o p e r t i e s of the
a t m o s p h e r e , and to c o m p u t e t h e s p e c t r u m of the e m e r g e n t r a d i a t i o n .
T h e s o l u t i o n s a r e s u c h t h a t p, p and T d e c r e a s e o u t w a r d s . High in
t h e a t m o s p h e r e , p and p d e c r e a s e e x p o n e n t i a l l y with height and T t e n d s
to a c o n s t a n t v a l u e T fl (the " s u r f a c e t e m p e r a t u r e " ) . T h e o u t w a r d d e c r e a s e
of T i s e s s e n t i a l to an u n d e r s t a n d i n g of the o b s e r v e d s p e c t r u m . It i s , of
c o u r s e , o b v i o u s t h a t the h i g h e s t l a y e r s m u s t be the c o l d e s t , s i n c e t h e s e
l a y e r s c a n r a d i a t e f r e e l y to o u t e r s p a c e .
C o n s i d e r a p h o t o n , c r e a t e d at a p o i n t r , which m o v e s in t h e o u t w a r d
d i r e c t i o n r . T h e p r o b a b i l i t y t h a t t h i s photon e s c a p e s , without being r e -
absorbed, is ехр(-ти ) where

(1.5)
Г

T h e o b s e r v e d a t m o s p h e r e , at f r e q u e n c y v, e x t e n d s down to a depth r such


t h a t Ту (r) = 1. C o n s i d e r s o m e s u i t a b l e m e a n v a l u e , т , of tv . If т(г) = 1
and r ( r + A r ) i s s m a l l , s a y т ( г + A r ) - 0.01, t h e n A r i s the t h i c k n e s s of
the a t m o s p h e r e .
L e t u s c o n s i d e r how, in p r a c t i c e , our e q u a t i o n s m i g h t be s o l v e d . We
s t a r t with s o m e e s t i m a t e of T ( r ) and of Iv (r, 6). T h e n , using E q s (1.1)
and (1.2), we c a n c a l c u l a t e p ( r ) and p ( r ) and, a s s u m i n g a l l of the n e c e s s a r y
a t o m i c p h y s i c s to be known, we c a n c a l c u l a t e the a b s o r p t i o n c o e f f i c i e n t
к у ( r ) and the e m i s s i v i t y j v ( r ) . We c a n then s o l v e the t r a n s f e r e q u a t i o n (1.3b),
s u b j e c t to t h e b o u n d a r y c o n d i t i o n s but — u n l e s s we had b e e n given the c o r r e c t
solution to s t a r t with— the condition (1.4b) w i l l not be s a t i s f i e d . We m u s t
t h e r e f o r e a d j u s t T ( r ) until t h i s c o n d i t i o n i s s a t i s f i e d . We t h u s obtain new
e s t i m a t e s of T ( r ) and I (r, 0) and the p r o c e s s c a n be r e p e a t e d and, one
hopes, will be c o n v e r g e n t . F i n a l l y , if one i s t r y i n g to m a t c h t h e o r y and
o b s e r v a t i o n s f o r a r e a l s t a r , one m u s t a d j u s t F , g and c h e m i c a l c o m p o s i t i o n
so a s to get a g r e e m e n t b e t w e e n t h e c o m p u t e d and t h e o b s e r v e d s p e c t r a .
T h e g e n e r a l p i c t u r e on a b u n d a n c e s i s t h a t h y d r o g e n i s by f a r the m o s t
abundant e l e m e n t . Next c o m e s He, with a b u n d a n c e 0.1 t i m e s t h a t of H,
by n u m b e r s of a t o m s . All o t h e r a t o m s have m u c h l o w e r a b u n d a n c e s — in
total about 10" t i m e s t h e H a b u n d a n c e . S p e c t r u m l i n e s of H and He a r e ,
h o w e v e r , p r o d u c e d e f f i c i e n t l y only at r a t h e r high t e m p e r a t u r e s . In m a n y
a s t r o n o m i c a l s p e c t r a m o s t of the o b s e r v e d l i n e s a r e p r o d u c e d by e l e m e n t s
o t h e r t h a n H and H e .
What a t o m i c p h y s i c s i s r e q u i r e d ? Given the t e m p e r a t u r e , p r e s s u r e
and r a d i a t i o n field one m u s t f i r s t , f o r e a c h e l e m e n t , c o m p u t e the n u m b e r
of a t o m s in e a c h i o n i z a t i o n s t a g e and t h e n , f o r e a c h s t a g e , the n u m b e r in
e a c h e x c i t e d s t a t e . Knowing a l l r a d i a t i v e t r a n s i t i o n p r o b a b i l i t i e s , KV and
j„ c a n now be c o m p u t e d . E v i d e n t l y t h i s i s a p r e t t y daunting t a s k .
L e t us c o n s i d e r a s i m p l e r a p p r o x i m a t i o n . V e r y f a r f r o m the s u r f a c e
(t » 1), c o n d i t i o n s m u s t be c l o s e to t h o s e .in a b l a c k body at the l o c a l
264 SEATON

temperature T(r). We then have local t h e r m o d y n a m i c e q u i l i b r i u m ( L T E ) .


F o r a b l a c k body, = B„(T) w h e r e

1 1 (i 6)
^ m ^ W s ) " } ' -
i s the P l a n c k i n t e n s i t y . F o r a black body we a l s o have dl^ / d i = 0 and
hence, f r o m ( 1 . 3 a )

(]„/*„) = B„(T) (1.7)

T h i s i s K i r c h h o f f ' s l a w . But now the r a t i o (j / к ) d e p e n d s only on the


s t a t e of t h e m a t e r i a l p a r t i c l e s . If t h i s s t a t e i s c o n s i s t e n t with t h e r m o d y n a m i c
l a w s (Maxwell law, B o l t z m a n n law and Saha law of i o n i z a t i o n e q u i l i b r i u m )
t h e n (1.7) w i l l be s a t i s f i e d . In t h e L T E t h e o r y of s t e l l a r a t m o s p h e r e s ,
the K i r c h h o f f law (1. 7) i s a s s u m e d , but t h e P l a n c k law, I „ ( r , 6) = B „ ( T ( r ) ) ,
i s not a s s u m e d . C l e a r l y one could not a s s u m e the P l a n c k law, c o n s i s t e n t
with t h e b o u n d a r y condition that, at t h e top of the a t m o s p h e r e , a l l r a d i a t i o n
i s in t h e o u t w a r d d i r e c t i o n . T h e LTE a s s u m p t i o n w i l l be v a l i d if c o l l i s i o n a l
p r o c e s s e s a r e m u c h m o r e i m p o r t a n t than r a d i a t i v e p r o c e s s e s in d e t e r m i n i n g
the i o n i z a t i o n e q u i l i b r i u m and the level p o p u l a t i o n s . In the L T E a p p r o x i m a t i o n ,
c o l l i s i o n c r o s s - s e c t i o n s a r e not r e q u i r e d , but we s t i l l n e e d to know all
radiative transition probabilities.
In o r d e r to a p p r e c i a t e s o m e of the e s s e n t i a l s of the p r o b l e m , let us
now c o n s i d e r an e v e n s i m p l e r m o d e l . As a l r e a d y m e n t i o n e d , the o b s e r v e d
s p e c t r u m d e p e n d s in an e s s e n t i a l way on the t e m p e r a t u r e g r a d i e n t . In the
s i m p l e s t m o d e l one c o n s i d e r s a r e g i o n which e m i t s a p u r e continuum
s p e c t r u m , with i n t e n s i t y and above it a c o o l e r r e g i o n (the " r e v e r s i n g
l a y e r " ) w h i c h m a y be c o n s i d e r e d to a b s o r b r a d i a t i o n in s p e c t r u m l i n e s ,
but not to e m i t r a d i a t i o n . The o b s e r v e d i n t e n s i t y i s t h e n

I , = 1= e x p ( - r j (1.8)
where
rv = JPKV dr (1.9)
lev.
layer

C o n s i d e r a s p e c t r u m l i n e , involving an u p p e r l e v e l u and a l o w e r
l e v e l ft. T h e e m i s s i o n c o e f f i c i e n t i s given by

pj„= h a
uí hy
o ( 1 Л 0 )

the f a c t o r (l/Лтг) i s i n c l u d e d b e c a u s e the e m i s s i o n i s counted p e r unit


solid angle; N u i s t h e n u m b e r of a t o m s p e r unit v o l u m e in l e v e l u; A u {
i s the spontaneous t r a n s i t i o n probability; i s the f r e q u e n c y at the line
c e n t r e (hv 0 = (E u - E { ) w h e r e Е ц , E { a r e the a t o m i c e n e r g y l e v e l s ) ; and
<p(v) i s a n o r m a l i z e d line p r o f i l e f a c t o r ,

<p(v) di/ = 1 (1.11)


I A E A - S M R - 1 2 / 4 4 , 46 , 4 8 265

The a b s o r p t i o n c o e f f i c i e n t i s obtained using E q . (1. 7) and the B o l t z m a n n

= i£u exp (-hy 0 /kT) (1.12)

(u u , u e being s t a t i s t i c a l weights).
We obtain
2
pKv = — N, f i l - exp(-hi/ 0 /kT)} <p(v) (1.13)

where

f = A 1 4
8тг2 е 2 1/2 I T U £ ( ! • >
1
0
i s the a b s o r p t i o n o s c i l l a t o r s t r e n g t h . The f a c t o r {1 - exp(-hy Q /kT)} i s
a c o r r e c t i o n for s t i m u l a t e d e m i s s i o n : c o n s i s t e n t with the neglect of
spontaneous e m i s s i o n f o r the r e l a t i v e l y cold r e v e r s i n g l a y e r , we m a y
put t h i s f a c t o r equal to unity. We then have
2
(1Л5)

where

Л =/ N J dr (1.16)
rev.
layer
i s the n u m b e r of a t o m s in a column of unit a r e a , in the r e v e r s i n g l a y e r .
A s p e c t r u m line has a p r o f i l e a s shown in F i g . 1.

»V

FIG. 1. L i n e p r o f i l e ( i n t e n s i t y versus f r e q u e n c y ) .

The amount of a b s o r p t i o n in the line i s

f a l - i j d v (1.17)

The equivalent width of the line i s defined a s

Ay = / a s y ^ d v (1Д8)
266 SEATON

T h i s i s a u s e f u l q u a n t i t y , s i n c e no a b s o l u t e i n t e n s i t y c a l i b r a t i o n i s r e q u i r e d
and — so long a s t h e l i n e c a n b e c l e a r l y s e e n — the m e a s u r e d e q u i v a l e n t w i d t h
i s i n s e n s i t i v e to f r e q u e n c y r e s o l v i n g p o w e r .
F r o m E q . (1.9)

A v = / (1 - ехр(-т„ )) dy (1.. 19)

S u p p o s e t h a t t h e l i n e i s w e a k , so t h a t r v « 1 f o r a l l p o i n t s in t h e l i n e .
P u t t i n g (1 - expf-Tj, )) = т и and using (1.11) w e o b t a i n

2
f
Ли = Л Í1-20)
mť i

F o r s t r o n g e r l i n e s w e have to c o n s i d e r the f o r m of t h e p r o f i l e f a c t o r <p(v).


F o r p u r e t h e r m a l D o p p l e r b r o a d e n i n g w e h a v e <pv = cp® w h e r e

Л - i r f h - е х р { - Ы * - vü)/v,}2} (1.21)

and w h e r e

a = [Mc2/(2kT)]1/2 (1.22)

M being the atom m a s s . T h e f u l l w i d t h of t h e a b s o r p t i o n c o e f f i c i e n t , a t


half-maximum, is

= lü> [in(2)]1/2 (1.23)

(i.e.
S u p p o s e t h a t rv i s l a r g e at the l i n e c e n t r e , т„о » 1. F o r | v - v0 | > i Д°,
soon b e c o m e s s m a l l . All absorption is t h e r e f o r e effectively confined
to t h e r e g i o n (vQ - т Д ° ) S v S (v + | Д ° ) a n d w e h a v e

Ap^KAd (1.24)

w h e r e К i s a c o n s t a n t of o r d e r u n i t y .
F i n a l l y , f o r v e r y s t r o n g l i n e s , we h a v e to c o n s i d e r the a d d i t i o n a l
a b s o r p t i o n w h i c h o c c u r s f a r f r o m t h e l i n e c e n t r e . In t h i s r e g i o n t h e p r o f i l e
f a c t o r <p(v) i s d e t e r m i n e d by the f a c t t h a t a r a d i a t i n g a t o m s t a y s i n t h e
upper level for a finite time, t . This gives a profile

<p„2 = ^ {(v- y 0 ) 2 +Ó 2 }" 1 (1.25)

w h e r e 6 = l / ( 2 j r t u ) . W h e n t h e l o w e r l e v e l i s a l s o a n e x c i t e d s t a t e of f i n i t e
l i f e t i m e t h i s b e c o m e s б = (1/2тг) (t^ 1 + t j 1 ) . In g e n e r a l t h e l i f e t i m e s t , t t
a r e d e t e r m i n e d b o t h by r a d i a t i v e t r a n s i t i o n p r o b a b i l i t i e s and by c o l l i s i o n s .
T h e f o r m (1.25) i s r e f e r r e d to a s a d a m p i n g p r o f i l e o r L o r e n t z p r o f i l e .
C o m p a r e d w i t h (1.21) we s e e t h a t (1.25) d e c r e a s e s m u c h m o r e s l o w l y f o r
(v - y 0 ) l a r g e . T h e D o p p l e r p r o f i l e (1.21) u s u a l l y a p p l i e s n e a r t h e l i n e
c e n t r e ( (v - i/0) s m a l l ) , a n d t h e d a m p i n g p r o f i l e (1.25) a p p l i e s in t h e line
I A E A - S M R - 1 2 / 4 4 , 4 6 , 48 267

w i n g s . F o r v e r y s t r o n g l i n e s a b s o r p t i o n in the d a m p i n g wings i s i m p o r t a n t
and one o b t a i n s i n c r e a s e d e q u i v a l e n t w i d t h s , such t h a t
1/2
Av x (jrs f) (1.26)

C o m b i n i n g all t h e s e r e s u l t s , we m a y plot the e q u i v a l e n t width a s a


f u n c t i o n of J f t i ( n u m b e r of a b s o r b i n g a t o m s t i m e s o s c i l l a t o r s t r e n g t h ) .
Using l o g a r i t h m i c s c a l e s we o b t a i n F i g . 2. T h i s i s known a s the c u r v e
of g r o w t h .

log(ův)fconst

FIG.2. C u r v e of growth ( e q u i v a l e n t w i d t h versus n u m b e r of a b s o r b i n g a t o m s x o s c i l l a t o r s t r e n g t h ) .

We have 3 r e g i o n s : in r e g i o n A we have w e a k l i n e s and t h e l i n e a r r e l a t i o n


(1.20) holds; in r e g i o n В we have m e d i u m - s t r o n g l i n e s and the e q u i v a l e n t
width i s d e t e r m i n e d by the width of the D o p p l e r p r o f i l e , E q . (1.24); f i n a l l y
in r e g i o n С we have v e r y s t r o n g l i n e s , f o r which t h e r e i s a p p r e c i a b l e
a b s o r p t i o n in t h e d a m p i n g w i n g s , given by (1.26).
A m o r e r e f i n e d t h e o r y g i v e s a c u r v e of g r o w t h s i m i l a r to t h a t obtained
using o u r v e r y s i m p l e m o d e l of an a t m o s p h e r e containing two r e g i o n s . L e t
us c o n s i d e r t h e c a s e of the s o l a r s p e c t r u m . If we plot the o b s e r v e d
e q u i v a l e n t w i d t h s a g a i n s t ^f e f (as c o m p u t e d f r o m a model) we do i n d e e d
obtain a c u r v e of g r o w t h s i m i l a r to that shown in F i g . 1 — but with, of c o u r s e ,
a c e r t a i n a m o u n t of s c a t t e r .
We m a y now d i s c u s s in m o r e d e t a i l the a t o m i c d a t a needed f o r the
i n t e r p r e t a t i o n of the o b s e r v a t i o n s . F i r s t , the a s t r o p h y s i c i s t n e e d s to
know the o s c i l l a t o r s t r e n g t h s f. In r e c e n t y e a r s a g r e a t deal of w o r k h a s
b e e n done. A c c u r a t e a b s o l u t e m e a s u r e m e n t s have b e e n m a d e f o r s e l e c t e d
l i n e s , and f o r l i g h t e r a t o m s good a b s o l u t e r e s u l t s can be obtained f r o m
q u a n t u m m e c h a n i c a l c a l c u l a t i o n s . L a r g e n u m b e r s of r e l a t i v e f - v a l u e s c a n
be obtained f r o m o b s e r v e d l i n e i n t e n s i t i e s using l a b o r a t o r y light s o u r c e s
f o r which L T E can be a s s u m e d ; the data have to be c a l i b r a t e d a g a i n s t
a b s o l u t e m e a s u r e m e n t s . B u t d e s p i t e all t h e e f f o r t which p h y s i c i s t s have
put into t h e d e t e r m i n a t i o n of f - v a l u e s , the a s t r o p h y s i c i s t s a r e a l w a y s h u n g r y
f o r m o r e good new d a t a .
If one i s c o n c e r n e d with a b u n d a n c e a n a l y s i s f o r the sun, o r f o r b r i g h t
s t a r s , one m a y r e s t r i c t a t t e n t i o n to weak l i n e s on the l i n e a r p o r t i o n A of
the c u r v e of g r o w t h . F o r f a i n t e r s t a r s , h o w e v e r , one m u s t w o r k with
s t r o n g l i n e s , on the d a m p i n g p o r t i o n С of the c u r v e of g r o w t h . In m a n y
268 SEATON

c a s e s d a m p i n g i s due to c o l l i s i o n s with H a t o m s . No e x p e r i m e n t a l data


are available. Crude theoretical e s t i m a t e s can be made assuming van der
W a a l s f o r c e s . E x p e r i m e n t a l data a r e a v a i l a b l e f o r damping by c o l l i s i o n s
with r a r e g a s a t o m s . T h i s p r o v i d e s a c h e c k on the t h e o r y , and shows t h a t
the a s s u m p t i o n of van d e r W a a l s f o r c e s can give r e s u l t s in e r r o r by a
f a c t o r of 3 o r s o . A c c u r a t e c a l c u l a t i o n s have b e e n m a d e f o r a few s i m p l e
c a s e s — such a s d a m p i n g of Na l i n e s by H - a t o m c o l l i s i o n s — but no a c c u r a t e
data a r e a t p r e s e n t a v a i l a b l e f o r the g r e a t m a j o r i t y of l i n e s of i n t e r e s t to t h e
astrophysicist.
So f a r we have c o n c e n t r a t e d attention on the s p e c t r u m l i n e s . Let us
now t u r n to a d i f f e r e n t t o p i c , t h e continuous a b s o r p t i o n kv . T h i s m u s t be
known in o r d e r to c o n s t r u c t a model of a s t e l l a r a t m o s p h e r e . In t h e sun,
and in s t a r s not too d i f f e r e n t f r o m the sun, the c o n t i n u o u s a b s o r p t i o n in
the v i s i b l e i s due to H ,

H" + hv Ï* H + e (1.27)

Good a b s o l u t e c r o s s - s e c t i o n s a r e known both f r o m t h e o r y and f r o m l a b o r a t o r y


m e a s u r e m e n t s . In the i n f r a - r e d the f r e e - f r e e p r o c e s s

H + e + hi/s*H + e (1.28)

i s d o m i n a n t (the p r o c e s s H + e - ^ H + e + hy c a n be u n d e r s t o o d a s r a d i a t i o n
by an e l e c t r o n a c c e l e r a t e d by the field of an H a t o m ) . Good t h e o r e t i c a l
data a r e a v a i l a b l e .
M o s t of the H i s n e u t r a l and the e l e c t r o n s involved in (1.27) and (1.28)
c o m e f r o m i o n i z a t i o n of m e t a l a t o m s , having low i o n i z a t i o n p o t e n t i a l s . .
All the r a d i a t i v e and c o l l i s i o n a l p r o c e s s e s d e t e r m i n i n g the a m o u n t of H~
p r e s e n t have b e e n studied c a r e f u l l y , and it h a s b e e n shown that, f o r the
sun, the a s s u m p t i o n of L T E f o r the c a l c u l a t i o n of the c o n t i n u o u s a b s o r p t i o n
c o e f f i c i e n t i s a v e r y good a p p r o x i m a t i o n .
L e t us now t u r n to the h o t t e r s t a r s . F o r t h e s e , m o r e of the h y d r o g e n
i s i n e x c i t e d s t a t e s . Also m o r e r a d i a t i o n i s in the u l t r a - v i o l e t r e g i o n f o r
which p h o t o - i o n i z a t i o n of g r o u n d - s t a t e H c a n o c c u r . The c o n t i n u o u s
a b s o r p t i o n i s t h e n m a i n l y due to p h o t o - i o n i z a t i o n of H, f r o m the ground
s t a t e and f r o m e x c i t e d s t a t e s . P h o t o - i o n i z a t i o n of o t h e r a t o m s m u s t a l s o
be t a k e n into a c c o u n t . A f u r t h e r p r o c e s s of i m p o r t a n c e i s t h e s c a t t e r i n g
of r a d i a t i o n by f r e e e l e c t r o n s ,

e + hv - e + hy' (1.29)

which can c h a n g e the d i r e c t i o n of the photon and m u s t t h e r e f o r e be allowed


f o r in solving the t r a n s f e r equation, T h e p r o c e s s (1.29) which i s known a s
T h o m s o n s c a t t e r i n g , g i v e s only a s m a l l change in the photon e n e r g y (due to
the D o p p l e r e f f e c t a r i s i n g f r o m the e l e c t r o n v e l o c i t y ) .
In the m o s t e l a b o r a t e c a l c u l a t i o n s f o r m o d e l s of hot s t a r s , the L T E
a s s u m p t i o n h a s not b e e n m a d e : t h e H l e v e l p o p u l a t i o n s a r e c o m p u t e d
allowing f o r all p r o c e s s e s thought to be of i m p o r t a n c e . The c o n t r i b u t i o n
of the s t r o n g e r l i n e s to the t o t a l a b s o r p t i o n h a s a l s o b e e n t a k e n into a c c o u n t
in computing the m o d e l s .
F o r h o t t e r s t a r s the p r o f i l e s of the H l i n e s a r e of g r e a t i n t e r e s t . Due
to Í - d e g e n e r a c y , H e n e r g y l e v e l s have a l i n e a r S t a r k e f f e c t . The b r o a d e n i n g
I A E A - S M R - 1 2 / 4 4 , 46 , 48 269

i s t h e r e f o r e due to a v e r a g e e l e c t r i c f i e l d s p r o d u c e d by n e i g h b o u r i n g c h a r g e d
p a r t i c l e s . A g r e a t d e a l of e f f o r t h a s gone into p e r f e c t i n g the t h e o r y , which
is quite e l a b o r a t e . T h e H line w i d t h s depend on the p r e s s u r e in the a t m o s -
p h e r e which, in t u r n , d e p e n d s on the g r a v i t a t i o n a l c o n s t a n t g. The H line
p r o f i l e s a r e t h e r e f o r e used to d e t e r m i n e g.
If the L T E a s s u m p t i o n i s m a d e f o r hot s t a r s , it i s found that one c a n n o t
obtain a g r e e m e n t with o b s e r v a t i o n s f o r both the e q u i v a l e n t w i d t h s and the
p r o f i l e s of h y d r o g e n l i n e s . F u r t h e r m o r e , the v a l u e s of g deduced f r o m
the p r o f i l e s a r e not in a g r e e m e n t with v a l u e s deduced by o t h e r m e a n s .
T h e n o n - L T E c a l c u l a t i o n s a r e found to give m u c h m o r e s a t i s f a c t o r y r e s u l t s .
F o r m o s t s t a r s p r a c t i c a l l y a l l of the s p e c t r u m l i n e s a p p e a r in a b s o r p t i o n
but f o r c e r t a i n hot s t a r s with extended a t m o s p h e r e s one a l s o o b s e r v e s m a n y
e m i s s i o n l i n e s . C l e a r l y the L T E a s s u m p t i o n i s not v a l i d in the l o w - d e n s i t y
o u t e r l a y e r s of t h e s e s t a r s . Some p a r t i c u l a r l y i n t e r e s t i n g p r o b l e m s a r e
p o s e d by t h e s p e c t r u m of N III, f o r which s o m e of the l i n e s a p p e a r in e m i s s i o n
and s o m e in a b s o r p t i o n . E v e n f o r the c a s e of hot s t a r s which do not have
l o w - d e n s i t y extended a t m o s p h e r e s , s o m e of the N III l i n e s a p p e a r in e m i s s i o n .
T h e s e o b s e r v a t i o n s c a n be explained s a t i s f a c t o r i l y when one t a k e s e x p l i c i t
a c c o u n t of all the d e t a i l e d a t o m i c p r o c e s s e s which p o p u l a t e and depopulate
t h e N z + e n e r g y l e v e l s . F o r n o n - L T E c a l c u l a t i o n s , one r e q u i r e s l a r g e
a m o u n t s of a t o m i c data on r e a c t i o n r a t e s f o r c o l l i s i o n a l p r o c e s s e s , I s e e
t h e p a p e r by M i h a l a s and H u m m e r ] .

2. THE SOLAR CORONA

T h e r e g i o n of the s o l a r a t m o s p h e r e which g i v e s m o s t of the o b s e r v e d


r a d i a t i o n i s r e f e r r e d to a s the p h o t o s p h e r e . In the t h e o r y d i s c u s s e d in
s e c t i o n 1 it h a s b e e n a s s u m e d that t h i s r e g i o n i s q u i e s c e n t , that i s to s a y
t h a t t h e r e a r e no m a s s m o t i o n s . Having c o n s t r u c t e d a m o d e l we c a n c h e c k
on the c o n s i s t e n c y of t h i s a s s u m p t i o n .
Suppose that a s m a l l p e r t u r b a t i o n a c t s on an e l e m e n t of m a t e r i a l at r ,
and d i s p l a c e s it to r + S r . A l m o s t i n s t a n t a n e o u s l y t h i s e l e m e n t will r e a c h
p r e s s u r e e q u i l i b r i u m with i t s s u r r o u n d i n g s , but a m u c h l o n g e r t i m e will
be r e q u i r e d to r e a c h t h e r m a l e q u i l i b r i u m . We m a y t h e r e f o r e a s s u m e an
a d i a b a t i c change ( i . e . no h e a t e x c h a n g e ) . T h e new t e m p e r a t u r e of the
d i s p l a c e d e l e m e n t i s then T ( r ) + Ó T | a w h e r e A s t a n d s f o r a d i a b a t i c :

6T ЭТ ЭТ Эр
L (ár) (ár) (2.1)
Эг Эр А Эг M

w h e r e (dp/dr)|M i s the p r e s s u r e gradient for the model, calculated using


the m e t h o d s d e s c r i b e d in s e c t i o n 1. T h e t e m p e r a t u r e of the m o d e l at
r + 6r is T(r) + 6TIM where

dT
« T L = («г) d r (2.2)

In (2.1) the p a r t i a l d e r i v a t i v e (Эр/ЭТ) А i s e v a l u a t e d using the a d i a b a t i c


e q u a t i o n T 5 , p 1 _ ï = c o n s t a n t , w h e r e 7 i s the u s u a l r a t i o of s p e c i f i c h e a t s .
270 SEATON

If the d i s p l a c e d e l e m e n t i s c o l d e r than i t s s u r r o u n d i n g s , it will be d e n s e r


and will f a l l back to i t s o r i g i n a l p o s i t i o n . In t h i s c a s e t h e a t m o s p h e r e i s
s t a b l e and c o n v e c t i v e m o t i o n s will not d e v e l o p .
T h e condition f o r s t a b i l i t y i s

6T|A<6T|M (2.3)

F o r a m o d e l of the s o l a r a t m o s p h e r e it i s found that (2.3) i s s a t i s f i e d


only in t h e u p p e r l a y e r s , т <, 1. Below т convective motions occur
and t h e a c t u a l t e m p e r a t u r e g r a d i e n t i s then c l o s e to ( Э Т / Э г ) | А .
In t h e u p p e r l a y e r s m a s s m o t i o n s tend to be d a m p e d but s t i l l o c c u r
and m u s t be t a k e n into a c c o u n t in c o n s i d e r i n g the D o p p l e r b r o a d e n i n g of
the s p e c t r a l l i n e s .
T h e e x i s t e n c e of a c o n v e c t i v e r e g i o n at g r e a t e r d e p t h s , т > 1, p r o f o u n d l y
m o d i f i e s the c o n d i t i o n s in the v e r y h i g h e s t l a y e r s of the a t m o s p h e r e . T h i s
m a y be s e e n a s f o l l o w s . Convection p r o d u c e s a c o u s t i c e n e r g y , and an
a c o u s t i c e n e r g y fl ux, F sounc j, in the p h o t o s p h e r e . T h i s flux i s s m a l l c o m p a r e d
with the r a d i a t i v e flux, and t h e r e f o r e d o e s not s e r i o u s l y p e r t u r b the m a i n
p h o t o s p h e r i c l a y e r s . But what h a p p e n s f o r the u p p e r m o s t l a y e r s ? We have

r
sou„d = i P "s Л - (2.4)

w h e r e u s i s the a m p l i t u d e of p a r t i c l e d i s p l a c e m e n t v e l o c i t y due to the sound


wave, and v s = (ykT/ц) 1 ^ 2 i s the v e l o c i t y of sound. F o r the m o d e l we have
t h a t T -*• T„и a s r i n c r e a s e s , and hence t h a t vs t e n d s to a c o n s t a n t . But the
d e n s i t y p d e c r e a s e s e x p o n e n t i a l l y and c o n s e r v a t i o n of a c o u s t i c e n e r g y
t h e r e f o r e r e q u i r e s t h a t u s i n c r e a s e s e x p o n e n t i a l l y . E v e n t u a l l y the point
i s r e a c h e d w h e r e u s a p p r o a c h e s vs . At t h i s point the sound wave b e c o m e s
a s h o c k w a v e , and t h i s h e a t s t h e g a s . Beyond t h i s point all the a s s u m p t i o n s
m a d e in c o n s t r u c t i n g o u r m o d e l c e a s e to be v a l i d . In p l a c e of a c o n s t a n t
s u r f a c e t e m p e r a t u r e T 0 we have a t e m p e r a t u r e i n c r e a s e in the o u t e r m o s t
layers.
T h e t h e o r y d e s c r i b e d above i s a g r o s s o v e r - s i m p l i f i c a t i o n , but the
m a i n c o n c l u s i o n i s c o r r e c t : the e x i s t e n c e of a c o n v e c t i v e r e g i o n at g r e a t e r
d e p t h s p r o v i d e s a s o u r c e of e n e r g y which h e a t s the h i g h e s t l a y e r s . How
hot c a n t h e s e l a y e r s b e c o m e ? T h e e s c a p e v e l o c i t y v e , f o r an a t o m of
m a s s M, i s given by \ M v 2 = G M M 0 / R 0 w h e r e M Q i s the m a s s of the sun,
its r a d i u s .
O i 2
An e x t r e m e u p p e r l i m i t f o r T i s obtained on putting 2"Mve = k T . T h i s
g i v e s T = 2 X 10 K. In f a c t the o u t e r m o s t l a y e r s of the s o l a r a t m o s p h e r e —
the s o l a r c o r o n a — have a t e m p e r a t u r e of about 2X 10 6 K. At t h i s t e m p e r a -
t u r e t h e r e i s a s t e a d y outflow of m a t e r i a l , s i n c e p a r t i c l e s in the t a i l of the
Maxwell d i s t r i b u t i o n c a n e s c a p e (the " s o l a r w i n d " ) .
T h e t o t a l r a d i a t i o n f r o m the c o r o n a i s about 10" 6 of the r a d i a t i o n f r o m
the p h o t o s p h e r e . T h e c o r o n a can be o b s e r v e d d u r i n g an e c l i p s e (when the
p h o t o s p h e r i c r a d i a t i o n i s o b s c u r e d by the moon), o r by using a c o r o n a g r a p h
( i . e . an " a r t i f i c i a l e c l i p s e " ) . It can a l s o be o b s e r v e d a t u l t r a - v i o l e t and
X - r a y w a v e l e n g t h s (but only above t h e e a r t h ' s a t m o s p h e r e ) and at r a d i o
wavelengths.
In the c o r o n a we a r e c o n c e r n e d with t e m p e r a t u r e s of about 2 X 10 6 К
and d e n s i t i e s of o r d e r 2 X 10 8 cm" 3 , o r l e s s as^one g o e s f u r t h e r out. T h e
g a s i s c o m p l e t e l y i o n i z e d . M o s t of the f r e e e l e c t r o n s c o m e f r o m i o n i z a t i o n
I A E A - S M R - 1 2 / 4 4 , 46 , 48 271

of H and H e . W i t h a H e / H a b u n d a n c e r a t i o of 0.1, by n u m b e r s of a t o m s ,
the e l e c t r o n d e n s i t y i s N e = 1.2 N(H + ). C o n d i t i o n s in the c o r o n a a r e f a r
f r o m u n i f o r m . M a g n e t i c f i e l d s , a s s o c i a t e d w i t h s u n s p o t s , a r e of i m p o r t a n c e .
T h e h i g h e s t t e m p e r a t u r e s o c c u r a t t h e m a x i m u m in t h e 1 1 - y e a r s u n s p o t c y c l e ,
and a r e a s s o c i a t e d w i t h a c t i v e s u n s p o t r e g i o n s .
The f r e e e l e c t r o n s in the corona s c a t t e r photospheric radiation (Thomson
s c a t t e r i n g ) . Since t h e s c a t t e r i n g c r o s s - s e c t i o n , ae = (ire2/mc), is inde-
p e n d e n t of f r e q u e n c y , t h e c o n t i n u u m s p e c t r u m of the c o r o n a i s s i m i l a r to
t h a t of t h e p h o t o s p h e r e . T h e r e a r e , h o w e v e r , two i m p o r t a n t d i f f e r e n c e s :
(i) t h e c o r o n a l c o n t i n u u m i s p o l a r i z e d ( t h i s i s a f e a t u r e of T h o m s o n s c a t t e r i n g ) ;
(ii) t h e p h o t o s p h e r i c a b s o r p t i o n l i n e s do not a p p e a r in t h e c o r o n a l c o n t i n u u m —
the e l e c t r o n v e l o c i t i e s a r e so h i g h t h a t a l l d e t a i l in the s p e c t r u m i s s m e a r e d
out by D o p p l e r e f f e c t s .
In t h e s p e c t r u m of the c o r o n a a t o p t i c a l w a v e l e n g t h s o n e o b s e r v e s
s p e c t r u m l i n e s due to t r a n s i t i o n s b e t w e e n f i n e s t r u c t u r e l e v e l s i n h i g h l y
i o n i z e d a t o m s . E x a m p l e ^ a r e F e X, 3p 5 2 P 1 / i 2 2
P3/2 6375 A, F e XIV
3p 2 P 3 / 2 - 2 P 1 / 2 a t 5303 A and C a XV 2p 2 3 Р г - 3 P 0 at 5694 A . T h e i o n i -
z a t i o n p o t e n t i a l s f o r p r o d u c t i o n of t h e o b s e r v e d i o n s a r e i n t h e r a n g e 200
to 1000 e V . T h e t e m p e r a t u r e c a n b e d e d u c e d f r o m c a r e f u l m e a s u r e m e n t s
of t h e l i n e w i d t h s , a s s u m e d due t o t h e r m a l D o p p l e r b r o a d e n i n g . T h e i o n i -
z a t i o n e q u i l i b r i u m i s d e t e r m i n e d by e l e c t r o n i m p a c t i o n i z a t i o n

X + e ->• X + e + e (2.5)

and r a d i a t i v e r e c o m b i n a t i o n ,

X + m + 1 + e - (X™ )* + h v (2.6)

It s h o u l d be n o t e d t h a t r e c o m b i n a t i o n m a y t a k e p l a c e to any e x c i t e d
s t a t e of X ™ , d e n o t e d by (X + m )*. Since t h e r a t e s of (2.5) a n d (2.6) a r e both
p r o p o r t i o n a l t o the e l e c t r o n d e n s i t y N e , t h e i o n a b u n d a n c e r a t i o N ( X + m ) /
N(X ) i s i n d e p e n d e n t of N e b u t i s v e r y s e n s i t i v e to t e m p e r a t u r e . One
can compute the f r a c t i o n a l ionization

Rm = N(X+m)/£N(X+n) (2.7)
n

It i s f o u n d t h a t , f o r a g i v e n i o n i z a t i o n s t a g e m , R m a p p r o a c h e s unity only
f o r a r a t h e r s m a l l r a n g e of T , a n d t h a t R m i s v e r y s m a l l o u t s i d e of t h i s
r a n g e . If s t r o n g r a d i a t i o n f r o m a g i v e n i o n i s o b s e r v e d the t e m p e r a t u r e
c a n be d e d u c e d . E a r l i e r c a l c u l a t i o n s of R m ( T ) g a v e t e m p e r a t u r e s a good
deal l o w e r than those deduced f r o m line p r o f i l e s . This d i s c r e p a n c y was
r e s o l v e d by B u r g e s s , who s h o w e d t h a t the r e c o m b i n a t i o n p r o c e s s (2.6) c a n
proceed via doubly-excited auto-ionizing states,

X + e ü (X )-'--'- -» (X )"- + hv (2.8)

T h i s i n c r e a s e s the r e c o m b i n a t i o n r a t e by a f a c t o r of o r d e r 10 1 - 10 2 , a n d
b r i n g s the t e m p e r a t u r e s d e d u c e d f r o m the i o n i z a t i o n e q u i l i b r i u m i n t o a g r e e -
m e n t with t e m p e r a t u r e s f r o m line p r o f i l e s .
272 SEATON

T h e s p e c t r u m l i n e s in the v i s i b l e c a n n o t be due to e l e c t r i c dipole r a d i -


ation, s i n c e t h e r e i s no c h a n g e in the p a r i t y of the i o n . T h e y a r e due to
m a g n e t i c dipole r a d i a t i o n . T h e r a d i a t i v e t r a n s i t i o n p r o b a b i l i t i e s c a n be
c a l c u l a t e d without d i f f i c u l t y . E x c i t a t i o n c a n be due to a n u m b e r of d i f f e r e n t
mechanisms.
(i) E x c i t a t i o n by a b s o r p t i o n of photo s p h e r i c r a d i a t i o n ,

X1 +hi/^X2 (2.9)

(ii) D i r e c t e x c i t a t i o n by e l e c t r o n i m p a c t ,

x ; m + e - X™ + e (2.10)

(iii) E l e c t r o n i m p a c t e x c i t a t i o n of h i g h e r l e v e l s , followed by c a s c a d e

Xj + e -» X 3 + e

m
x; - x ™ + hv (2.11)

If t h e t r a n s i t i o n 1 3 i s allowed f o r e l e c t r i c dipole r a d i a t i o n , and 1 2


f o r b i d d e n , t h e c r o s s - s e c t i o n Q ( 1 -<• 3) m a y be a f a c t o r of 10 o r so l a r g e r
t h a n Q(1 - 2).

(iv) E l e c t r o n i m p a c t e x c i t a t i o n v i a a u t o - i o n i z i n g l e v e l s ,

X™ + e к ( X ' ! n : - : ; ) - - X;m + e (2.12)

(v) E x c i t a t i o n by p r o t o n i m p a c t ,

X ™ + H + ~ X ™ + H+ (2.13)

In g e n e r a l , a l l of t h e s e p r o c e s s e s c o n t r i b u t e s i g n i f i c a n t l y . High in
the c o r o n a , w h e r e N e i s s m a l l , p r o c e s s (i) i s d o m i n a n t , while at l o w e r
l e v e l s p r o c e s s e s (iii) and (iv) a r e g e n e r a l l y d o m i n a n t . A g r e a t d e a l of
a t o m i c data i s r e q u i r e d in o r d e r to m a k e good c a l c u l a t i o n s of t h e i o n i -
z a t i o n e q u i l i b r i u m and of e x c i t a t i o n r a t e c o e f f i c i e n t s , and it i s only in
r e c e n t y e a r s t h a t t e c h n i q u e s f o r the c o m p u t a t i o n of t h e s e data have b e e n
d e v e l o p e d . F o r the q u a n t i t a t i v e i n t e r p r e t a t i o n of c o r o n a l line i n t e n s i t i e s ,
a g r e a t d e a l m o r e w o r k r e m a i n s to be done.
R a d i a t i o n f r o m i n t e r m e d i a t e i o n i z a t i o n s t a g e s (say 5 t i m e s i o n i z e d ,
r a t h e r than 10 to 15 t i m e s ) i s g e n e r a l l y not o b s e r v e d in t h e o p t i c a l r e g i o n ;
f o r t h e s e s t a g e s e l e c t r i c dipole t r a n s i t i o n s give r a d i a t i o n in the u l t r a -
v i o l e t and t r a n s i t i o n s b e t w e e n f i n e s t r u c t u r e l e v e l s give r a d i a t i o n in the
i n f r a - r e d . B u t e v e n in t h e u l t r a - v i o l e t ( o b s e r v a t i o n s f r o m r o c k e t s and
s a t e l l i t e s ) r a d i a t i o n f r o m t h e s e i o n s i s found to be c o m p a r a t i v e l y w e a k .
Such o b s e r v a t i o n s have b e e n v e r y i m p o r t a n t f o r gaining i n f o r m a t i o n about
t h e t e m p e r a t u r e s t r u c t u r e of the s u n ' s a t m o s p h e r e . In the p h o t o s p h e r e ,
at T — 1, the t e m p e r a t u r e i s T = 6000 K. At the " t o p " of the p h o t o s p h e r e
the t e m p e r a t u r e r e a c h e s a m i n i m u m v a l u e c l o s e r to 5000 K. It then r i s e s
to v a l u e s in the r a n g e 1 0 ' to 10 ü К i n t h e r e g i o n known a s the c h r o m o s p h e r e ,
and finally, r i s e s v e r y s t e e p l y to 2 X 10® К in the c o r o n a . The t e m p e r a t u r e
in t h i s s t e e p t r a n s i t i o n r e g i o n i s m a i n l y d e t e r m i n e d by t h e r m a l conduction.
I A E A - S M R - 1 2 / 4 4 , 46 , 48 273

S o l a r c o r o n a l i n e s o b s e r v e d at u l t r a - v i o l e t and X - r a y w a v e l e n g t h s
(the XUV r e g i o n ) a r e e x c i t e d by e l e c t r o n i m p a c t . A t t e m p t s a r e being m a d e
to d e t e r m i n e t e m p e r a t u r e s and d e n s i t i e s f r o m o b s e r v e d l i n e - i n t e n s i t y r a t i o s .
T h e XUV o b s e r v a t i o n s have b e e n of p a r t i c u l a r i n t e r e s t f o r the study of
l o c a l i z e d " a c t i v e r e g i o n s " , w h e r e T m a y be a s high a s 107 К o r m o r e .
In t h e s e r e g i o n s one o b s e r v e s i o n s s u c h a s F e XXV, i . e . h e l i u m - l i k e
i r o n . One a l s o o b s e r v e s m a n y l i t h i u m - l i k e i o n s .

3. GASEOUS N E B U L A E

In t h e i r a s t r o n o m i c a l s i g n i f i c a n c e the d i f f u s e e m i s s i o n line n e b u l a e
and the p l a n e t a r y n e b u l a e a r e quite d i f f e r e n t t y p e s of o b j e c t s . T h e d i f f u s e
n e b u l a e a r e a s s o c i a t e d with r e g i o n s of g a s and dust having a t o t a l m a s s of
o r d e r 1 0 5 M e (M Q = t h e m a s s of the sun). They a r e r e g i o n s of s t a r f o r -
m a t i o n . A m o n g t h e s t a r s f o r m e d a r e the hot, m a s s i v e and l u m i n o u s О
and В s t a r s . T h e s e s t a r s have an a p p r e c i a b l e e n e r g y output with f r e q u e n c y
v > v-y, w h e r e hp-y i s the t h r e s h o l d e n e r g y f o r i o n i z a t i o n of H ( l s ) . In c o n s e -
q u e n c e the g a s in the n e i g h b o u r h o o d of t h e s e s t a r s b e c o m e s i o n i z e d , and
g i v e s the o b s e r v e d e m i s s i o n - l i n e s p e c t r u m .
A p l a n e t a r y n e b u l a i s p r o d u c e d when an old, highly evolved s t a r e j e c t s
an o u t e r e n v e l o p e , having a m a s s of about 0.1 M Q , and l e a v e s behind a hot
c e n t r a l s t e l l a r c o r e , which p r o d u c e s r a d i a t i o n c a p a b l e of ionizing the
ejected gas.
The p h y s i c a l p r o c e s s e s in t h e s e two t y p e s of n e b u l a a r e v e r y s i m i l a r .
The p r i m a r y p r o c e s s i s p h o t o - i o n i z a t i o n . M o s t of the f r e e e l e c t r o n s c o m e
f r o m i o n i z a t i o n of H ( l s ) :

H ( l s ) + hp - H + + e (p> vx) (3.1)

If the a m o u n t of g a s p r e s e n t i s s u f f i c i e n t to a b s o r b all of the ionizing


r a d i a t i o n , it c a n be shown t h a t t h e r e i s a r a t h e r s h a r p b o u n d a r y b e t w e e n
the ionized g a s , and the n e u t r a l g a s which o c c u r s f u r t h e r away f r o m the
hot s t a r . W i t h i n t h e i o n i z e d r e g i o n the a m o u n t of n e u t r a l g a s i s s m a l l
N(H°)/N(H + ) being of o r d e r 10" 3 to 10" 4 .
The p r i m a r y p h o t o - i o n i z a t i o n p r o c e s s i s e v e n t u a l l y followed by r a d i -
tive r e c o m b i n a t i o n , which can be to any e x c i t e d s t a t e ,

H + + e - H(ni ) + hp' (3.2)

The excited s t a t e s d e c a y r a d i a t i v e l y

H(nf> ) -» H ( n ' i ' ) + hf n n . (3.3)

giving r a d i a t i o n which can be o b s e r v e d . E v e n t u a l l y the a t o m r e a c h e s the


g r o u n d s t a t e . The c o n d i t i o n s of d e n s i t y and of i n t e n s i t y of r a d i a t i o n a r e
such t h a t m o s t n e u t r a l H i s in the g r o u n d s t a t e . In c o n s i d e r i n g the i o n i -
z a t i o n e q u i l i b r i u m , i o n i z a t i o n f r o m the g r o u n d s t a t e i s the only i o n i z a t i o n
p r o c e s s which n e e d be c o n s i d e r e d .
E l e c t r o n - e l e c t r o n c o l l i s i o n s a r e v e r y e f f e c t i v e in r e d i s t r i b u t i n g
e l e c t r o n k i n e t i c e n e r g y and it m a y t h e r e f o r e be a s s u m e d t h a t the e l e c t r o n s
have a Maxwell d i s t r i b u t i o n and an e l e c t r o n t e m p e r a t u r e , T . T h e e l e c t r o n
d e n s i t y i s denoted by N e .
274 SEATON

In the p r e s e n t s e c t i o n we t a k e r a d i a t i o n i n t e n s i t y I to be m e a s u r e d in
q u a n t a p e r unit a r e a , p e r unit t i m e , p e r unit solid angle (in s e c t i o n 1 we
took I to be in units of e n e r g y p e r unit a r e a , e t c . )

The i o n i z a t i o n e q u i l i b r i u m . With N(H°) = N(H(ls)), the n u m b e r of ioni-


z a t i o n s (3.1) p e r unit v o l u m e p e r unit t i m e i s
oo
N(H°) 4 т г J , dy (3.4)
"i
w h e r e a 1 (i/) i s the c r o s s - s e c t i o n f o r (3.1) and w h e r e J^ i s the i n t e n s i t y
averaged over direction,

3 5
= / ^ < - >

w h e r e du i s an e l e m e n t of solid a n g l e . The n u m b e r of r e c o m b i n a t i o n s to