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Wave Functions for the Hydrogen Atom in Spheroidal Coordinates II: Interaction with a Point

Charge and with a Dipole

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 828

Wave Functions for the Hydrogen Atom in Spheroidal Coordinates

11: Interaction with a Point Charge and with a Dipole

BY I?. D. ROBINSON
Mathematical Institute, Oxford

Commuiiicated by C. A. Co:ilson; iMS. received 30th Deceinbev 1957, aizd zit fitial forlli
12th Febviia~y1958

Abstract. T h e interactions of a point charge and of a point dipole with a hydrogen

atom are investigated. Interaction energies, dipole and quadrupole moments
are calculated using exact perturbation theory. Spheroidal coordinates are
necessary to solve the differential equations which arise, and wave functions for
the atom in these coordinates are seen to be the correct zero-order ones to use,
T h e exact form of the perturbing potential is employed, giving results with both
polynomial 2nd exponentially decreasing terms. These are compared with the
simpler but less accurate results obtained when the expanded form of the
perturbation is used. i
Ej 1. INTRODUCTION
Part I of this paper (Coulson and Robinson 1958) wave functions for the

1
N
hydrogen atom were developed using spheroidal coordinates ( f , ? ,$) in the
form
$4l,lIL.Ir==xP 1- w(5+rl)ln1:(52- 1)(1-?‘)i’”“’~I~(EZfr,(rl)exP
( k m+),
f , ; ( t ) being a polynomial in t of degree n - lml - 1 ; the atomic nucleus was at
one focus of the coordinate system ((= 1, 7 = - 1) while the second focus
(6 = 1, 71= 1) was chosen at an arbitrary point in space. It was seen that if a point
charge was now placed at this second focus, then the resulting addition H to
the Hamiltonian had zero off-diagonal matrix elements with respect to the set
of functions {y!rll, ? I I . ,-}, i.e.

unless we have m, = m B and k , = k,. This means that spheroidal wave functions,
with foci at the nucleus and at the point charge respectively, are the correct
zero-order ones for a perturbation investigation of the effect of a point charge
on a hydrogen atom. Conventional non-degenerate perturbation theory zan
then be used with these functions, even for the degenerate excited states of the
atom. In this way we avoid the difficulties of Coulson and Gillam (1947), who
mistakenly used parabolic wave functions to study the interaction of a proton
and an excited hydrogen atom. As was shown in Part I, the parabolic wave
functions are the limiting cases of the spheroidal ones as the interfocal distance
R+ Co.
Dalgarno and Stewart (1956 b, 1957) have made perturbation calculations
of properties of HeH2+, taking as their model a hydrogen-like atom with nuclear
 Wace Functions j o y the Hydrogen Atom in Spheroidal Coordinates : 11 829

charge j perturbed by a point charge 5'. They set 5= 1, 5' = 2 for the l s a state
of the ion, and 6 = 2, 6' = 1 for the 2pa state, each with the 1s hydrogen-like wave
function; for the 2p.rr state they used the 2p, function with 5= 2, j ' = 1, and so
of their unperturbed wave functions was degenerate. Dalgarno and
Stewart, like Coulson and Gillam, employ the form of the perturbation H'
]Vhich is expanded in powers of 1/R, i.e. they use
m
- 2 rpnP,(cos6')/Rn+l
,1=1
of ( 1 / R - I / % ) (see figure 1). This treatment leads to results given by
Series which are asymptotically divergent for all values of R (Dalgarno and
Lewis 1956), and it also neglects the exponentially decreasing terms which arise
wth the unexpanded form of H . T o avoid these shortcomings spheroidal
coordinates are necessary, not only to take care of any degeneracy but also to
solve the differential equations which arise when exact second-order perturbation
theory is used with the unexpanded form of H'.
The effects of a point charge (the energy of interaction and the dipole and
quadrupole moments induced in the atom) are discussed in $342 and 3, while
in $ 4 the effects of a charge dipole are investigated. It is not easy to proceed
using the exact form of H if the hydrogen atom is in a general excited state,
for we do not know the explicit form of the polynomial fk occurring in +,, k.
In principle its coefficients can be found numerically for any given state, but for
simplicity we will here content ourselves by considering only the cases of K- and
L-shell wave functions.

Figure 1.

$ 2 . ENERGY OF INTERACTION WITH A POINT CHARGE

+
In figure 1, the atomic nucleus is at A, the electron at P and the point charge 4
1s at B. The spheroidal coordinates of P are 5 = ( T + ~ rb)/R,q = (rp - rb)/R and 4,
the azimuthal angle round the axis AB, The unperturbed wave functions
considered are
(1) K shell, n= 1, m=O:
exp [ - i R ( f + ~ ) ] / d(the
n 1s function),
L shell, n = 2 , Iml= 1 :

-
(11)

R
162/7r
(f2- 1)1'2(1 - q2)1,2exp [ - &R(E+ q)] exp ( f id) (the 2pi, functions),
(iii) L shell, n = 2, m = 0 :
830 P.D.Robinson
where u2-4w./R - 1= 0. (There are two degenerate functions for the same n- and
m-values here, one from each root for cc. They are linear combinations of the zg
and 2p, spherical polar functions.) All these functions are correctly normalized,
and in atomic units.
We can treat q as a parameter, writing the perturbation to the Hamiltonl,,,
as q H ' = q ( l / R - l/rb), and we shall use the exact second-order perturbatlo,,
theory of Dalgarno and Lewis (1955). If w e set V = - 1/rb= - 2 / R ( [ - 4
and if F ( f ,7) is an acceptable solution of the differential equation
V2F+ 2 grad F , grad (In i,b) = V -
i' 4," V# d r . .. . . . (1)
where # is the unperturbed wave function of the state considered, then this
theory gives for the interaction energy
AE = q( 1/ R + E('))+ q2E(2 ) + O ( q 3 ) (in atomic units),

T h e notation
J' #++L#dr=(#ILI#) will be used, so that
E(1)=(#lVl#), and E(2)=2{(#IVFI#)-E(1)(#IFI#)1. . , . . . (2) .
The function F ( 6 , q ) is introduced as an ingenious means of summing the infinite
series which normally occurs in the second-order energy term. Equation (1)
can only be solved analytically if spheroidal coordinates are used, and so if n e
want to retain the exact form of V these coordinates are necessary even with the
non-degenerate wave functions (i) and (ii).

2.1. Case (i), n = l , m = O

This is equivalent to the work of Dalgarno and Lynn (1957), but it is given
here both for completeness and also because the results obtained are used later
in os3 and 4.
I n this case we have $=exp [ - &R(e+q)]/4772nd

'1
E(1)= -
i7
exp[-R(f+q)]

Equation (1) for F becomes

- -fR2E(1'(62-q2)- i,R((i-?).
This is separable in the form F ( f , q )= Fl(6)+ F2(q),and if we choose the arbitrar!
constants which arise so that F ( f , q ) is well-behaved along the axis where
and = i 1, then F ( f ,q ) is uniquely determined as

- 4 (1+ k) [ln(l-q)+Ei*(R(l-q))]

+ 4 e--2R(1 + i) [In (1 + q ) - Ei[R( 1 +?);I*

 Wane Functions for the Hydrogen Atom in Spheroidal Coordinates : II 83 1

Here
-1
Ei(t)=
J
I --m
eL/xdx
'00
and = J
Ei++(t) e-x/xdx= - (Ei - t)

are the usual exponential integrals.

The following expression is finally obtained (from formula (2))
5
2R2
1.
+e+R [2 (1+ k ) 2 ( y + l n 2 R ) -
(2 + - + - j 2 )
- (1-
\ R 1
+e-A" [2 (1- k)2 7
2 R
4
( y + l n 2 R ) + 2 R + .- + - + -
2R25 1

~
2
R R2
3
+Ei*(2R) [1+ - - - + - I + - e-2R
:( A) 1
\there y is Euler's constant. This agrees with the result of Dalgarno and Lynn
apart from a factor of 2 whlch arises from their use of the Rydberg rather than
the strict atomic unit as unit of energy. If the asymptotically divergent series
for the exponential integrals
n! (n 9
Ei(2R)=e2R -
n=o (2R)"+l '
Ei*(2R) = e-2R I t2
=0
( - ) ) t on+'
are substituted in the expression, and the exponentially decreasing terms are
neglected, then
E@)=- 2 (2s- 1)2!2(2s+ l)(s+2)
~~29+2
s=l
in agreement with Dalgarno and Stewart (1956 b). Dalgarno and Lynn give
a table to show the accuracy of this series expansion; it is very accurate for
large R and quite useful for R as small as 4a,. The error arising from the
asymptotically divergent nature of the series is small compared with that which
arises from neglecting the exponentially decreasing terms.

2.2. Case (ii), n = 2, Iml= 1

Here we have

It can be shown that

and that the equation for F is :

832 P. D.Robinson
If, as before, the finiteness conditions are applied along the axis, we get

etR e4R
7-1 ?+1
+ K z(4R-1)e~R[ln(1-~)+Ei*{+R(1-7))]
1
+K,(+R+l)e-~R[ln(1+7)-Ei{+R(1+y))],
where

K l ( l + i ) +44E(1)+1=0 and

Using this, we obtain the expression

=

+ exponentially decreasing terms,

If the series are substituted for the exponential integrals, E@)becomes
--
78 + 2400
RB I 2(2s- 1) ! (s+2)(2s3+3s2-13s-8)
R4 S= J (S - 1)(s - 2) R 2 s + 2

i n agreement with Dalgarno and Stewart (1957), apart from the factor of 2,
They obtained this series result using the expanded form of H'.
Table 1 shows the error caused by neglecting the exponentially decreasing
terms in E(1)+1/R, and also the error resulting from the use of the series rather
than the exact expression for E ( 2 ) . T h e coefficients of the series increase rapidh
the next terms being
20400 + 1169280 + 106686720 + 14497781 760
RS RIO RI2 R14

It is convenient to sum the series for a given value of R by including termsup

to but not including the smallest term, plus half the smallest term (Dalgarno
and Lewis 1956, Jeffreys and Jeffreys 1956). We see from the table that serious
errors arise if the series form of E(2)is used for R < 9. It is to be expected that
the error in neglecting the exponentially decreasing terms in the unexpanded
form of E(2)(the labour involved was thought too great to justify finding then11
will be comparable with that in neglecting them for the q term. Consequentl!,
for this L shell state of the hydrogen atom, with the electron generally furthe:
out from the nucleus than in the K shell, the error inherent in the series for 3''
is of importance below R = 7, and it is essential to use the exact form of tht
perturbation H'.
wave Functions f o r the Hydrogen Atom in Spheroidal Coordinates : 11 833

I I .^
h
c)

-
c
A 0 0 0 0
U

13:
h

w
834 P. D.Robinson
2.3. Case (iii), 72 = 2, m = 0
This time

where U satisfies the equation u2- 4a/R - 1 = 0, the two roots giving two differer,
functions 4. These functions, although degenerate, are the correct zero-ordt
ones to use, as explained in 5 1.
We obtain
EP)= - -1
R
-+('+--")(-)
+ R2a
3 1
3 R R% 1-a
l+a
exp(-R).

T h e procedure for finding E(2)is the same as in the previous cases, but the workln:
involved is more tedious. T h e equation for F is

which has for its acceptable solution

x [ln(l+~)-Ei{~R(l+~))J+ (=
l2
- -1
1 [ln(l-17)+Ei*~-~R(l-~)~~

where
&(I-&) = ~ ( 1 + 6 E ( ~ ) ) - 1 - 4 E ( 1 )and K 3 = 2 a + -12 - K 3 .
R
T h e expression for E(2)is found to be

-11
+ - 162 + 1798
- + 7728
- a
+ 2 5 +; -: 3 , -
lST
' 2) + 240(1- Ra/2)
R6(1+ $R2)
T
2 R2 R4 Re

+ exponentially decreasing terms.

T h e expansion of AE in powers of 1/R starts

which agrees with the results of Coulson and Gillam (1947) (with q = 1) as far
asthe term in 1IR4.
 Jvaae Functions for the Hydrogen Atom in Spheroidal Coordinates : II 835

Table 2 shows the importance of the exponentiaily decreasing terms in the

first-order energy

for the two values of a, denoted by

+ (1+ 4/R2)Il2 and
U + = 2/R a- = 2/R- (1+ 4/R2)1/2.
It is clear from table 2 that the exponentially decreasing terms can only be
sJfely ignored for R < 12 when the positive root is taken for a ; this is the case
\,hen the charge cloud is concentrated more between the nuclei. The exponentially
decreasing terms arise from considering values of Y~ greater than R, for they
do not appear at all when the expansion
m
HI=- 2 ra2LP,z
(COS O)/R'i+l
11 = 1

\\hich is only valid for T?, < R is employed. Such a startling difference in the two
cases however would not have been anticipated.
The formula for E@)with the positixre root for a should be accurate for quite
small values of R.

8 3. DIPOLEAND QUADRUPOLE MOMENTS

INDUCED CHARGE
BY A POINT
The presence of the point charge q in the neighbourhood of the hydrogen
dtom not only alters the energy of the system but also changes the shape of the
charge cloud. Suppose the wave function is perturbed by q to
$ = $(")+ q$(" + q j w + . ...
Then quantities like the dipole moment ( $ I ~ ~ P ~ ( O)l$)
c o s and the quadrupole
moment ($]~~*P~(cosO)l$) of the charge cloud will be different from their
ialues with q=O. The differences in these values are the moments induced
by the charge q, and these are investigated here.
-kcording to conventional perturbation theory,
$(l)= 2u l ~ r and $@)=Cb,d,,
1 =U

the summations being over the complete set of orthonormal eigenfunctions f+,),
of which +(O) = Co. The coefficients a, and b, are given by

E,, E,. . . are the energy eigenvalues corresponding to +,., 4,. . . , and ( Y ( H I s )
+
lS written for (#,,lwl#,5).is now correctly normalized to order q2 (see for
example Schiff (1955)). H ' = l / R - l / ? b = l / R +V , and H may be replaced
v in the above formulae because of the orthonormal properties of the functions
If the complete set of eigenfunctions {d,} is taken to be the set in spheroidal
then me shall not be worried by questions of degeneracy.
836 P . D.Robinson

We will consider the value of (#lJl#), whereJ will be put equal to r2P1(cos~
or to ra2P2(cos8). Expanding in powers of q, we have
(4IJI#> = (OlJlO> +4{(#'"IJlO)+ <O"lt',"'>>
+ q y ( + q ~ p+) () p q ~ l p )+)( ~ ) I J I o(q3). +~ ) ~
If now well-behaved functions F and G are defined a s solutions of the different,,
equations
V 2 F + 2 g r a d F . g r a d (lnt,bO)=V - (OlVlO),
as in $2, and
P2G+ 2 grad G .grad (In = J - (OlJ IO),
then using the summation methods indicated by Dalgarno and Stewart (1956 a),
it can be shown that
(4IJI4) = (OlJlO) + 4Q{(OIGVlO)- ( 0 l ~ l O > ( O I ~ l O >:
+ 4q2((OIF2JIO)+ 2(OIFGVIO) - 4(OIFIO)(O(GV10)
+
- 2(01 VlO)(O1FG)O) ( O l J l O > [ (OJFIO)2 - ( O ! F 2 ( 0 ) ]
+~ ~ ~ ~ - (~0 l F ~ l o~) l :+ 0 (~q 3 ) . ) ~ ~
Matrix relations such as
2 ( O I S l ~ , ) (4 TIS) = (OISTls) - (01SlO) (01 TIS)
r#lJ
have been employed. Equalities like (01GViO) = (OIFJ 10) allow alternatirr,
forms and also serve as a useful check on results. As before, results 11-ill on11
be obtained for the K and L shells of the hydrogen atom.

3.1. Case (i), n = l , m=O

3.1.1. Induced dipole naoment: c a k e of 2.
Here J = r a c o s O = x , andcbo=exp (-ra)/d.rr=exp [ - & R ( t + q ) ] / \ / r .
(OIJ(0)= 0 by symmetry. C(l*a,e ) = - i r 2 ( l + 3 r 2 )cos 0 and (OlGlO) also
vanishes. As in $2.1,

+ +(I+ k) e-ZR [ l n ( l + ~ ) - E i { R ( l + ~ ) 1 ] .

After fairly lengthy working the following result is obtained for the induced
dipole moment :
4 47 - -
114
2= 2122
-{9-(2R1+10R3+18R2+18R+9)e-2")+iq2 -2R- -
R RJ {
+(R2-R) 2 - - 12 + -27 - 33
-+-
R( R2 R3 R4
18) e2"Ei" ( 2 R )

+(R2+R)(2+
,
+ exponentially decreasing terms) + O(q3).
 Wave Functionsfor the Hydrogen Atom in Spheroidal Coordinates : II 837

If the series are substituted for Ei(2R) and Ei*(2R), the first three terms in the
of the q2 term are

r:
213
;q2 R j
+-
104625) .
Rg
120
'
I

the first two agree with Dalgarno and Stewart (1956 b ) who used the expanded H'
but did not give the 1/R9 term. Values of the q term as R varies are given in
table 3.

1.1.2. Induced quadrupole mcments, Q.

Here J = Jra'(3 cos '8 - 1 ) for the Qzz component, and (OlJlO) = 0. W e find
that G = - $ra2(f + 4 ~ a ) ( COS'
3 0 - 1) and that (OlGlO) = 0. T h e q term can b e
found quite easily, but the q2 term necessitates heavy integrations and was not
evaluated. It would take a similar form to that in above, and the expansionz
of it (without exponential terms) is given by Dalgarno and Stewart (1956b).
We get

Q-,= 2 {
R3 1 5 - [ y+ E 3 +10R4+20R3+30R2+30R+15] e-PH) +O(q2).

The other quadrupole moments can be deduced from symmetry considerations,

folQsJ = Ql,,? = - $ Q g z and Qyz= Q,, = Qzu = 0.
Table 3 compares the importance of th.e exponentially decreasing terms
(nhich are not obtained by Dalgarno and Stewart) for the induced dipole and
quadrupole moments. It is seen that the error involved in their neglect is more

Table 3
(1) 3 4 5 6 7 8 9 10
(2) 0.40952 0.28125 0.17723 0,12453 0 09176 0 07030 0*05556 0.04500
(3) 18.1 5.67 1.54 0.38 0.09 0.01 0.004 0.001
(4) 0.27077 0.17703 0.10854 0.06722 0.04333 0 02922 0.02056 0 01500
(5) 5 1 *3 24.5 9.55 3.20 0.93 0.26 0 07 0.02

(1) R (units of no) ; (2) coefficientof q in z;

(3) %error* ; (4) coefficient of q in Q,,; (5) %error*
* from neglecting the exponentially decreasing term.
serious with Qzz than with 2. This i s because J has a factor of ra2 in the QZz
case, but only ra in the Fcase, and the contributions to the integrals when ra.> R
giving rise to the exponentially decreasing terms should therefore be greater
for Qzz.

3.2. Case (ii), n = 2 , Im(=1

Here we have nothing to add to the work of Dalgarno and Stewart (1957),
although the more reliable expressions involving exponential integrals could be
derlried using the function F ( ~ , Tof) 82.2.

3.3. Case (iii),n=2, tn=O

The theory is illustrated by finding the q term of the induced dipole moment,
This time
+o= -
R ( I + ,)-1'2 exp[-g~(5+?1)1(t-Y.)(T--)
164r
838 P. D . Robinson

J = z = hR(& + 1 ) and (O[JlO)= 3 R / ( 2- x R ) , not zero as in the previous cases,

F ( ( , ? ) is given in $ 2.3 and after performing the integrations we ohinin

15(1
(1+$R2)2
7
J
1
+exponentially decreasing terms + O(q2).

This expression can be expanded as a convergent power series if R > 2 ; the first 1
few terms are
q{$ + 4-p-
320 (ig+ ”””) Rj +.(&)).
T h e minus sign is taken with the root xL = 2 / R + ( 1 + 4/R2)lI2. The exponential]\
decreasing terms can only he expected to he insignificant with this value of >,
as was the case in $2.3.
z
T h e result for in case (ii) is quoted for comparison ; it is

p=4 { - 4320
R4 + exponentially decreasing terms) + O(q2).

$ 4 . THEEFFECTS
OF A POINTDIPOLE
PERTURBING
Here we consider what happens when a hydrogen atom is in the presence
of a charge dipole of strength p, distance R from the nucleus. I n figure 2, the
nucleus is at A, the electron at P, and the dipole is at B pointing along BB’,
k is a unit vector along AB, i is a unit vector perpendicular to k in the plane ABB,
and j makes up the right-handed orthogonal triad. 4 is the angle between the
planes APR and ABR‘, and r 2 , Y b and 6’ have their previous definitions.

Figure 2.

The dipole can be thought of as the limiting case of charges - 4 at I3 and

3
+p at B’, provided that B’+B and q+w in such a way that qRB’=qdR+P
Thus the effect of the dipole on the atom will be the same as the limiting cast
 Waze Functions f o r the Hydrogen Atom in Spheroidal Coordinates : II 839

ofthe sum of the effects of ( a ) a charge - p a t B on an unperturbed state of the

atom, +o say, and ( b ) a charge + q at B' on the state perturbed by - q at B to

" ,
The notation is that of $ 3 , { $ r } again being the set of eigenfunctions in spheroidal
coordinates to take care of degeneracy.
,ISan example of this technique, the energy of interaction of the dipole with
the hydrogen atom will be investigated. By conventional perturbation theory,
the contribution from ( a ) is
- d O l H ' ( R ) l O ) + p2 z
r#O
(olH'(R)IY>(rlH'(R>Io)+ q q 3 ) ,
Eo - E,
and that from ( b ) is
tq(40-P
1
L:
a , ( R ) ~ I . ! H ' ( R + d R ) I ~ o -L:
+o rzo
q a7.(R)$r.)

+q2 z: + R + dR)IO)
(OlH'(R d R ) I r )( r JH'(
+ 0(P3)-
rfO EO - Er
.idding the two contributions, we get the following expression for the interaction
energy :
(01SH'Ir )(r18H'(O)
A E = lim p(01SH')0)+p2 2 Eo - E,, +0(P3)
gdR-y 1 +O
n here SH' = H'( R + d R ) - H'( R ) .
I n terms of V ,
(OlSH'lO)=S(l/R) + ( O l S V l O ) ,
and
(OlSH' I T ) ( r lSH'10 ) = (018 V i r ) ( r IS VI0).
We can now re-introduce the function F ( f , q ;R ) defined by equation (l),
SOthat we finally obtain
+
I E = lim p{S(1/ R ) (018 VI0)} + 2q2{(018 V8FlO ) - (018 VI0) (OlSFlO )} + O ( p 3 ) .
wlR+
The integrations present some difficulty ; for instance (OlSV(0)+3(0( V\O)
unless n - Iml= 1, in which case $o((, q ) is expressible in a form independent of R.
Furthermore (Oli3VSFlO) can never be deduced from (OlVFlO); both SV and
SFwili have to be found. For simplicity we will consider only the ground state
of the hydrogen atom. $o, F ( ( , q ; R ) and E ( l ) ( R )are just as in $2.1.
x o m for any function g(R) of the magnitude of R ,

lysing this we can show that

2sF=k.dR{raTa E(1' + [$
-e-2R(2+ - 2 + -)]
1 ln(f+1)
R R2
1
+- R2
[In (1 - 7 ) + Ei*{R( 1 - q)]] -
(2 + R- + -
R2
840 P.D.Robinson
where b is a unit vector along PB.
SV=S($) = - b1. d R =
Also b.dR.
Yb R2(6-
Since 4" is independent of R in this case, the first-order term of 4E can Soon
be found; it is
{--+
lim qS 1 (OlVlO)\ = - 2 + - 2 + e-2Rk.y, )'
pdR-p .R J R R2(
(because 1/R+(OlVlO)= (1 + l/R)e-2R).
T h e only case when the second-order term can be obtained at all easily 1s
when the axis of the dipole is perpendicular to AB. Then k . d R = 0 as well as
j .dR, and SF simplifies considerably. I n this case,
dR ((2- 1)112(1 -v2)'l2
b . d R = b . i d R = -r,sinOcos$- =- cos #I dR,
Yb 5-1
and

(OlSVSFlO) is the only non-vanishing contribution, and after some long but
fairly straightforward integrations the interaction energy is found to be

I n the asymptotic series form,

1 1
- + - + 1 - - e2REi*(2R)-
R2 R4 ( iR)
1 +
(s 3)(2s 4) ! + . . . . . . (3)
16R282
N - -

=o (2R)25
T h e right-hand side of (3) begins with
- (" 45 1575
+ - +-
2116 Ra 2RI0
+...).
Table 4 shows how important the exponentially decreasing terms are, particularl!'
when R<7, and also gives values of the left-hand and right-hand sides of
equation (3).
5 5. DISCUSSION
T h e relative merits of the difTergllt forms of the various results should first
be discussed. For the K shell, table 4 above and the table 1 of Dalgarno and
Lynn (1957) both indicate that the error which arises from the use of an
asymptotically divergent series is small compared with that arising from the
neglect of the exponentially decreasing terms. These latter do not become
negligible until R> 7 or Sa,, when the series form might just as well be used*
For the L shell, however, table 1 above shows that with the states n = 2 , Iml *
it is the use of the series expansion which incurs the greater error, and that even
 PVaae Functionsfor the Hydrogen Atom in Spheroidal Coordinates : II 841

the exponentially decreasing terms were neglected it would be still essential

use the unexpanded form for R < 7. As Coulson and Gillam (1947) observed,
due to the divergence of the series will be far more serious with excited
states of the atom. Even SO, it is necessary to get some idea of the magnitude
of the exponentjally decreasing terms before neglecting them. With the
degenerate states n = 2, m = 0 , table 2 shows that the second-order energy term
alll be subject to grave errors for R < 10 with the negative root for a unless the
exponentiallydecreasing terms are found, but with the positive root for ct it should
be accurate for quite small values of R without them.
We see, therefore, that it is desirable to use the unexpanded form of the
H' and SO obtain results free from asymptotically divergent series
and complete with the exponentially decreasing terms. T o do this, spheroidal
coordinates are best employed, even when they are not necessary to take care of
degeneracy, as they are with states where n - Iml> 2. T h e only limitations on
these results now will be the errors arising from the neglect of third and higher
order perturbation terms. A precise assessment of these further errors is not
easy; an estimate of them which might be affected by the inherent faults in the
use of the expanded form of H', can be made from the work of Dalgarno and
Stewart (1956b, 1957). It is not likely that they will be significant for R > 5
uith the R shell and for R > 7 with the L shell.
The main drawback to the use of spheroidal coordinates lies in the heavy
analysis involved in all but the simplest cases. This is contributed to appreciably
by the complicated function F ( ~ , T which
) is vital to the exact second-order
perturbation theory. Although it is preferable to persist with this function
wherever possible and so obtain exact results, the use of the usual Unsold
approximation (1927) for the second-order perturbation term would allow wider
applications of the coordinates.
A word should be said about the results of $$ 2 and 3 in the special case when
q=1, i.e. if the hydrogen atom is perturbed by a proton. Further degeneracy
now arises because of the identity of the protons at A and B, and any theory not
taking account of the existence of a centre of symmetry at the mid-point of the
two nuclei is bound to be inaccurate (Dalgarno and Lewis 1956).
APPENDIX : THEINTEGRATIONS
The integrals can usually be broken down in a straightforward manner to
depend on the basic functions
A,(h) = jm
e-Aetndt,
1
B,,(h)= 1'
-1
e-At)$'d7
and on the exponential integrals. T h e tables of Coulson (1941) and of Kotani,
-hemiya, Ishiguro and Kimura (1955) were found useful, and in $ 4 the reduction
formula of Bartlett (1931) for

was employed where

ACKNOWLEDGMENTS
I would particularly like to thank Professor C. A. Coulson for proposing
this work, and for his continued interest and many helpful suggestions. I am
grateful to the Department of Scientific and Industrial Research for a
maintenance grant.
842 P.D.Robinson
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