The multipole Hamiltonian and magnetic circular dichroism

W. P. Healy

Citation: The Journal of Chemical Physics 64, 3111 (1976); doi: 10.1063/1.432646
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 The multipole Hamiltonian and magnetic circular
dichroism
W. P. Healy
Department of Mathematics, University College London, Gower Street, London WCIE 6BT, England
(Received 17 March 1975)

The Power-Zienau-Woolley transformation in molecular quantum electrodynamics is carried out for a

molecule in an external static magnetic field. From the gauge-independent multipole Hamiltonian thus
obtained the Einstein B coefficients for the absorption of left and right circularly polarized photons by an
oriented molecule in a uniform magnetic field are evaluated. The B coefficients are related to the
macroscopic absorption coefficients by treating the line shapes phenomenologically and by introducing a
Boltzmann factor. A familiar expression for magnetic circular dichroism in a dilute medium is thereby
recovered; the calculation is extended beyond the electric dipole approximation so as to include the leading
contribution of natural circular dichroism. A simple use of the appropriate Kramers-Kronig dispersion
relation leads to the deduction of the optical rotatory dispersion, both natural and magnetic, in spectral
regions far removed from absorption bands.

I. INTRODUCTION proceeds in Sec, III. The B coefficients are related to

the macroscopic absorption coefficients by treating the
We consider the circular dichroism of a tenuous me-
absorption lines, as regards their shape and their dis-
dium, consisting of independent molecules or atoms,
placement with the Zeeman shift, in a phenomenological
when placed in a homogeneous static magnetic field of
fashion and by introducing a Boltzmann factor. In Sec.
flux density B, A substance is said to display circular
IV we extend the calculation of the usual expression 1a,2
dichroism when it differentially absorbs left and right
for the MCD so as to include the leading contribution of
circularly polarized light. For randomly oriented mole-
natural circular dichroism and finally show in Sec. V
cules in solution and in the absence of external fields, a
how the form of the Kramers-Kronig dispersion relation
conditio sine qua non for circular dichroism is that the
applicable to optical activity6,7 may be used to obtain in
molecules be dissymmetric, i. e., they must be inherent-
a simple way the concomitant optical rotatory dispersion,
ly optically active. The effect of the B field on the solu-
both natural and magnetic, in transparent spectral re-
tion is such that this becomes circularly dichroic whether
gions.
or not the molecules are naturally optically active. This
phenomenon is known as magnetic circular dichroism
II. MULTIPOLE HAMILTONIAN
(henceforth abbreviated to MCD) and is the absorptive
counterpart of magnetic optical rotation (the Faraday The Hamiltonian for the complete dynamical system
effect). comprising the quantized radiation field together with a
Previous theoretical treatments of MCD have, for the molecule whose ath nucleus of charge Zae (e > 0) can be
most part, been based on the semiclassical theory of regarded as fixed at Ra and whose ath electron of charge
radiation. 1a,2 Quantum electrodynamics was employed 1b - e and mass m has position operator <la and conjugate
momentum P a isS,s
by Hameka when considering, on the basis of the Heitler-

~ 2~ [Pa+~ a(qa)Y +U,

Ma radiation damping theory, the related problem of
magnetic rotation spectra, and by Atkins and Miller, who H'=Hrad + (1)
used the Stokes operators in conjunction with the S-ma-
trix formalism when discussing several aspects of mag- where Hrad is the radiation Hamiltonian,
netic field-induced optical birefringence occurring at
transparent frequencies. Recently Power and Thiruna- H rad = :11' f (e L2
+b
2
)
3
d r, (2)
machandran3 used molecular quantum electrodynamics
to work out a general theory of the Einstein B coefficients' and U is the instantaneous electrostatic energy of the
for single photon absorption in natural circular dichro- electrons,
ism.
To approach the problem of MCD we consider in Sec.
U=L a<Jl
(3)

II the theory of the quantized radiation field interacting

,with a single molecule or atom, in an external static mag-
netic field. The interaction Hamiltonian to be used 4 ,s is
gauge invariant and readily expressible in multipolar
form through the use of Cartesian tensors. A static
magnetic field as well as adding magnetization and dia-
magnetic terms to the molecular Hamiltonian also modi-
fies the magnetic multipoles appearing in the interaction.
The evaluation of the Einstein B coefficients for the ab-
sorption of left and right Circularly polarized photons by
an oriented molecule in a uniform magnetic field then
In terms of the vector potential a, which satisfies the
Coulomb gauge condition V· a = 0, the transverse electric
and magnetic field operators are, respectively,
eL =_ (l/c)a (4)
b=V"a. (5)
For a molecule in an external static, though not neces-
sarily homogeneous, magnetic field B, the canonical
quantization procedure of the Coulomb gaugeS-when ap-
plied to a classical Lagrangian that yields as equations

The Journal of Chemical Physics, Vol. 64, No.8, 15 April 1976 Copyright © 1976 American Institute of Physics 3111
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 3112 W. P. Healy: Magnetic circular dichroism

of motion for e and b Maxwell's equations with the elec- larization field of the electrons is defined by
tronic charges and currents as sources and for the elec-
trons Newton's law with the Lorentz force due to both the
static and dynamic fields-gives instead of (1) the Hamil-
P(r)=-eL (q",-R)
'"
f
0
6[r-R-,\(q",-R)]d,\, (8)

tonian
then the required transformation is achieved through the
H"=Hrad+~ 2~(Pa+~[a(qa)+A(qa)]r+u. (6)
unitary operator

The vector potential A for the static field is determined (9)

by
In a similar fashion we may transform HI! in (6), using
V><A=B, v·A=o. (7)
now
A canonical transformation4 ,5 may be applied to H' in
(1) to obtain a Hamiltonian that is manifestly gauge in- (10)
variant and in which the multipole form of the interac-
tion is evident. If for a molecule located at R the po- to obtain as the new Hamiltonian

H =. J\. /I HI! A"-1

= H rad + ~ 2~ p~ + U - f i 3
P' e d r - f 3
M' (b +B) d r + ~f f Ojj (r, r')[bi(r)+Bi(r)][b,(r') +Bj(r')] d r d 3 r' +21T
3
f p i2 d 3r,
(11)
where the magnetization vector field is

M(r)=--2e- L
me '"
i0
l
,\{la 6[r-R-,\(qa- R)] +6[r-R-,\(q",-R)]la}d,\, (12)

1'" being the operator for the angular momentum about R of electron Ct', and where the diamagnetic tensor field is

Oi/r,r/)=~
me
L
a
[(qa-R)21i/J_(q",;-Rj)(q",j-Rj)] fl
0
A6[r-R-,\(q",-R)]d,\ t
Jo
,\'Ii[r'-R-,\'(q",-R)]d,\'. (13)

The order of the operators P'" and q"" which is immate- pole contributions to H~ol in (15). Similarly, for the
rial in (6)because of the solenoidal nature of a and A, is field M we obtain from (11) and (13)
prescribed in (12) by the canonical transformation and is
such as to make M Hermitian. Mj(r) =Mj(r) - f °ij(r, r')B j (r')d 3 r'
Considering now only uniform B and taking the mo-
lecular center R as the origin of the coordinate system,
we rewrite (11) as
(14) x f o
A6(r-,\qa)dX. (19)

where the Hamiltonian for the molecule in the external

The contribution to Hint from the terms in (11) quadratic
field is
in b and pi has been discarded, as these terms are ir-
H' ,,1 p! + u - m' , B relevant to the process to be discussed, namely single
mol = L....J 2m photon absorption. The multipole expansions of the po-
a
larization and magnetization fields are
=Hmol-m', B (15)
Pj(r) =Il j 6(r) - QjjV j 6(r) + ••• , (20)
and the radiation-matter interaction energy is
Mi(r) =mili(r) +"', (21)
H 1nt =- J(P'e i
+M'b)d 3r. (16)
where
Some of the diamagnetic terms have been regarded as
B-dependent corrections to the magnetization field. Thus
Ili =-e L a
q"'i (22)

and
(17)
QiJ=- ~ L q",iq",j (23)

the components of the magnetic dipole moment being '"

are, respectively, the components of the electric dipole
e and electric quadrupole moments and
ml=--2
me
L'" lOll' (18)
_ e e2
Because of the uniformity of B there are no higher multi-
mi =- 2me L l",; - 4me2 L (q!liij - q a/ q aj) B J (24)
'" '"
J. Chern. Phys., Vol. 64. No.8, 15 April 1976
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 w. P. Healy: Magnetic circular dichroism 3113

are those of the magnetic dipole moment, again with a
B-dependent correction term. 9 That this correction
term is twice that occurring in (17) is indicative of the
fact that - m ' • B contains the energy of the B-induced
part of the dipole moment in the field B itself, whereas
in (16) m interacts with the radiation field b.
III. GENERAL EXPRESSIONS FOR ABSORPTION
COEFFICIENTS
In the usual experimental arrangement for the mea-
surement of MCD the magnetic field B and the wave vec-
tor k of the incident light are parallel. We therefore
put B=Bk and assume, moreo~er, that the medium is
isotropic in any plane to which k is normal. This situa-
tion holds, for example, for propagation along the optic
axis of a uniaxial crystal or in a solution, where the me-
dium is isotropic in the absence of B. The optical activ-
ity is not then superimposed on linear birefringence and
left or right circularly polarized light propagating along
it is unchanged in its polarization character by passage
through the sample. The circular dichroism at frequen-
cy W =c I k I is defined by
(25)
dn =sine dcj> de dl/J. (30)
ll
The use of Eq. (28) presupposes that the molecules
form a dilute system in thermodynamic equilibrium with
its surroundings at temperature T and that the intensity
of the incident radiation is sufficiently low for shifts of
the level populations to be negligible. Then
(31)
C(T, n) is a normalizing factor and K Boltzmann's con-
stant. Furthermore, if the transition g' - n I is an elec-
tronic one, the population of the excited state at room
temperature is insignificant.
The circular dichroism of a dilute medium has by
(25) and (28) been referred back to the Einstein B coef-
ficients for an oriented molecule. These may be evalu-
ated as follows. 3 The polarization and magnetization
fields (8) and (19) are combined into a single complex
field
d=P+iM, (32) .
and similarly the transverse electric and magnetic field
operators are combined to give
f =e1 +ib (33)

where €(Ll and €(Rl are the left and right absorption co- so that from (16)
efficients and are such that the intensity of incident light
H tnt =-!f(d'f t +d t 'f)d 3r
falls off for a path length 1 according to the Lambert- 2 . (34)
Beer law
f and f t have expansions over the allowed modes in a
I(Z) =1(0) exp[ - E(L}/(Rll]. (26) hohlraum of volume V,
We are using the chemists' convention lO for the handed-
ness, so (25) agrees with the definition for natural cir- f(r) =i ~(81T:wy/2
cular dichroism.
The eigenstates and eigenvalues of H~Ol in (15) are x [e(Lla(L) (k) e lt • r _ e(R)*a(R)t (k) e- Ik 'r], (35)
functions of the orientation of the molecule in the mag-
netic field and are denoted by g' (ground state) with ener- ft(r) =i ~(8lT~W y/2
gy E" and n ' (excited state) with energy En" Those of
Hmol are denoted by g and n with corresponding energies
x [e(R~a(R}(k) elk'" _ e(LI* a(L)t(k)e- lt ' r J. (36)
E, and En. It is assumed that the bases of the spaces G a(~)(k) and a(~)t(k) are, respectively, the annihilation and
and N of the substates of levels E, and En diagonalize creation operators for photons of polarization ~ and wave
- m'· B, so that g and n are the zero-field limits of g' vector k. The polarization vectors are
and n I. The zero-field transition frequency W NG is given
by e(L)(k) = 2- 1 / 2[ e(l) (k) +i e(2)(k)], (37)

liw NG =E n - E, . (27) e(R)(k) = 2- 1 /G[ e(l) (k) - i e(2)(k)] (38)

A(l) A(2) A
The integral over the absorption line g' - n I of the and e ,e ,k form a right-handed orthonormal triad.
contribution to an absorption coefficient (left or right) The transition probabilities per unit time for the absorp-
by molecules with a given orientation is l l tion of left and right circularly polarized photons by a
molecule undergoing the transition g' - n I are
f €"n,(w/)dH dw ' = 2;1i wn'" N"B"n' (wn",)dn, (28)
r(L) = 21T
Ii Ik
I(n ' .' OIH\ a t , e(LI., g') 12p I , (39)
N"dfl. is the number of molecules/cm 3 in state g', and
B"n' is the Einstein B coefficient for the absorption of r!R) = 21T
Ii
I(n ' '· 01 H t nItk" e(R). g') 12p.
t •
(40)
photons of the appropriate helicity and whose frequency
is determined (within the linewidth) by PI is the density of initial states given in terms of the in-
(29) tensity I(erg cm- 3 Hz-1 ) of the incident beam by
V
dn is a differential volume element in the space of the PI = 2lTli2w I. (41)
variables specifying the orientation of the molecules
with respect to a laboratory-fixed coordinate system. The Einstein B coefficientsll are the transition rates di-
Taking these to be the Euler angles cj>, e, and l/J, we have vided by I, and so from (34), (35), and (36),

J. Chern. Phys., Vol. 64, No.8, 15 April 1976

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 3114 W. P. Healy: Magnetic circular dichroism

n'
=;: e:L)e~L)* (n' I f di e It'r d 3r Ig')
FIG. 1. Time-ordered Feyn-
it r man graph that gives the ma-
x (n'l!dje • d
3
r Ig')* (42)
trix element for the absorp-
and tion of a photon of wave vector
k and circular polarization
A by a molecule undergoing
the transition g' --. n' .

The Feynman graph corresponding to the matrix elements

occurring here is shown in Fig. 1. '" En- rn~nB, (46)
The use of the B coefficients gives, through Eq. (28),
the strength but not the shape of an absorption line. 12 and for the kets 14
To distinguish the various effects that give rise to the
MCD, the line shapes must therefore be treated phe- In')= In)- L' I k) (k1rna In)B
k En - Ek
nomenologically and specific assumptions concerning
their variation with molecular orientation in the mag-
netic field must be made. 1,2 In introducing a line shape
'" In) - L' Ik) ~~n B
k nW NK
(47)

function to obtain the absorption coefficients, we meet

an ambiguity as to whether the frequency occurring in
the line strength should be the running frequency w or
the transition frequency wn',' , For simplicity we sup-
pose1 3 that
21Tn
E,'n' (w) dn = - wNI , B"n' (w)fl'n' (w)dn
c B coefficients we go beyond the electric dipole approxi-
and that f is chosen to satisfy (28). In any case f is
supposed to be significantly different from zero only for
frequencies near w n',' -for the application of the disper-
sion relation made in Sec. V it can be treated as a delta
function. Summation over the Zeeman components and
integration over n yields the total absorption coefficient,
due to all molecules, for light of polarization A and fre-
quency w near w NG as
with analogous expressions for E g , and I g'). The prime
on a summation symbol denotes the exclusion of those
states I k) which would give a zero denominator in a
summand. That (46) and (47) are valid expansions when
En is a degenerate level follows from the basis of the
space N being chosen as indicated in Sec. III. For the
(44)
mation and, in order to include the natural circular di-
chroism in a consistent way, consider also the contribu-
tion of the magnetic dipole and electric quadrupole mo-
ments, 15 obtaining from (20), (21), and (32)
f dldt'rd3r=lli+i(mj+Qijkj), (48)
(49)

o.} ( ) - 21Tnw
f.G~N W - C
f (45) If the unit vectors of the laboratory-fixed 123 frame are
taken to coincide with e(l), a(2}, and k, then from (42)
and (43)
with the B coefficients given by (42) and (43).
t:.Bg'n' '" Bif.! -Bi!;,
IV. CIRCULAR DICHROISM
41TI ( ,'n' n',' ,'n' - n',' ,."' - n','
= nZ m Ilz III + III rnl + Ilz m 2
As an illustration of the use of the foregoing, we con-
sider the circular dichroism of a line spectrum in which
+t• ~ (
IlzI ' n' Q13
n' " -
r,I'
't'23
n' IIIn' " ))
the Zeeman energies are much less than KT 1• Z and ex- c
pand the various quantities in (45) up to first order in B (50)
using the stationary perturbation theory for the energies and from (47), to first order in B,

t:.B - 41T I (,n nJ{ ,n - nJ{ ,n - nr . W ( ,n nI r,ln nJ{)

,'n' - n2 m Ilz III + III rnl + Ilz mz + t ~ Ilz Ql3 - 't'Z3 III )

- ~ B 1m {~' n~GK [rn~"( Il ~n Il~ + Il~n rn~ + Il~n rn~ + i ~ (Il~n Q~ - Q~; Il~))
+ III ( ,n nIl In nil ,n nk . W ( ,n Qnk
rn3 Ilz III + III rnl + Ilz rnz +t ~ 112 13
r,ln
- 't'Z3
nil))]
III

J. Chem. Phys., Vol. 64, No.8, 15 April 1976

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 W. P. Healy: Magnetic circular dichroism 3115

+ ~' IiW~K [m~n( j1.~" j1.~ + j1.fkm~ + j1.~k m~ +i; (j1.~k Q~ - (/z~ j1.~))
+ m~ (j1.~n j1.~ + j1.fnm~ + j1.~nm~ +i ~ (j1.~nQ~ - ~~ j1.~)) ] } (51 )

The expansion of the other quantities in (44) and (45) has
been discussed in detail by Stephens. 2 Because to each
zero-field ket Ik) there corresponds a conjugate ket
Ik*), having equal but opposite first-order perturbation
energy, the normalizing factor C(T, n) in (31) is field-
independent, correct to first order in B. Hence, to this
same order, the Boltzmann factor is
ground state and d G is the degeneracy of this state. If
the linewidth is much less than the Zeeman splitting,
then the partial circular dichroism corresponding to
the transition g' - n' and due to molecules with orienta-
tion n is obtained from (25), (44), (51), and (52) as
27T 2 W
Bg~n(w)dn" - 3lic NG(n)dn[(J3g~n +eg~n/(KT)lBf(w)

(52) 47T 2 W
+ 3lic NG(n)dnCRg~nf(w) , (53)

where, in the absence of B, NG(n)dn is the number of where the line shape functionj(w) has been assumed to
molecules/ cm 3 with orientation n and occupying the be independent of A and where

+m~k[j1.~nj1.~ + J-Lfnm~ + j1.~nm~g +i(w/c)(j1.~nQ~ -~~J-L~)]}) , (54)

(55)
eg~n= - (3/d G)Im{[ ~n j1.r + J-Lfnmr + J-L~nm~ +i(w/c)( ~nQ~ - ~~j1.r)lm~g},
CRg~n =(3/2d G) Im[ j1.~n J-L~g + J-Lfnmr + J-L~nm': +i(w/c)( J-L~nQ~ - Q~~j1.r)l ' (56)

These expressions are generalizations of the param- shift, that

eters given by Buckingham and Stephens 1 for the case
when the Zeeman components are well resolved.
When the Zeeman energies are much less than the
linewidths we have, assuming that f depends on molecu-
lar orientation only by moving rigidly with the Zeeman
f(w) =fo(w) + (m;n - m~g)(B/Ii)f'(w) , (57)
where fO(w) is the zero-field line shape function and
f'(w) is its derivative with respect to w, Combination
of (25), (45), (51), (52), and (57) then gives the total
circular dichroism in the vicinity of w NG as

with

aG~ N" :G t; 1m {[j1.~n J-Lr + j1.fnm r + ~nm': +i;( J-L~nQ~ - ~~J-Llg)J(m~g - m3n)} ,
" .!. L Im[ ~n J-Lr (m~g - m~n) 1,
d g,n
G
(59)

(60)

(61) "~ " Im[ 1--'1

2d L...J . .cnmnK
1
+ ,....2
lI'"mng2
G ',n

J. Chem. Phys., Vol. 64, No.8, 15 April 1976

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 3116 W. P. Healy: Magnetic circular dichroism

(62) RTlI: is the optical rotatory strength for the transition

g-n.
The simplification of these expressions that follows on
summation over the Zeeman components is due 2 to the The contributions of higher multi pole moments 9 can
fact that under the operation of complex conjugation m readily be included by following the general treatment
changes sign, whereas p., Qjj, and the field-dependent of Sec. III and by making use of available explicit for-
part of m are unaltered. Thus the term involving (}t in mulas 3,7,17 for the averaging of CarteSian tensors.
(58) is independent of the magnetic field and is the con-
tribution of the natural circular dichroism. 3 The other V. APPLICATION OF DISPERSION RELATION
term in (58) gives the MCD and is proportional to B. So It is of interest to deduce the optical rotatory disper-
to the order considered the natural circular dichroism sion from the circular dichroism by making use of the
and the MCD are simply additive. <1, <E, and e are the generalization of the Kramers-Kronig dispersion rela-
Faraday parameters2,16 describing the effects of, re- tions to optically active media. 6,7 This can be done very
spectively, the Zeeman energy shifts, the mixing of un- simply by assuming sharp absorption lines and taking
perturbed states by the magnetic field, and the popula-
tion changes due to the splitting of a degenerate ground jO(w) =1i(w - WNG), (71)
state.
f'(w) =~ 1i(w - w NG ). (72)
If the medium is isotropic before the magnetic field is oW
applied, then For in a transparent spectral region the partial opti-
1 cal rotation having its origin in a remote absorption line
NG(n) = 8rr2 N G , (63) or narrow absorption band will not much depend on the
fine details of the line shape but will rather be deter-
where NG is the total number of molecules/cm 3 in the mined by the strength of the line and its location. The
ground state. The n integration in (58) can then be optical rotation is given by
carried out by using the averages
¢G_N(W)
2w
=--;- P
2
i° oo
8 G_ N (w') d '
w'(w1'2 _ w 2 ) W , (73)
(64)
with P meaning that the integral has its Cauchy principal
(65) value. This dispersion relation is valid if the direction
of propagation is such that circularly polarized light is
Here (Rj~) is the 3 x 3 orthogonal matrix of direction transmitted through the medium and if the effect of high
cosines specifying the relative orientation of the molec- multipoles is neglected7; it can therefore be applied to
8 G_ N as given by (66). Using (71) and (72), we obtain
ular and laboratory frames, which are assumed to have
the same (right) handedness. Because of the symmetry
of Q"V and the antisymmetry of E~"v, the contracted
products of the form E ~w Il~Q w can give no contribution
when the parameter iR for the natural circular dichroism
in Eq. (62) is spatially averaged. The other terms are
easily evaluated and lead to (74)
2
2rr N - I
8G_ N(W) = - ~ w[ (<1 G_ N/n-)f (w) The first term here is just the Rosenfeld-Condon ex-
pression lB for natural optical rotation by isotropic media.
- - 0 4rr2NG - 0) The other two terms give the magnetic optical rotation
+(ffiG_N+eG_N/KT)f (w)]B+"""3'ii'"CWiRG-Nf (w ,
in the Faraday effectI,16,19 and may be written as VB
(66) with the Verdet constant
with 2
- 4rrNG (2W NG W <1 G-N
V- -
W2[(.iiG_N+e~_N/(KT)1)
(fG_N= 2~ LIm[,f"xP.n.I'. (mnn_mU)], (67)
3nc n WNG - W2)2 +
(2
W2NG - W •

G K.n (75)

ACKNOWLEDGMENTS
I am grateful to Dr. T. Thirunamachandran for sug-
-L k
I 1
--,f"x
nW GK
p."k. mkz) , (68) gesting this field of work and to both him and Professor
E. A. Power for discussions and a critical reading of
(69) the manuscript. This research was carried out during
the tenure of a UK Science Research Council Student-
ship.

l(a) A. D. Buckingham and P. J. Stephens, Ann. Rev. Phys.

(70) Chern. 17, 399 (1966); P. N. Schatz and A. J. McCaffery,
Quart. Rev. 23, 552 (1969); D. Caldwell, J. M. Thorne, and

J. Chem. Phys., Vol. 64, No.8, 15 April 1976

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 W. P. Healy: Magnetic circular dichroism 3117

H. Eyring, Ann. Rev. Phys. Chem. 22, 259 (1971); P. J.

Stephens, Ann. Rev. Phys. Chem. 25, 201 (1974); (b) H. F.
Hameka, J. Chem. Phys. 36, 2540 (1962); P. W. Atkins
and M. H. Miller, Mol. Phys. 15, 491 (1968).
2p. J. Stephens, J. Chem. Phys. 52, 3489 (1970). See also S. Kielich, Acta Phys. Pol. 29, 875 (1966).
3E. A. Power and T. Thirunamachandran, J. Chem. Phys. 10D• Caldwell and H. Eyring, The Theory at optical Activity
60, 3695 (1974). (Wiley, New York, 1971).
4E. A. Power and S. Zienau, Philos. Trans. R. Soc. Lond. l1 B. I. Stepanov andV. P. Gribkovskii, TheoryojLuminescence
A 251, 427 (1959); P. W. Atkins and R. G. Woolley, Proc. (!liffe, London, 1968).
R. Soc. Lond. A 319, 549 (1970); R. G. Woolley, ibid. 321, 12For a calculation from the theory of resonance scattering
557 (1971); M. Babiker, E. A. Power, and T. Thirunama- of the natural line shape due to radiative damping in natural
chandran, ibid. 332, 187 (1973), and 338, 235 (1974) •. circular dichroism see V. Lawetz and D. A. Hutchinson,
5E. A. Power, Introductory Quantum Electrodynamics (Long- Can. J. Chem. 47, 576 (1969).
mans Green, London, 1964). 13See also Schatz and McCaffery, Ref. 1, and Stephens, Refs.
6A. Moscowitz, Adv. Chem. Phys. 4, 67 (1962); C. A. Emeis, 1 and 2, whose definition of circular dichroism differs from
L. J. Oosterhoff, and G. de Vries, Proc. R. Soc. Lond. our Eq. (25) by a factor of w/(2c). In the first (electric di-
A 297, 54 (1967); w. P. Healy and E. A. Power, Am. pole) approximation, the B coefficients are frequency inde-
J. Phys. 42, 1070 (1974). pendent, but even then there is still an wn'g' appearing on the
lW. P. Healy, J. Phys. B 7, 1633 (1974). right-hand side of Eq. (28).
8W. Heitler, The Quantum Theory oj Radiation (Clarendon, 14Note that if the kets I n) are normalized, then the kets I n')
Oxford, 1954); P. A. M. Dirac, The Principles oj Quantum are not. However, the departure of ftz'l n') from unity is of
Mechanics (Clarendon, Oxford, 1958). order B2 and so the error involved in using the unnormalized
9The nth terms of the expanSions (20) and (21) are kets to calculate the transition rates in (39) and (40) is also
of order B2.
(_1)"-1 P['j>"'k Vi ". V k6 (r)
15If we make the estimates f.l ~ eao, in ~ O'eao, Q ~ ea~, and
"-1 -( ) nw ~ e 2/ ao, where ao is the Bohr radius and 0' the fine struc-
and (-1 ) MI;'''kV, "'Vko(r)
ture constant, then m~ Qk ~ O'f.l. In Eq. (50), all terms of
with the 2"-pole moments
order f.l2 or 0'f.l2 have been retained.
p(n) _.!!... ""
L.J
Ij ' ' ' k - - nl
q q ' •• q
",I fY.j fY.k
16R • Serber, Phys. Rev. 41, 489 (1932).
. '" 17S. Kielich, Acta Phys. Pol. 20, 433 (1961), and Bull. Soc.
and Amis Sci. Lett. Poznan B 21, 47 (1968/69).
18L. Rosenfeld, Z. Phys. 52, 161 (1928); E. U. Condon, Rev.
Mod. Phys. 9, 432 (1937).
19M. P. Groenwege, Mol. Phys. 5, 541 (1962).

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