1959 RSTA Coulomb Gauge in Non-Relativistic Quantum Electro-Dynamics and The Shape of Spectral Lines

PHILOSOPHICAL TRANSACTIONS
OF THE
ROYAL SOCIETY OF LONDON

Series A. Mathematical and Physical Sciences
No. 999 Vol. 251 pp. 427-454 15 September 1959
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C o u l o m b g a u g e i n n o n -r e l a t i v i s t i c q u a n t u m e l e c t r o
d y n a m i c s AND THE SHAPE OF SPECTRAL LINES
By
E. A. P ow er and S. Z ie n a u
Published by the Royal Society

Burlington House
Piccadilly
London, W. i
Price Nine Shillings

[ 427 ]
COULOMB GAUGE IN NON-RELATIVISTIC QUANTUM ELECTRO

DYNAMICS AND THE SHAPE OF SPECTRAL LINES
B y E. A. P O W E R and S. ZIEN A U
University College London
{Communicated by H. S. W. asey, F.R.S.— Received 16

M
Revised 31 October 1958)
CONTENTS
PAGE pag e
1. I n t r o d u c t io n a n d sum m ary 427 3 2. The natural shape of spectral lines 438

2. C oulom b g a u g e in p e r t u r b a t io n 3 3. Resonant absorption and stimu
THEORY 431 lated emission rates 443
2 1 . Discussion and elementary 4. C a n o n ic a l e q u iv a l e n c e of H a m il
example 431 t o n ia n s 447

2-2. Propagation functions in 4 1 . Canonical transformation 447
Coulomb gauge 433 4*2. Non-relativistic Lamb shift 451
3. T he e l e c t r o m a g n e t ic f ie l d and the
6. C o n c l u s io n s 462
SHAPE OF SPECTRAL LINES 435
A p p e n d ix 453
3 1 . The electric dipole field transition
matrix 436 R eferences 454
An examination is made of the Green dyadic for the propagation functions of non-relativistic
quantum electrodynamics in the Coulomb gauge div A = 0. The existence of false precursors is
shown to be associated with singularities at the origin in certain momentum space representations
of the propagators and this allows a prescription to be given to eliminate such precursors. This
prescription is proved equivalent to an exact consideration of the near fields associated with
quantum transitions. The analogous treatment for the state vectors in decaying systems is carried
through and is applied in detail to the problems of the shape of natural spectral lines and the
transition rate for stimulated emission. It is shown that the expected line shape for the Lamb
1057 Mc/s line in hydrogen is Lorentzian within the context of Lamb’s experiments—intensity
against Zeeman splitting energy. This is in contradiction to the predictions of Arnous and Heitler.
The distribution in k (circular frequency) for a natural line, on the other hand, has a factor
times the resonant denominator. The definitive position between the conflicting transition rates in
the literature is given. The relationship of the calculations to a gauge-independent Hamiltonian,
considered in the paper, is investigated in detail. This Hamiltonian, transformed canonically from
the conventional one, is shown to be valid for internal, dynamical, quantized electromagnetic fields;
its analogue in the case of external applied fields being well known. It is demonstrated that the
transformation eliminates many of the difficulties associated with the false near fields and that it also
allows certain radiative effects, where the atom acts as a whole, to be computed in a straight
forward manner.
1. I ntroduction and summary
T he non-relativistic quantum theory of radiation has been standardized for m any years
(Fermi 1932; H eitler 1954; Kram ers 1957). In this theory it is possible to consider a one-
body problem and the sources may be treated non-relativistically in configuration space,
with possible extra spin-dependent terms in the interaction energy. The covariant Lorentz
Vol. 251. A. (Price 9s. ) 54 [Published 15 September 1959

428 E. A. PO W E R AND S. Z IEN A U O N T H E C O U L O M B
gauge used in relativistic electrodynamics leads to difficulties in the treatm ent of bound
charges, and it is thus preferable to use the so-called Coulomb gauge (Heitler 1954) in
non-relativistic problems. In this gauge the radiation field is described w ith the aid of
a vector potential A and its conjugate variable, and the conservative p art of the electro
magnetic field is eliminated in favour of the static Coulomb interaction between charges.
The transversality condition on the radiation field variables can be handled in several ways.
T he H am iltonian for the radiation field in interaction w ith charges is
H = H rad+H an. + U
,(1)
/ / rad being the energy of the free, transverse electromagnetic field expressed through the
conjugate field variables —(1/47r) E x, A ; C7(q(Z)) is a potential function for the electrostatic
interaction between the charges and the energy of coupling to any external potential field,
and /7kin is the kinetic energy operator of the charges which also couples their m otion to the
radiation field through the substitution p© -> p (/)—^ A(q©) in the free-particle kinetic energy.
In this paper we impose the transversality condition on A, nam ely div A = 0, by giving up
the canonical com m utation relations between the field operators A and —(1/4 t7) E x in
favour of the modified com m utation relations
~ h E‘ (x )> 4 ( y )] = - i y ( x - y )
(cf. H eitler 1944, appendix I I ; and §4). This enables one to m aintain div A — 0 as an
operator identity and at the same time allows the conventional Bose com m utation rules
[ctkA>stk'A'] = ^kk'ÂA' (2')

for the quantized amplitudes in the expansion of the field ‘ co-ordinate'
A (x, t) -- H aexp { i( k .x - ti) } + c .c .] (3)
in plane running waves. T he polarization index A takes the values 1 and 2: e(A)(k) being the
direction of polarization. (Units h = c = 1 are used, and e, the electr
in Gaussian units.)
T he non-relativistic radiation theory mostly deals with long-wave phenom ena (wave
length of light large com pared with dimension of radiating systems, atoms or molecules) and
accuracy to w ithin a given multipole order only is aimed at. In electric dipole approxim ation,
the dependence of A on q® is suppressed completely in in and the conventional interaction
H am iltonian is 2
f f r = i { - | p ®.a (o) + a A 2(o)}, (*)
the common origin within the charge distribution being placed at the co-ordinate origin, f
Obvious modifications are to be m ade if several 6natural ’ charge centres enter into
a problem.
T he great advantage of the Coulomb gauge formalism lies in the fact th at the in
stantaneous electrostatic interaction between charges provides a good and convenient
zero-order approxim ation to the force between slowly moving charges, so th at w ithout this
splitting off of the conservative p art of the electromagnetic field the non-relativistic two-body
f A( 0) is not a constant but retains in interaction representation the time dependence as in (3).
G A U G E IN N O N -R E L A T IV IS T IC Q U A N T U M EL E C T R O D Y N A M IC S 429
problem would be of com parable difficulty to the two-nucleon problem in meson theory.
However, in higher-order calculations on the interaction between point charges and in
certain situations where atoms or molecules as a whole interact with radiation, the conven
tional Coulomb gauge formalism can lead to ambiguities, which m ay appear as singularities
and require subtle physical interpretation. In a recent paper we have draw n attention to
this problem (Power & Zienau 1957 a ),w h ic h does not appear to have been m uch com
m ented on before (c£, however, Casimir & Polder 1948).
In this paper this question is re-exam ined from a somewhat different point of view. We are
prim arily concerned w ith the electromagnetic field associated w ith the radiative transitions
of atoms. It is shown th a t the conventional theory in Coulomb gauge does not provide the
most convenient quanta! extension of the well-known semi-classical prescription for treating
non-relativistic radiation problems. T he Green function for the electrodynamic potentials of

the Coulomb gauge may lead to instantaneous false precursor signals unless special care is
taken w ith the projections on to the Fock space basis of the theory. Difficulties of this type are
avoided if a canonical transform ation is carried out to incorporate the atom consistently as
a source of the quantized radiation field. In electric dipole approxim ation, the conventional
interaction H am iltonian transforms to
M - - i M s M . (5)
i
which was used by early workers in quantum radiation theory (Kramers & Heisenberg
1925; Weisskopf 1931; G oppert-M ayer 1931). T he previous theoretical foundation of Hu
(G bppert-M ayer 1931; Richards 1947) is incomplete and does not apply when atom and
radiation are treated as a closed dynam ical system. A derivation of (5) which avoids this
lim itation was given by us previously (Power & Zienau 1957 a, 6), bu t the related derivation
given here in § 4T is more general and lays the foundation for a m ethod of treating non-
relativistic radiation problems concerning atoms, molecules, etc., which is in accord with
the correspondence principle and m aintains the advantages of the Coulomb gauge. It is
not confined to the electric dipole approxim ation. The canonical transform ation with
generating function S is actually a device which imposes explicitly on the formalism the
recognition of the physical restrictions brought about by the absence of free charges and the
bounded nature of the system of charges with natural charge centres envisaged in this paper.
As in classical electrodynamics these restrictions can be handled most conveniently with
the aid of a polarization vector field P (x ) defined through a multipole development. For
a single neutral system (atom) with centre at the co-ordinate origin P can be w ritten as
P (x) U 2 elqm {x) -§ 2 . V)
i i
This vector field is an operator in the quantum theory and S is found to be given, in terms of
A (x) and P (x ) by S = expîjA (x) .P (x ) d rj. The H am iltonian (1) for one neutra
transforms to
H = 2 2 ^ ( p(Z))2+ U ( q(Z)) + i - J ( | ^ | 2 + |^ |2 ) d r —J<^x . P d r + |P |2dr
. , [q»X JT (0)]«+.... (6)

54-2
430 E. A. PO W E R AND S. Z IEN A U O N T H E C O U L O M B
In equation (6) is the magnetic field strength operator and x the transformed transverse
electric field strength operator. The magnetic interaction terms have been w ritten down up
to those terms involving spatial derivatives o f ^ ; (xis the magnetic m om ent arising from the
orbital motion of the charges. A closed form is not achieved for the magnetic interaction
since P (x ) itself is defined through its m ultipole development. In (6) the conjugate variables
are —(1/4 tt) S’1-A
, and p(Z), q(Z), so th at the m atrix representations of <ix and of the Ex fie
operator in (1) can be taken to coincide. The introduction of the usual annihilation and
creation operators for the quantized transverse electromagnetic field therefore proceeds in
the well-known m anner in this transformed H am iltonian, and there is in fact no need to
distinguish S 1-typographically or otherwise from Ex for the purposes of calculation
Nevertheless, it will be shown th a t the relation between Ex and its transform F x is such as to
eliminate completely the difficulties associated w ith false instantaneous signals.
The term 27 is, in the case of a single atom, merely a self-energy which, never
theless, is of im portance in considering the transform ation within a system. To illustrate
this the Bethe non-relativistic Lam b shift energy is com puted in §4-2 using H am iltonian (6).
In the case of more than one centre besides self-energies there are conservative potential
energies between systems in 2t7J | P |2dr. A lthough the entire contribution of the longitudinal
electric field to the total energy resides in this term cancellation has occurred, to w ithin the
above terms, w ith p art of the transverse energy (cf. Power & Zienau 19570, ^)*
To bring out quite explicitly the type of difficulty to which the conventional theory is
prone, the natural shape of spectral lines is discussed in some detail. The natural line shape is,
of course, closely connected with the structure of the actually radiated field, in contrast to
quantities such as the transition probability, which are on the energy shell. In the literature
a variety of formulae are quoted for the line shape and the resonant absorption rate (see
Lam b 1952, §§59, 60). In § 3 a definite decision between these conflicting variants is
obtained. The final near-Lorentzian shape for the natural line is plotted in figure 2 and given
by equation (53). The resonant absorption rate formula is given in equations (59) and (65)
and it appears th at the experiments of Lam b on the resonant absorption from the metastable
2 Sistate of hydrogen favour decisively the formula proposed in this paper (cf. somewhat
similar conclusions already reached by L am b ). For a detailed discussion and exposition of
the literature we refer to the last paragraphs of § 4*3.
The contents of the paper may be summarized as follows. The general aspects of the
conventional Coulomb gauge theory are reviewed in § 2. This section also contains a treat
m ent of the singular propagation functions in this gauge. T he natural shape of spectral lines
and the transition rate in resonant absorption or stim ulated emission are re-exam ined in § 3.
No explicit appeal to the general theory of radiation dam ping in its modern version is made,
the treatm ent being confined to the one photon and electric dipole approximations.
Section 4 demonstrates the general transformation of the conventional theory to the form (6)
which avoids explicitly the appearance of static fields when no free charge sources are present.
The equivalence of this formalism to the conventional one is illustrated through considera
tion of the non-relativistic Lam b shift. A discussion of the resonant energy denom inator in
a typical m atrix element, of im portance in § 3, is relegated to an appendix.
G A U G E IN N O N -R E L A T IV IS T IC Q U A N T U M EL E C T R O D Y N A M IC S 431
2. C oulomb gauge in perturbation theory
2 1 . Discussion and elementary example

T he most significant aspect of the Coulomb gauge is th a t the static Coulomb interaction
between charges is separated off exactly. However, there is no room at all for any instan
taneous interaction between accelerated charges in M axwell’s theory, and the appearance of
this Coulomb interaction in the formalism can be paradoxical. Crudely speaking, a static
interaction occurs only in completely static situations. Acceleration, w hether due to electro
dynam ic interaction between charges or in consequence of external forces, immediately
leads to retarded interaction. Speaking quantally, the charge density has both diagonal and
non-diagonal m atrix elements, the words diagonal being understood in the sense of per
turbation theory or w ith reference to an interaction representation, using a suitable unper

turbed H am iltonian after all radiation interaction is turned off. T he diagonal parts of the
charge density occur in connexion with truly static interactions, whereas the non-diagonal
parts of the charge density are associated w ith energy transfers propagating w ith the speed
of light. T he non-diagonal parts of the charge density can always be eliminated in favour of
the current density. The current density is an essentially non-diagonal operator and only
couples to the transverse p a rt of the electromagnetic field. The Coulomb field is conservative
and cannot transm it energy changes, hence it can play no role when the non-diagonal parts
of the charge density are involved in the transition. If one carries through the perturbation
theory w ith such interactions, terms must arise from transverse photon exchanges which
cancel the static Coulomb interactions. Casimir & Polder, who com puted the interaction
energy between two neutral atoms (oscillating dipoles) to the first significant, i.e. fourth
order in the charge, encountered this fact. In this situation the interaction at each vertex
only involves the non-diagonal parts of the charge density (dipole moment) and the instan
taneous dipole-dipole interaction is indeed cancelled by a term which arises naturally from
the transverse photon exchanges between the two atoms, leaving one w ith an obviously
retarded interaction (Casimir & Polder 1948).
To illustrate this cancellation in a straightforw ard second-order problem we consider
the interaction between two Dirac electrons moving in a common external potential using
old-fashioned, one-electron theory. T he m atrix element for this interaction energy, due to
H ulm e 1936 (see Lethe & Salpeter 1957) is of course closely connected with M uller’s
formula (cf. Heitler 1954), but it is preferable in the present context to remove the
m om entum conservation which necessarily fixes the photon wavelength in the free particle
collision m atrix element (cf. Fierz 1950 for a somewhat similar consideration). T he Dirac
electron has been chosen in this example as one obtains the m atrix element for the
transverse interaction in the required form almost at once, whereas for spinless charges
(interaction H am iltonian (4)) an explicit symmetrization of the — p .A p art of the
interaction H am iltonian is first required and complicates the algebra. In this problem
a residual monopole interaction will rem ain when the energy exchange vanishes, which is
the static case. We examine the situation when the energy change of either electron is
77 — 77(1) _ Ml) — 77(2) _ 77(2) ^ J~jr ,
n,m, p, r being positive energy levels of the Dirac electrons in the common potential field,
432 E. A. POWER AND 8. ZIENAU ON THE COULOMB
when all interaction is switched off. Using a H am iltonian of form (1), the interaction
H am iltonian now being
H x + U = A (xt) +g 2ot(2). A( x2) + ............| , (7 )

IX1 X2|
the m atrix elements for transverse photon exchange on the energy shell are read off the two
tim e-ordered Feynm an graphs of figure 1. T he electron lines are single electron bound
E? E 4 2)
/
*/
/
/
X
tp
1 2 1
Figure 1
state propagators and the energy exchange at each vertex is Using

(<x(z). V,) / ( x z) = i [a(z). p (Z)+ 8®m + F ,/( x z)]
and Af 4A,(k) cjA,(k ) = (4 = (8)
the two m atrix elements combine into the expression

2el e2/f 00
° - i r \ S o (e + (gll>-g8)- F j - g ~ > - <»>
H ere = |X j—x 2| and explicit use has been m ade of the energy conservation relation.
The positive im aginary infinitesimal e has been added to take care of the radiation condition.
An examination of the integrand shows th at while the ie indeed suppresses all contributions
of form z~lER\R corresponding to ingoing radiation, the device does not ensure th at only
outgoing radiation contributes to the interaction. To see this consider the p art of the
integral arising from the E 2/k 2term, which of course is the one originating fr
tudinal p art of the current density. This is
2el e2 p 2/ s'” dk sin k R \
*^2 — ~7T \J
o ( £ + k ) 2- A 2 kR / '
The integrand is regular at the origin. The radiation condition is conventionally complied
with by transforming to
2exe2
n
7T ^ \ 2 i J _ a [ ( . E + L ) 2- ^ P ] ~ T / 3
gauge in n o n -r e l a t i v i s t i c quantum e l e c t r o d y n a m ic s 433
and proceeding to evaluation by closing the contour in the upper h alf complex A>plane.
A part from the singularities at k= (±£ + k ) , the integrand now
where the integral must be evaluated as a principal value. Thus
It must be emphasized th at the last term appears if other methods of evaluation are used, and
in particular this contribution is unchanged if the outgoing wave or standing wave boundary
conditions are imposed at k— IE
. t is only if the integrati
m anner to comply with the radiation condition th a t the static contribution to the integral
derives from a residue at k = 0. It will be convenient on future occasions to
admixtures, like the one in (10), as deriving from a pole at the origin of Æ-space, it being
understood th at this is strictly true only if the integration is effected as in the present example.
It is noticed, however, th at by considering the static contribution to arise from a pole at
k — 0 , one obtains a means to isolate this contribution. R earranging the integrand in as
E2 I k
= > ( 11 )
it is easily verified th at the static contribution arises from the first term, whereas the second
one can now be evaluated unambiguously by imposing the radiation condition. Again,
using the same criterion, one verifies the absence of a static adm ixture to the a(1La® p art of
the interaction.
Finally, we obtain , .
^ ( 12 )
so th a t /,, , 1 /, ,
\ U +H El?+ E $ - H ° H / = *2 \ (1 - « 0 • «(2)) >
the static Coulomb interaction cancelling with the last term in of equation (12). For
energy change zero the formula reduces correctly to the electrostatic monopole interaction
and the static magnetic interaction between the convection currents.
The example illustrates the occurrence of static contributions associated with the inter
mediate state summations of the perturbation theory when transverse photons are exchanged
in Coulomb gauge theory. In the conventional m anner of effecting these interm ediate state
summations over the photons exchanged, a singularity at the origin of the associated A>space
integration occurs and removes the ‘false’ static interaction associated with non-diagonal
electric multipole transitions. Interesting cases where such cancellation occurs can be found
in the theory of electromagnetic excitation of nuclei by accelerated ions (Alder, Bohr, Huus &
Mottelson 1956), and in the theory of internal conversion. These problems are best handled
with spherical wave expansions for the radiation field and will not be treated here.
2 2. Propagationfunctions in Coulomb gauge

The static contribution from the interm ediate state summations when Coulomb-gauged
transverse photons are exchanged is closely connected with the com m utation relations in
434 E. A. PO W E R AND S. ZIEN A U O N T H E C O U L O M B
this gauge for the vector potential operator. The analogue of the function of relativistic
radiation theory is the dyadic S z..(x),
[4 (* ),4 (if)] = i m ^ u(x-y),(14)
(k = (k,k„),kx -- k . x - * 0<). (15)
In m om entum space, the singular functions of the Coulomb gauge are all derived from
(16)
M -k r
using one or other prescription for the ^-integration. T he propagation function (dyadic)
with the retarded boundary condition is
@ij{x) — 4 Jd4A: (17)

[|k | +Æ0+ie] [|k | —^0—ie] ’
and satisfies □ ^ ^ ( x ) — —S(t) Æy(x). (18)

Sj-(x)} the transverse ^-function, represents the transverse p art of the singular dyadic field
< w ,
H (x ) = Sv S (x) - H ( x ) = (2*)-’J d k e * -‘( i y - ^ ) = f StjS ( x ) (19)
whereas Æjj(x) is a representation of its longitudinal p art (cf. Belinfante 1946).

T he physical properties of S ^ fc*(x) are perhaps best brought out by picking up its Fourier
com ponent at circular frequency k0> 0,f
k„) ( 20 )
T he rem arkable feature in the propagator for the electrodynamic potential A of the Coulomb
gauge is its static part. In Sf?*- ( x ; k0) this appears as a term not containing eikor (last sum m and
in (20)). If the A>space integration is carried out in the conventional m anner to satisfy the
outgoing boundary condition on ^ ^ - ( x ; k0)t, his static adm ixture ari
origin |k| = 0 . There are no static contributions of order r~1 or and if in the result of the
angular integration
er.[kr) ‘■'(Stj-M j)
sin 'cos krsin

(8ij - x iX j) - jir-+ ( % - 3 xtXj)
_ k 2r2 Æ3r3 J
(k (21 )
the r~l or r~2terms are picked out, no pole at |k | = 0 is encountered in the final integration,
irrespective of the m anner in which this integration is effected. For this reason the static
contribution appears to have been ignored previously, since m ajor interest normally centres
on the wave zone fields varying like r~l.
f It may be noted that the positive frequency part of SZ, the Feynman function of the Coulomb gauge,
equals the positive frequency part of which establishes the relevance of (x, k0) to the perturbation
theory (Fierz 1950).
G A U G E IN N O N -R E L A T IV IS T IC Q U A N T U M EL EC T R O D Y N A M IC S 435
T he m om entum space propagator can be decomposed into
kj 2
%(*) | k 12, i] (% ( 22 )
oS
kl
1
M
This decomposition separates off the static adm ixture explicitly and has more than formal
significance. 3>W(K) is, in fact, the singular function governing the propagation of the trans
verse electric field strength
[Ef(x),Ej-(y)] = 4?ri W W - A (23)
= —i(27T)~3j d 4k e ikxS(k2) e(k) ( | k | 2 ^ . — = (27i)~4J d (24)

T he associated retarded propagator, which satisfies

□ — —(curl curl)^-F(x) (25)
has Fourier com ponent at frequency k0> 0:
— im —3*i%) (26)
Since the field strength is the measurable operator, the decomposition (22) expresses
a physical property of the propagated field. By considering (26), (19) and (22) one sees th at
the retarded Green dyadic AA^(x; k0) can be considered as the sum of the transverse
electromagnetic field radiated by an oscillating dipole singularity and the instantaneous
electrostatic field of the dipole. (It should be observed th at the spatial Fourier transform of
k) in (22) gives <^)(x) irrespective of the boundary conditions imposed on ^^(k ), which
only affects S>^[k).)
There are problems where it is useful to recognize explicitly the physical significance of
the propagation functions for the transverse vector potential operator A of the Coulomb
gauge, and for this reason the well-known subject-m atter of the present paragraph has been
recalled. In the next paragraph it will be shown th at failure to do so vitiates a num ber of
formulae for the natural shapes of the emission and absorption lines of atoms. In energy
calculations, such as in the work of Casimir & Polder on the L o n d o n -v an der Waals
interaction energy between neutral atoms or in problems like the one treated in §2-1, one
will of course hardly overlook to add the contribution of the static Coulomb interaction in
each order of the perturbation calculation. T he perturbation theory then so to speak
autom atically effects the cancellation of static contributions in the interaction connected
w ith non-diagonal m atrix elements of the charge density.
3. T he electromagnetic field and the shape of spectral lines

In this section we consider the radiation field and the shape of the spectral line emitted by
an atom making a transition from an excited state to one lower in energy. For the sake of
ease we work in dipole approxim ation and to the lowest order in the charge coupling. In
general we treat transitions from the first excited /^-states to the ground state of an idealized
hydrogenic atom, but we make an application to the Lam b line between the and the
2 levels of hydrogen.
55 V ol. 251. A.
3 1 . The electric dipolefield transition matrix

The non-relativistic H am iltonian for an atom with Z electrons coupled to the radiation
field is almost always w ritten in the form
H = 2 (p < » -« A (q ® ))^ -Z ^ 2 + ^ J (Ex2(x) + H 2(x)) dr. (27)
Since the recoil of the atom is neglected, only the electronic variables p®, q® and the rad ia
tion field —(I /4 tt) E x, A appear. The longitudinal p art of the field is considered elim inated
in favour of the electrostatic potential energy between the charges, terms representing the
electrostatic self-energy having been dropped.
In the so-called semi-classical theory of radiation developed by K lein (1927) and others
(see Pauli 1958 or K ram ers 1957 for detailed accounts) the non-diagonal m atrix elements of
charge and current associated w ith an atomic transition act as sources of the radiation field,
which is treated classically. These Klein correspondence charge-current matrices satisfy the
continuity equation and vanish, if integrated over a sufficiently large sphere about the atom
centre, provided only at least one of the states is in the discrete spectrum. For dispersion
problems, one requires, of course, these matrices to a higher th an first order in T he entire
theory proceeds in the closest possible correspondence w ith classical electrodynamics. In
classical electrodynamics, it is well known th at the continuity equation for the current and
the vanishing of the latter over the surface of a certain sphere enclosing volume V imply
/0*(x) being the Fourier com ponent of the charge density /?(x, t) at frequency This in tu rn
leads to the absence of a monopole contribution to the radiation field outside V at fre
quency k.If the potentials A A of such a charge current distribution are com puted in
Lorentz gauge, a multipole expansion contains the monopole contribution at frequency k
only in the form of a longitudinal field
0 = ikS A = VS,
yielding a vanishing radiation field. T he classical theory and its quasi quanta! extension
correctly associates w ith an oscillating dipole, real or virtual, a retarded radiation field,
which is purely transverse outside V.A monopole contribution to th
outside V may rem ain, but this is static and is derived from the total static charge enclosed in
V. It necessarily vanishes when the system in V is overall neutral.
A formulation of the quantum theory of radiation which proceeds on completely parallel
lines to these classical considerations was published by Heisenberg (1931). H e uses the
electrodynamic potentials 0, A in Lorentz gauge and it is now known th at the treatm ent of
the scalar and longitudinal photons, which arise through quantization of the radiation field
in this gauge, requires care. T he calculation which runs parallel to the classical or semi-
classical one, in fact requires the G upta—Bleuler treatm ent of the subsidiary condition,
V . A + (f>= 0, and of the vacuum state (G upta 1950; Bleuler 1950).
The essential physical features of the radiation field of an oscillating system of charge
currents, confined to a region V,must of course be m aintained independe
GAUGE IN NON-RELATIVISTIC QUANTUM ELECTRODYNAMICS 437
appearance of a static monopole contribution to the electric field of the atom can arise only
from the diagonal elements of the total charge and, if the atom is neutral, this contribution
can be avoided by adjusting the charge density, so th at
« x ) L = 2 e [ s^*(q(1)jq(2), •••,q(Z))T*„(q(1)q(2), . . q(Z)) IIdq^T

1=1 LJ J 4(»)= x
(28)
(cf. Dsjaloshinsky 1956).
We now examine the analogous situation in the conventional form ulation of the Coulomb
gauge. T he radiation field is most readily obtained in Heisenberg representation from the
integral equation for the operator A (x, t),
4 (x> t) = d 4y,(29)
where j (x, t) is the current operator in Heisenberg representation.
To order e,th e m atrix element of A (x, t)corr
system requires only the m atrix element of the current operator in zero order, so th at in
dipole approxim ation
<4 (X- P))mn= ^ ( P j ) m n
where knm — En—E m> 0, p is the total m om entum operator of the atom, p = p® and th
i
atom is considered fixed at the co-ordinate origin. The corresponding expectation value of
the transverse, radiated electric field strength is
< ^ (X , t))mn= Km
(Pj)m
n^ti^Km
)exP ( “ *Km*)
met (?i>M § lj)ret'(X» U eXP ( “ I exp ( - i k„mf) . (
This result appears baffling because of the instantaneous adm ixture in the electric field
at x given by the last term (cf. (22)), which one does not expect to find associated with the
radiative transition n>- mfothe atom. The paradox is rem
removal of the Coulomb interaction between the charges, the atom as a whole still acts as
a source of an electrostatic field in the Coulomb gauge formalism.
T he Coulomb energies in (27) do not exhaust the content of the longitudinal p art
of the total Ham iltonian. The electrostatic potential p is of course a redundant variable, but
nevertheless an operator, since its source is the quantized p. A multipole development of p
for a neutral atom gives rise to these Coulomb terms, the contribution from the higher
multipoles being readily obtained using an auxiliary vector field P. Let
p= - V . P = - V . P 11,
so th at —V0(x, t) —E ^ x , /) — —47tP ii(x ,
which reduces the energy contributions of the higher multipoles to Lf11to
277J | P 11(x) |2dr = ^ J | E 11(x) |2dr. (35)

55-2
438 E. A. POWER AND S. ZIENAU ON THE COULOMB
A multipole development of the vector P then im m ediately gives the desired multipole
expansion of the electrostatic field. In dipole approxim ation, the electrostatic field asso
ciated w ith the transition n>- ms i
<£|'(x, t))mn = -±'ne{qj ) mJ t j {'K) exp ( - i
= exP * W (36)
z
H ere q is the total mechanical m om ent of the atom, q = 2 <l(z)- Using (33), (19), the con
nexion between E and A and Z=1
(Pj^mn ^(37)
one verifies th at for |x| + 0 (36) subtracts out the static p a rt in the electric field m atrix
<E(x, t))mn. Finally
<£ -(X>*) >«. = 5 K J <Pj>«n a P { l *7 (f~ ' 1} ~ %) + to, (38)
which is the result expected by the correspondence principle.

The argum ent leading up to (38) clearly shows th at care is necessary in interpreting the
development coefficients of the state vector in the Fock space of the Coulomb gauge for
malism if one uses the conventional H am iltonian (27). The development of the state func
tional *F(Eq 0) which arises through the radiative coupling from the unperturbed vacuum
state of the radiation field |0) and the first excited /--state (f>m(E) at energy E of the atom
(m = 1, 2 , 3), is in Schrodinger representation, using (3), (27) and dipole approxim ation,
Y (£ ; 0) = {!"(£) \0) + 2j ~ ^ m (39)
The pole at k — eExhibits the real decay probability of the atom from its excited state, b u t
the singularity at k = 0 rules out the interpretation of the development coefficien
probability amplitudes for the presence of a photon of mode k, polarization e(A)(k), for the
fraction of time the atom spends in its ground state.
T he static adm ixture in the expectation value of the field operator A (x, ), shown in (30),
corresponding to a transition n>- m,is a grad
(27) is known to be gauge invariant, one expects th at a gauge transform ation exists which
eliminates this adm ixture and is a gauge transform ation except at the origin. This unitary
transform ation will be exhibited in §4. The existence of this transform ation which is
canonical, guarantees in a general way the correctness of transition probabilities, cross-
sections and lifetimes computed conventionally. These quantities are all evaluated on the
energy shell and are invariant against canonical transform ation. The canonical transform a
tion, however, changes the basis vectors of the Fock space and the developm ent of the
transformed state functional 0) in the old basis will have different projections on to the
transverse photon states than th at in equation (39).
3 2. The natural shape of spectral lines

The time development of the state vector T*(£) defined in a particular interaction repre
sentation, plays a central role in the theory of natural line w idth of spectral lines. In this
theory one distinguishes between two problems. The *natural ’ w idth and shape of a spectral
line, say in emission, is defined somewhat unphysically from the distribution of emitted
radiation after an infinite time interval, assuming th at the radiative coupling could be
turned on at an instant when the atom is in the excited state w ith certainty. The actually
realized shape and w idth of the line depends, however, very critically on the mechanism of
excitation. T he situation when the excitation is by means of absorption of light will be
briefly discussed later.
T he quantum theory of the natural line shape was developed by Weisskopf & W igner
(Weisskopf 1930). These authors achieved an im proved solution to the tim e-dependent
equations of m otion for the coupling of an atom to radiation in an interaction representation
w ith an initial condition at a time t —0, using dipole and a o
L ater work on the general theory of radiation dam ping (Heitler 1954; Arnous & H eitler
I 953) is prim arily concerned w ith higher radiative corrections and incorporates the Weiss-
kopf-W igner theory as a first-order approxim ation. In addition this later work avoids the
W eisskopf-W igner assumption of exponential decay e~in of the initial excited state for all
values of the time param eter in 0 < t < co; this assumption is irrelevant
behaviour of the exact formal solution for small times. W ithin the one photon approxim a
tion, the general equations of the radiation dam ping theory become soluble in closed form,
the integral equations for the dam ping operator T and the transition m atrix (cf. H eitler
1954, §§ 16, 18) reducing to trivial algebraic relations.
The equation for the state vector T ’(^), using an interaction representation, is
(40)
S( 0 ) — 1.
The distinguishing feature of the dam ping theory is simply the initial condition at 0 and
the irreversible nature of the solution looked for. The initial condition or the transform ation
operator S(t)cannot be imposed at t = —00, as in collision pr
(f){E) |0> has a short duration and would certainly dissociate by the time t reaches a finite
value. In the interaction energy the operators q®, p®, A, —(l/4zr) E x carry the
usual time dependence of the interaction representation, otherwise is given in dipole
approxim ation by (4). T he one photon approxim ation consists in only adm itting the states
0 (0) |k,A> as interm ediate states in the m atrix m ultiplication of the system (40). For times
t > 1/E, and assuming MY <4 iEt is found th at
«„(<) = < M ) ; 0 W 10; M ) > ~ e - « \
=<m; a |S (f)|0 ; }}(£))
(41)
are the development coefficients of XF(^)>. The result for akX(t) is valid at such times t where
a0(t) decays exponentially. The real p art of is, within good approximation, the total
transition rate out of the initial excited state at energy to the ground state 0(0):
\(HM-)\2S (E -k ) = I e2E 3 |<q>|2. (42)
kA
It may be rem arked th at it is im m aterial for (42) w hether H int- is used in form (4) or inform
(5), the one-photon m atrix elements of and being identical on the energy shell.
The im aginary p art of T representing the level shift of (j>{E) will be neglected in w hat follows.
Since the instant from which decay starts is fixed with precision at 0, one expects to
find no field am plitude at distance r from the atom for times To see w hether this is true
we shall com pute a m atrix element of E ±(x, t)in the inte
(40), correct to order e,by using (41). T he required m atrix element is
C F (0 ;0 ) \Et(x,t)\Y(t))(43)
w ith Y (0; 0)> = m0| > + 2 |

which may be considered a stationary state to the order required. (It is again assumed th a t
only the first excited /estate contributes significantly.) At times sufficiently large so
th at the am plitude of the initial state (j)m[)E |0) may already be n
kA
and therefore
< f ( o ; o) |£ « x , t) | ¥(<)> ~ - ^ < f e > ogJ " ^ d^ ' (fr) [^ p_{g + f i r f r ) <}~ e~‘M] (44)
is the expectation value of the field strength at distance r from the atom at > 1/T, correct to
order e and within dipole approxim ation. T he function « ^ j ( i s given by (21). I f one argues
entirely from the 1/r proportional parts of the field
<T(0; 0) \E t( x ,t) \'¥ ( t) ) ~ [e x p { -i(£ -liD

(45)
The integral receives its m ajor contribution from the neighbourhood and the lower
limit of integration may be extended to —co. Contour integration then shows
<T(0; 0) |£ f(X ,t)|¥ (< )> ~ - , < 6»,>£«i(% -$ ,% ) exp{i(r-< ) ( L - j i l H - s t - r ) , (46)
verifying th at the field strength com ponent of order 1/ remains zero at x , unless The
same argum ent can be carried through for the r~2 contribution to the field. However, as
soon as the r~3 parts of ^ {kr) are considered, the argum ent is spoilt. A precursor, static,
contribution appears in the field proportional to r~3, independently, of course, of the
m anner in which the integration is carried out, which may be considered to arise from the
singular behaviour at k= 0 of <zkA(<) (equation (41)).
O ne can remedy this, by separating out of akX(t) the physically admissible p art through
a decomposition closely analogous to th at of the propagator @ij(k) in (22),
JL _ ___ ?____ =* _______ !)-i-Q(g2)

j k k - E +\ir £ U -£ + !ir
The infinity at k = 0 is now explicitly separated out of akA(t) and the rest of the expressi
leads to the required field structure. A consideration of the Coulomb field accompanying the
time developm ent of the state T*(f) can be carried out in a m anner similar to th at dem on
strated in § 2 for the analogous stationary state problem to exhibit the explicit cancellation of
the factor ~ 1/1 I f the preceding argum ents, leading up to (44), were carried out with
Æ $! D as an interaction energy, the entire difficulty is avoided and the
decomposition of stkA(f), removing the 1/k da m ixture, in fact re
developm ent coefficient by the unitary transform ation given in § 4 (correct to order
I t may be m entioned th a t the same difficulty is encountered in a problem considered by
K ikuchi (1930) and Ferm i (1932), which has played a role in the early history of the subject.
Two identical atoms situated a t distance Rpart,
a again w
above, are considered, it being assumed th a t at tim e — 0, when the radiation interaction is
turned on, atom A is w ith certainty in the excited state at energy the other, atom
in the ground state. T he non-stationary developm ent of the state vector Y(f)> from the
initial state <f>0(B) $E(A) |0> is examined. In lowest order the radiative reaction of atom on
A can be neglected when the rate of change w ith time of the projection of 'F(f)> on to the
state (j)E{B) $0(A) |0> is com puted. This coefficient determines the build-up of the excitation
on atom B ,atom Ahaving decayed to its ground state. O ne finds, letting
~eir°1exp {i (E — —1^”
x < M A);k, A\Hint-1
(A
) 0£(A ); 0 ) exp e
* -£ + iir0 _ + 0 (*4),
(47)
r 0 being the radiative transition rate out of the excited state, the interaction H am il
tonians are in Schrodinger representation and W is the total energy of the state
<!>e (B) ^ o(^) |0> at time tc( f. H eitler & M a (1949) for derivation of (47)).
approxim ation, the conventional interaction (4), summing over the polarizations and all
directions of the photon k ,the factor
nm2 ^ ^0
)Eso
appears under the ^-integration sign of (47). Picking out the p art proportional to
d f>2 . «i ER
(48)
which is the result quoted to show that the interaction between the atoms propagates with
speed of light. Yet here again a closer exam ination of the p art of (47) reveals a static,
instantaneous precursor. There is a difference com pared to the field of the single atom, in as
m uch as the Coulomb interaction between the atoms contributes in order to the energy of
interaction and will subtract off the instantaneous adm ixture in automatically,
which will be hardly overlooked. From the stationary point of view the radiation and
Coulomb interaction together remove the degeneracy between the two states
h ( A) M
|B
)0> and <f>E(B) |0>
belonging to energy E .In dipole approxim ation it is easy to verify th at the energ
to order e2is
(-5 ) ) eo ( E f ( R ) ) oe~ 2 e2( qi (B))£0( q j ( A ) ) 0E j (3 Xj — ) ~ E * /)j
(49)
<.E/-(Æ)>0£ being the electric field strength at the atom B due to the transition -» 0 of atom
A, as given by (38). This form ula is obtained most directly by using the dipole interaction
H am iltonian //JfS (5). In the static limit, R <4 1/E, it reduces as it should, to a static
dipole-dipole energy proportional to R~3.
We now return to the natural line-shape problem. So far we have shown th at the one
photon m atrix elements of the conventional interaction H am iltonian

( —{e/m) p . A(0) + A 2(0))
give rise to a false field structure for light em itted in an atomic transition, unless these m atrix
elements are explicitly corrected to give the physical retarded field. T he developm ent
coefficient <zkA(tf) of (41), as it stands, cannot therefore determ ine the shape of the em itted
spectral line, which must be obtained by Fourier transform ation of the actually m easurable
electromagnetic field in the wave zone of the atom. T he probability distribution of
em itted radiation at circular frequency k which results from
<->oo
t 1/r when emission has certainly occurred, is
2 . . . ... £ 2*
P{k)dÆ = ’2 odQ (k) M o o ) | 2/>(£) d dk (W rong). (50)
A n 3 ire ( * - £ ) 2+ i r 2
The intensity distribution in the em itted line is given by I{k) d — ) d In this form, the
form ula has been advocated by H eitler and Arnous (Arnous & H eitler 1953; cf. also H eitler
1953 and 1954, p. 353). T he crucial point is the behaviour of the num erator as a function
of Enda k .If the num erator is fixed on the energy shell, =
p {k) dk = — (A_ £ )2+ j r 2 (61)
(using (42), the im aginary p art of T being suppressed) in which form the line shape is quoted
in m any publications (cf. H eitler 1954, § 18, equation (13)). Weisskopf & W igner (Weisskopf
1930) obtained (50), b u t by a m ethod which does not really leave room for an energy
variation of the num erator, so th at (51) is the more consistent with the method of Weisskopf
& W igner, as reproduced in § 18 of H eitler’s book (Heitler 1954). The more recent investiga
tions of H eitler and collaborators show th at the energy variation of the m atrix element in
the num erator of (50) must be taken seriously (cf. Arnous & H eitler 1953).
O n the other hand, we have now shown th at the physically admissible p a rt of akX{co) is
m fact - 7(2**) <ft w m (82)

4 a (co)
m E*
This leads to a probability distribution of em itted quanta
9 Z-3
P{k) d£ = |<q>|2 (R i§h t)» (53)
and a corresponding intensity distribution. This is the probability distribution which would
be revealed by Fourier analysis of the actually em itted wave train of the radiation field.
Equations (50), (51) and (53) of course all agree in shape at the centre of the line, but
predict different shapes away from the centre. O f course no distribution is to be considered
too far off resonance. E quation (53) implies a displacem ent of the line m axim um by
3T 2/8£, whereas the displacem ent for (50) is F 2/8 £ .O n e is im m ediately lead to (53) if the
dipole interaction energy (5), is used in the formalism of the dam ping theory (cf.
equations (13), § 18 or equation (10), § 16 of H eitler 1954). This was noted by Lam b, who
rightly concluded th at (53) is the physically admissible formula. In figure 2 the distribu
tions (51) and (53) are draw n for the the case OTE = F.
Figure 2 . Graphs of P(k)for the Lorentz shape (51) and for the law (63). The latter is no
by putting JT = 1 and suitably cut off. In both cases F is chosen to be (ME. This displacement
o f the maxima is §F2/E.
3 3. Resonant absorption and stimulated emission rates

The experimentally observed shapes of spectral lines depend very critically on the m ethod
of excitation even if all external disturbances are removed. O ne m ethod of excitation is by
resonant absorption of light from the atomic ground state, followed by re-emission, the
so-called resonance fluorescence (Weisskopf 1931; Heitler 1954, §20; Arnous & H eitler
I953)- This process will be considered, again within dipole approxim ation and to order
assuming that only the first excited /--state at an energy E is involved. The w idth of the
ground state ^(0), non-vanishing in the presence of incident radiation, can nevertheless
normally be neglected against the w idth F of the excited state, so th at a variant of the
stationary 5-m atrix theory may be used (cf. Jau ch & Rohrlich 1955, § 14-7). The non
vanishing w idth yof the initial state ^(0) |k, A), a function of the incident light int
however, imposes an upper limit to the total interaction time at T = 1/y, so th at a total
probability can be defined within our approxim ation for the absorption of the prim ary
quantum (k, A) and the emission of the photon (k',//). If is not near any absorption
frequency En, this probability is
O'TT
A „ (k ',k ) = - 8{ k - k ’)n(k) |4 A>(k) k ') |2, (54)
56 V ol. 2 5 1 . A.
where J?iAk,k') is the well-known m atrix element of the K ram ers-H eisenberg dispersion
formula
,M I
T he interm ediate state sum m ation is over all excited/^-states and n(k) is the average occupa
tion num ber of photon modes near (k, A). According to Arnous & Heitler, the Thom son
term lsrr,T----- <L, which contributes to the coherent process, can be om itted if the be-
V (aK ) Tsl J
haviour near a resonance is investigated. However, closure with respect to the atomic
spectrum and the energy shell condition k=
of îj(k , k') into (cf. Dirac 1947)

{G\qi\ n ) <n\qj\G > (56)
«^(A, k') = 27 2
nL k-E n w m
O ne obtains k ')in this form if — —^ q .E x(0) is used in the second-order per
turbation calculation leading to (54). T he algebraic equivalence of (56) and (55) expresses
no more than the invariance of the ^-m atrix elements on the energy shell against a canonical
transform ation, which must be so since in the energy shell the ^-m atrix is a Heisenberg
operator.
O ne is now confronted w ith an am biguity according to which of the two alternative forms
for JKîkyk') should be used to extract a resonant contribution when k ~ E , the first
absorption frequency. JK^k^k') is finite a t k=
similar arguments to those used before, th at no infinities at — 0 should be introduced
through the m utilation of the m atrix element. Dropping non-resonant terms, either version
for Jl\j(k, k ')gives for knear E,
4 * (k ) ~ <G; k> A a>'1 ‘;l G;k- — > (57)
where a dam ping factor T has been introduced phenomenologically and is known to be the
radiative w idth of the interm ediate state | ;0). This facto
E
obtained either [a)by non-stationary means (H eitler 1954), or by considering 'Jfij(
as an element of the reactance m atrix rather than the S-matrix (W entzel 1948), or (c) by
summing a subset of radiative corrections to the transition m atrix elements (see A ppendix
for a simple derivation of T). According to w hether (55) or (56) is used as a starting point,
jjint. jn the m atrix elements of the num erator of (57) should be taken as (4), or as
Hlf*", (5). However, only in the latter case is the resulting am plitude finite at = 0.
In the non-stationary treatm ent of the resonance fluorescence (Weisskopf 1931; H eitler
1954) the time development of the state vector XF(^)) in an interaction representation w ith
an initial condition at t —0 is examined in detail. By considering the
expectation value with the aid of the projection coefficient br „.k>^(t) of XF(^)) on to the final
state I G ;k r,gju)iven, for example, in Heitler (1954, §20, equation (10)), a calculatio
similar to the one indicated in § 3 2 shows th at static instantaneous precursors in the field
result if the interaction H am iltonian Int*is used uncritically, th at
H
singularities at the origin in the m atrix elements. This procedure amounts to use of
G A U G E IN N O N -R E L A T IV IS T IC Q U A N T U M E L E C T R O D Y N A M IC S 445
In the neighbourhood of k ~ E ,the correct total scattering probabilit
Px,(hk') = — S(k—k') n(k) l<G ;k’ * I ^ M Æ ^0> N < £; 0 1 ^ 1 G y t ' , MW (58)
T h e structure of the emission line on the assum ption of continuous absorption need not be
investigated h e re : if the initial intensity distribution is so broad th a t the n a tu ra l emission line
can be realized, form ula (53) applies. For interm ediate cases, the form ula is given by Arnous
& H eitler (1953, equation (60)), except th a t the interaction H am iltonian should be in
the published form ula. O f more practical im portance is the resonant absorption rate, w hen
excitation is by a sharp line, sharp th a t is com pared to the n atu ral emission w idth. In this
case, the emission line also reduces to a sharp line, the entire process being coherent. To
define the absorption rate r _1, a transition probability p er un it tim e is obtained from (58)
and the integration over all incident q u a n ta w ithin a solid angle d G (k 1), and w ith frequency
n ear a given k x,and polarization e ( k 1) is carried out. T h e adm itted frequency interval
selected by n(k).In addition, all directions of propagation and polarization and all fr
quencies k 'of the em itted photon k are sum m ed out
m LX- I<G; k, A I f l r ) 0>|= |< £; 0 |f l p - |

X d(k-) (x A - Æ p + j r 2
= 27, S { ^ k \ |<£ |q | (R ight). (59)
This is the absorption rate for incident light a t circular frequency k lt polarized along e,
S being the intensity of this light incident w ithin solid angle dO(K1).
For the sake of completeness the form ula for r _1 w hich results from the conventional
interaction is q u o te d :
r-' - 2 E ) t& h |\<

Eq| G> I-) ( D * (
In both cases, the factor in curly brackets represents the transition rate out of the excited
state, F, b u t evaluated not w ith energy conservation k = E b u t a t k lt
{ } = 2 " / M § 6 Q ( L ) 2 KG; k,A 0>| ( 61 )

(2 jt)
T he transition rate T(k) associated w ith the transition is unam biguous only at
otherwise different values result for F according as H l or Hn is used as an interaction
H am iltonian. Both (59) and (60) m ay therefore be w ritten
|<G; K X \H ™ -\E ; 0 )\ z
t" 1 - 27nST^j) (62)
[k . - E Y + l Y * 5
and this is the result, to order e4,given by the formal theory of radiatio
1954, form ula (18), § 20. T h a t H eitier’s 7 is to be evaluated at = can be seen by tracing
back the derivation to his equations (8) and (9).) A ctually it can also be shown th a t the F in
the denom inator is to be evaluated at k = k x.
56-2
446 E. A. P O W E R AND S. Z IE N A U O N T H E C O U L O M B
Weisskopf (1931) derived (62) b u t w ith T on the energy shell. Weisskopf used the
interaction operator H n ——«q.Ex(0), whereas the earlier editions of H e
(1936 or 1944; § 15, equations (21) and (11)) reproduce W eisskopf’s derivations on the
assumption th a t the conventional interaction is inserted into the m atrix elements. O n
this basis, the two alternative variants of r _1 differ by the factor ( J 2, as is seen by com
paring (59) and (60). This was noticed by Lam b (1952) and has given rise to confusion."j"
L am b considers (59) w ith the T in the num erator (factor in curly brackets), fixed on the
energy shell as the prediction of the quantum theory of radiation. According to the m odern
version of the dam ping theory, the variation of T w ith incident frequency m ust be taken
seriously, the situation being analogous to the frequency variation of the transition m atrix
elem ent which appears in the num erator of the n atu ral line shape formula. T he simplified
derivation of r _1 given here correctly reproduces this.
Form ula (59) m ay be applied w ith some changes, to the transition rate out of a m etastable
state, as is m et in the experiments of L am b on the energy separation between the 2 and
2 levels of hydrogen. T he 2 P ^level has a w idth, due to the large probabi
ground state lS^. of approxim ately 100 Mc/s, whereas the spontaneous decay rate of the
level either to 2P ^by electric dipole radiation or to the ground state by tw o-photon emis
can be completely ignored. T he entire cascade 25^ -> 2 -> is an induced resonant
absorption process for incident radiation (r.f.) w ith frequency in the neighbourhood of the
L am b separation o)of approxim ately 1057 Mc/s. T he m atrix elem ent for this pro
dipole approxim ation and ignoring fine and hyperfine structure complications, is, ap art
from the factor n(k), the average photon occupation num ber near circular frequency
r.f. signal incident w ithin solid angle dO, the same as the m atrix elem ent
^ ( k ,^ ( M f
for the spontaneous decay cascade, photons (k, A) and (k',/<) being em itted w ith energy
conservation:
2tT62 1 •<a?i|AlP)<P |ft| is,) , < 2 ^|A |f)< f|A l i y (63)
îj(k,k')
J(kk') k<*{P) uU') f
T he sum m ation is over all Ptates
s in the hydrogen spectrum , being the ene
tion of the 2 state from these levels; this is negative except for the state (oj(2P^) — and
E( 2S$) — o){2P£} +E, E being the energy of 2 above the 1 ground state. Energy con
servation o)(2Pj) -j- E= k+ k 'is implied,
to the stim ulated emission process, this assumption requires verification in given experi
m ental situations, the w idth of the 2S^ level now being a function of the incident light
intensity. Equation (63) is the result of second-order perturbation theory on the conventional
interaction H am iltonian, Hl nt-,but the direct scattering term e2A 2 canno
to the m atrix elem ent in dipole approxim ation because the wave functions of the 2 and
lSi levels are orthogonal. Nevertheless, an algebraic transform ation analogous to the one
converting (56) into (57) can be carried through, assuming only closure and the energy
conservation condition, giving
|-< 2 ^ |g,.|f ) < f \ q j \ lSt) Iftl i y -1
J^{k,k') = -2 2 (64)
0(F )-k 0( P ) -k ‘ J
f It will be seen that the two alternative formulae (50) and (53) for the ‘ natural ’ line shape differ by
factor ( jkE2,)
and this is the explicit form of J). (k, k )which is obtained if the
calculation is carried through on A W (cf. G oppert-M ayer 1931; also Breit & Teller 1940).
In the experiments of Lam b (1950, 1952, 1953) the stim ulated decay process of the m eta
stable LH state is enforced by a very sharp prim ary line and there is no question of the
n a tu ra l' emission lines 2S± -> 2 or 2 -> 1 ^ . The requirem ent on the w idth of the 2»Sj
level in presence of the r.f. signal is am ply verified for all signal levels. The physically
im portant quantity for these experiments is therefore the induced radiation rate for incident
radiation (r.f.) with circular frequency k xin the neighbourh
completely parallel to the one carried out above and gives
(R ig h t) (65)
for the stim ulated decay rate of the state at frequency the incident signal of intensity
frequency k x,b eing polarized in direction e. T he factor in curly brackets is the total trans
tion rate T out of the 2 state, the photon E-\-o)—k lb eing em itted
since there is energy conservation, E^-co —In the beautiful an
experiments by Lam b, the incident r.f. signal frequency is kept constant and the energy
separation cobetween the n —2,
through the action of an applied static magnetic field which splits the levels into their
Zeeman components. This magnetic shift of course also affects the position of the Zeem an
components of 2 with respect to the ground state, th at is the value of Nevertheless, the
factor (E-Cco —k x)3is approxim ately constant as is varied in the neighbourhood of The
variation of the m atrix elements through the resonance, considered by Lam b, is negligible
and the Lam b lines—intensity against applied Zeeman splitting field— are Lorentzian to
w ithin about 1 %. This is in accord w ith the distribution of the decay rate as a function of
as given by (65). O n the other hand, if one were to proceed from the m atrix element in the
form (63), or else use the conventional H am iltonian /iijfii in the formalism of the dam ping
theory (cf. (62))
r->(25j; A,) = 2i , S { ^ ( E + o , - k 1) |<2P4 |q | 1S ^ } (Wrong).
( 66 )
If we again ignore the variation of the factor ) as a function of the Zeeman
splitting, the formula predicts a significant distortion in the distribution of in particular
a displacement of the m axim um by an am ount T2/4^1, because of presence of the factor
(co/k))2. Lam b has commented th at his results are definitely not compatible with the
presence of this factor in the resonance formula.
The experimental evidence therefore conclusively brings out the reality of the discrepancy
to which a straightforward perturbation theory on the conventional interaction H am il
tonian in Coulomb gauge can lead.
4. C anonical equivalence of H amiltonians

4 1 . Canonical transformation
It has been mentioned in the previous paragraph th at the use of the dipole interaction
energy (5), / / ”“ *• — eqE. ±(0) avoids the ambiguities which arise with the more conve
interaction H am iltonian (4). The dipole interaction was frequently used in the early
56-3
448 E. A. P O W E R AND S. Z IE N A U O N T H E C O U L O M B
days of quantum radiation theory and a proof for the equivalence of and was given
by G oppert-M ayer (1931). However, both G oppert-M ayer’s argum ent and a more recent
deduction by R ichards (iqqyâpply only w hen the electrom agnetic field can be considered
an external field w ith a prescribed equation of motion. I t is not clear, for instance, from
this work w hether the electric field strength E in the interaction is the total electric field
acting on the atom or merely its transverse com ponent. W e have already shown th a t the
equivalence of and Hjf*" can be established in the more general situation w hen atom
and radiation are considered a single, closed dynam ical system, provided only the Coulomb
field is carefully considered.
T he classical radiation field structure of a bounded oscillating charge-current system was
recalled in § 3 1 . O u r aim is to provide an approxim ation m ethod in the q u an tu m theory of

radiation which, for problems like those of the previous section, proceeds in closer corre
spondence to the classical formalism th an the standard treatm ent, b u t m aintains the
Coulomb gauge. Crudely speaking, it is desired to incorporate the entire atom w ith its
K lein correspondence charge and currents (Klein 1927; Pauli 1933/1958) as a source of the
transverse radiation field, whereas the standard formalism, modelled on the relativistic
theory, does the same for the point charge. T h a t such a form ulation of the theory leaves
room for radiative reaction in the accepted sense, is shown by the C asim ir-Polder work on
the influence of retardation on the London—van der W aals forqes and will be illustrated
further below through consideration of the non-relativistic Bethe (1947) approach to the
Lam b shift.
T he most elegant form ulation of the classical electrom agnetic radiation from an oscillating
charge current distribution uses the H ertz vector and avoids irrelevant monopole contribu
tions by introducing a fictitious polarization vector field P as a source for the electro
m agnetic field. This vector field is related to p and j by
j = P, />= - v . P (67)
and is assumed to vanish outside a certain volume P is a convenient representation for the
oscillating p a rt of the bounded charge current distribution. A static monopole contribution
to the electric field outside V m ay have to be added in if the system is not overall neutral
(Jeffreys & Jeffreys 1950, §24-23).
I t is this representation of the sources which we take over into q u antum theory. T he
possible additive monopole contribution to the energy, which is static and involves no
coupling to the radiation field, will be ignored. We assume therefore th at the atom is neutral,
b u t this is not a loss of generality, except in problems where the m otion of the ion cannot be
ignored.
T he non-relativistic coupling of charges to radiation cannot be expressed in the form
- J j . A dr in the H am iltonian and the incorporation of the polarization operator P (x ,
therefore requires a num ber of interm ediate steps. W e start from the H am iltonian
[p®-«A(q<0)]2+ E/(q®) + ^ / [ | E | 2+ |H|*] dr. ( 68 )
H ere E — E^ + E 11= —47r0* + E 11is the total electric field, being the field operator con
jugate to A. U contains the electron interaction w ith the nuclear electrostatic field and any
G A U G E IN N O N -R E L A T IV IS T IC Q U A N T U M E L E C T R O D Y N A M IC S 449
o th er external potential fields and the electrostatic repulsion betw een the electrons. T h e
lo ngitudinal electric field E 11is therefore to be derived from the longitudinal p a rt of P , as in
eq u ation (34). T h e polarization field operato r P is defined th ro u g h the m ultipole develop
m en t (cf. (33)) I K/ >‘ x
P (x ) = 2 H '> » (x )-1 2 ^ q ® (q ® .V )# ( x ) + ..., (69)
I I
w hich expresses the fact th a t we consider the atom as a b ounded system of charges confined
to the neighbourhood of the origin. This restriction can be in co rp o rated q u an tally only via
a m ultipole developm ent since, strictly speaking, the charge an d c u rren t density reaches to
infinity. H ence, by (34),
E f (x) = —4kfte§j H (x) + 477Q'jk dj Sfk{ x ) + ... (7°)
is the m ultipole developm ent of the longitudinal field, w here electric
q u ad rupole m om ent of the atom .

T h e re d u n d a n t variable E'*(x) is now elim inated from the form alism , and (68) has been
reduced to
H= 2 i [p(')-eA(q<»)]2+ < 7 + ^ j ‘[ |E ^ |2+ | H | 2] d T + 2 jrj |P " |2dr, (
w here P 11is the longitudinal p a rt of the vector field P .

T h e next step in the reduction of H is effected by a canonical transform ation S, w hich is so
chosen th a t the transform ed transverse electric field o p erato r no longer contains a static
adm ixture, w hen m atrix elem ents in the presence of an atom are com puted. This req u ire
m ent fixes Sun am biguously, if the corresponding classical situation is kept in m
A lthough the static adm ixture to { E f) m
nc om puted in (31) in d
found to be a gradient a t points x 4= 0, nevertheless, it is actually a transverse field, and the
canonical transform ation differs to this extent from a gauge transform ation. H ow ever, we
are assuming th a t the vector field P (x ) vanishes outside a certain region, and in this region,
w hich defines the outside of the atom in our approxim ation, P and P 11 are no longer
in d ependent quantities, their sum reducing to zero.
T h e transform ed electric field strength is required to satisfy
<fx(x) = E x(x) +47tP-l(x ), (72)
P x being the transverse p a rt of the vector field P , (59). O ne easily verifies th a t this tran s
form ation eliminates the unw anted static field adm ixture in the electric field strength
expectation values. < ^(x) is therefore to be considered as the physically m easurable
dynam ical variable and the H am iltonian H is to be expressed in term s of ra th e r th an of
E x. This transform ation is the central feature of our work and incorporates the atom w ith
its C oulom b field into the redefined modes of the quantized rad iatio n field.
T h e electrom agnetic field p a rt of the H am iltonian, / / rad. + 277j|Pll(x) |2dr, can now be
w ritten
ffMa. + 2» rJ|P "(x )|2d r = i J [ K ±|2+ |H |2] d 7 - J ^ . P J- d r + 2 7rJ |P ^ |2d r+ 2 7 7 j|P “|2d r
= 2 -J [|^ J -|2 + |H |2] d r - J . S ’-L.P d T + 2 ) r J |P |2dT. (73)

T he last term is a self energy of the atom and can often be neglected (cf., however, the
discussion at the end of this section). T he transform ation is canonical, since P
commutes w ith all field variables, and there is no longer any need to distinguish between the
operators E^ and in the transform ed H am iltonian (73), both being essentially the
conjugates of A.
It remains to transform the m atter p a rt 2[p$ —iA (q®) ] 2 of the H am iltonian (71). I t is
i 2m
convenient to use the transform ation function which converts E x into <?±:
= SEXS ~ \ (74)
S — exp / —i 0J p . A d r j .
To see th a t this is equivalent w ith (72), recall
-i^ (x -y ) (78)
for operators taken at equal times. T he atomic p a rt of the H am iltonian can only be trans
formed w ith the aid of a m ultipole expansion. T he electrodynam ic potential A (q(/)) is
expressed as A(q®) --- A(0) + (q® .V) A (0 )+ ...
and S = II exp ( —icq®. A(0) —Jie(q®(.V) q® .A (0) + . . . ) , (76)
I
introducing (69) into (74). C arrying out the two successive unitary transform ations ex
plicitly w ritten out in (76)
s - 12 ^ [ p ® - ^ ' 0)]2s = z ^ (p®)2- z i s w 0 x p®] -[ v x a ( o)]
+ | ^ [ q ® x [ V x A ( 0 ) ] ] 2+ . . . . (77)
T he second term in (67) is the m agnetic dipole contribution —{ju H(O) to the interaction
energy. This term , in interference with the electric dipole term Hlf^, has been used to discuss
the rotation of the plane of polarization of light in an optically active m aterial or through an
applied magnetic field in the F araday effect (Power & Shail 1959). Collecting terms, we
find as the total transform ed H am iltonian for an atom and the quantized electrom agnetic
field (cf. (6))
H = Z ^ ( P ® ) 2+ CW>) + ^ J [ K i 2+ |H |2] d r —*q .<T(0) —| + ...
- l l .H (0) + 2 ^ [ q ® x H ( 0 ) ] 2+ ...+ 2 7 r J |P |2dr. (78)
T he electric multipole interaction has been w ritten out here up to the quadrupole term , the
quadrupole m om ent
Qu - - 1 1 (79)
having been made traceless (this is possible since V — 0). I t will be noticed th a t the
longitudinal field variables are completely eliminated. T he usual plane wave expansion of
the Coulomb gauge is to be used for the operator <fx, and the conjugate field variables in (78)
—(I/477) <f-L and A. T h e great advantage of the interaction energies over those of the
conventional theory is their explicitly gauge invariant appearance. T he entire theory is now
in a form where the electric field of an oscillating dipole, etc., real or virtual, appears
purely retarded, and m ay be said to contain the consistent extension of the pure non-
relativistic q u an tu m mechanics of atoms and molecules to the closed system of atoms, etc.,
and the radiation fields.
4-2. N on-relativistic Lamb shift
T o complete this section we consider the non-relativistic Lethe corrections to the Lam b
shift by the transform ed H am iltonian. T he transform ed H am iltonian is of course not
particularly suited to this calculation, which should proceed from a consistent elim ination
of the unobservable field of a point particle, whereas the transform ation (72), (74) does this
for a collection of charges. In fact it appears a hopeless task at first sight to obtain the
required answer, since the S 1-factor in the interaction brings up too m any powers of in
the num erator. Since, however, the canonical transform ation has been carried out on the
entire system atom and radiation the internal field energy shifts m ust be present in (78).
^ - 3
0 / E_0^
HnHa
Figure 3
P art of the non-relativistic Lam b shift energy is obtained from perturbation theory
through the Feynm an graph in figure 3. T he interaction a t each vertex is .<f-L(0). T he
contribution to the energy shift of the state |0> in second order is
A £i -- 2^ < °k J£ > < Æ |g .l 0) = |<0 |q | £> l2£ “ ' J q ^ , (80)
assuming th a t only the nearest excited /--state | contributes. T he integral is cubically

divergent for large Æmax. There is, however, a further contribution to the transverse self-energy
of the atom, arising from the last term in (78). To order picking out the transverse, dipole
part, 27rJ|P-L|2dr contributes
A E 2= 27t*2<0|JV,-£$k(x) (x) dr |0>
A W
= ^ 2 |< 0 |q |£ > |2J>dA;. (81)
T he entire transverse energy shift to order e2

b ecomes
&E1+ AE 2 = A £(0) = |<0 |q | (82)
This expression is to be renorm alized by subtracting the unobservable transverse self-energy

of the free electron averaged over the state |0). T he transverse self-energy of the free charge
must be com puted from the conventionalH am iltonian, th at is i/^ M n dipole approxim ation.
The direct scattering term £2A 2(0)/2 mives
g rise to an energy shift
= ^ < 0 |A 2 (0 ) |0 > = ^ j k d k = | * £ | < 0 |q | E )\* jkd k (83)

452 E. A. POWER AND 8. ZIENAU ON THE COULOMB
assuming closure with respect to the excited state Hence
A £(0) - A E & - ^ |<0 |p | £ > l2j | f | > (84)
which is the same as Bethe’s (1947) expression and is converted in a well-known m anner
to a logarithmically divergent one by further renorm alization, using the rem aining
— (e/m)p . A(0) p art of the free-electron H am iltonian.
To obtain this result it is essential to consider the entire electric dipole p art of the trans
formed H am iltonian (78), which illustrates directly the extent to which previous derivations
of the. dipole interaction —^ q .E ±(0) rem ain incomplete.
C ertain obvious modifications are necessary in the general formalism if more th an one
atom is in interaction with the radiation field. An application to the effect of retardation on
the van der W aals forces, published previously (Power & Zienau 1957st, 3), shows th a t
considerable simplification is achieved through use of the transformed H am iltonian. Since
the transformed interaction H am iltonian no longer contains the electrodynamic potentials,
it is advantageous in certain situations to work directly from the equations of m otion for the
field strengths <fx, H using Heisenberg representation and the propagation functions
suitable for these operators. In this way a form ulation of the theory is achieved, in Coulomb
gauge, which runs completely parallel to the one proposed by Heisenberg m any years ago
(Heisenberg 1931).
5. C onclusions
A transform ation of the conventional H am iltonian in the Coulomb gauge formalism of
non-relativistic quantum electrodynamics is carried out which has the advantage th a t
certain singular aspects of the Coulomb gauge are completely removed. T he transformed
H am iltonian appears as a multipole expansion and the transform ation is therefore adapted
to the interaction of charge collections, such as atoms or molecules, possessing a well-defined
charge centre, w ith radiation. A detailed discussion of the natural shape of emission lines and
the resonant absorption on the ground state or m etastable states of atoms is given, to exhibit
the kind of error to which the conventional theory is prone and to set out the validity of
a num ber of competing formulae. The expressions for the natural line shape (equation (53))
and for the resonant absorption in induced emission rate (equations (59) and (65)) obtained
here, are believed to be new and to present the definitive prediction of the quantum theory
of radiation (within non-relativistic and electric dipole approxim ation). It is pointed out
th at the experimental evidence of Lam b on resonant stim ulated emission from the m eta
stable 2 level of the hydrogen atom is in accord with the form ula advocated in this paper
and rules out a competing formula current in the literature.
We thank Professor H. B. G. Casimir for a stim ulating communication. Helpful con

versations with our friend L. Castillejo and the encouragem ent of Professor H. S. W.
Massey, F.R .S., are gratefully acknowledged.
A ppendix (see § 3-2)

I t may be helpful to indicate briefly how the dam ping factor T, which was introduced
phenomenologically into the m atrix elements (57) and (59) to avoid a resonance catastrophe,
can be obtained in the framework of the stationary perturbation theory. The two-photon
emission m atrix element AC.(Æ, Z) (equations (63), (64)) will be considered.
N ear resonance, th at is when k~ co
E-\-(o = k+ k' is the energy conservation condition. We may neglect the non-resonant
second term in (64) and all summands involving ^-states above the I L state. The time-
ordered Feynm an graph of figure 4 exhibits the process which overwhelmingly contributes
near this resonance. It suffices to consider those terms in the ^-m atrix which have the
2§;
E+a) E 0
Figure 4
/
/
/
/
zMm
/
/ A ?2 pn ky
2^ z 2Pk,/lsA / >
E+w 0E E0 0 £ 0
F igure 5
structure shown in the time ordered Feynm an graph of figure 5 in order to obtain non
singular behaviour at resonance. These terms in the ^-m atrix give a m atrix element
y ) (k ,k ') using = as interaction,
M m 1 ( 277) —3n d p n(27r)”+1 (i)2(n+l)^2(»+ l)

n= 0 [/2 -fold]
s, { 2S \ qi\ 2P ) { 2P \qj\lS )J (k k ')

(o —k)n+l P1P21••
XI
<& 115) <1^ |qk e J M 12 ...(IS \u e J X ) |2
(E-\-(o— k— pP) —
-\o)
(E
K M i
i S l »-o
i {( D~ k)n
y s jg ^ p y ^ p jq p is y
■27ie2J\kk') {k' -\-k—
-k-\ ir
The polarization of the photons p^, p2, ...,p nh as been suppres
The real p art of F, which arises from the ^-function contribution to the denominators
454 E. A. POWER AND S. ZIENAU
(k' —pn)~1? which require definition at resonance, is easily seen to be the total transition rate
out of the 2Pj state by electric dipole radiation to the ground state, evaluated at
pn — E-\- o
j—k—
A somewhat more general treatm ent of the behaviour near resonance w ithin the ^-m atrix
formalism has been given by Low (1952).
R eferences
Alder, K ., Bohr, A., Huus, T. & Mottelson, B. 1956 Phys. 28, 432.
Arnous, E. & Heitler, W. 1953 Proq.Roy. Soc. A, 220, 290.
Belinfante, F. J. 1946 hysica, 12, 1 .
P
Bethe, H. A. 1947 hys.Rev. 72, 339.

P
Bethe, H. A. & Salpeter, E. E. 1957 Encyclopedia of , vol. 35. Berlin: J. Springer.
Bleuler, K. 1950 Helv. Phys. Acta, 23, 567.
Breit, G. & Teller, E. 1940 Astron. J. 91, 215.
Gasimir, H. B. G. & Polder, D. 1948 hys.Rev. 73, 360.
P
Dirac, P. A. M. 1947 Quantum mechanics, 3rd ed. Oxford University Press.
Dsjaloshinsky, J. E. 1956 J.Exp. Theor. Phys. 30, 1112.
Fermi, E. 1932 ev.Mod. Phys. 4, 87.
R
Fierz, M. 1950 Helv.Phys. Acta, 23, 731.
Goppert-Mayer, M. 1931 Ann.Phys., Lpz., 9, 273.
Gupta, S. 1950 Proc. Phys. Soc. 63, 681.
Heisenberg, W. 1931 Ann.Phys., Lpz., 9, 338.
Heitler, W. 1944 The quantum theory of radiation, 2nd ed. Oxford University Press.
Heitler, W. 1953 Proc. Int. Cons. Theor. Phys., Kyoto and Tokyo.
Heitler, W. 1954 The quantum theory of radiation, 3rd ed. Oxford University Press.
Heitler, W. & Ma, S. T. 1949 roc.Roy. Irish Acad. A, 52, 109.
P
Hulme, H. R. 1936 Proc. Roy. Soc. A, 154, 487.
Jauch, J. M. & Rohrlich, F. 1955 The theory ofphotons and electrons. Cambridge, M ass.: Addison-Wesley.
Jeffreys, H. & Jeffreys, B. S. 1950 Methods of mathematical physics, 2nd ed. Cambridge University
Press.
Kikuchi, S. 1930 Z. hys.66 , 558.
P
Klein, O. 1927 Z. Phys. 40, 407.
Kramers, H. A. & Heisenberg, W. 1925 Z. hys.31, 681.
P
Kramers, H. A. 1938/1958 Quantum mechanics, North Holland; also Hand. Jahrb. chem. Phys., vol. 1,
Leipzig.
Lamb, W. E. & Retherford, R. C. 1950 hys.Rev. 79, 649.
P
Lamb, W. E. 1952 hys.Rev. 85, 259.
P
Lamb, W. E., Dayhoff, E. S. & Triebwasser, S. 1953 Rev. 89, 98.
Low, F. 1952 hys.Rev. 88 , 63.
P
Pauli, W. 1933/1958 Encyclopedia of physics, vol. 6, part I; also Handbuch der Physik, vol. 24, part I, both
Berlin: J. Springer.
Power, E. A. & Zienau, S. 1957a Nuovo Cim. 6 , 7.
Power, E. A. & Zienau, S. 19576 J.Franklin Inst. 264, 403.
Power, E. A. & Shall, R. 1959 Proc. Camb. Phil. Soc. 55, 87.
Richards, P. I. 1948 hys.Rev. 73, 254.
P
Weisskopf, V. & Wigner, E. 1930 Z. hys.63, 54.
P
Weisskopf, V . 1931 Ann.Phys., Lpz. 9, 23. j
Wentzel, G. 1948 Helv. Phys. Acta, 21, 49. t
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1959 RSTA Coulomb Gauge in Non-Relativistic Quantum Electro-Dynamics and The Shape of Spectral Lines

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1959 RSTA Coulomb Gauge in Non-Relativistic Quantum Electro-Dynamics and The Shape of Spectral Lines

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PHILOSOPHICAL TRANSACTIONS

ROYAL SOCIETY OF LONDON

Published by the Royal Society

Price Nine Shillings

COULOMB GAUGE IN NON-RELATIVISTIC QUANTUM ELECTRO­

{Communicated by H. S. W. asey, F.R.S.— Received 16

1. I n t r o d u c t io n a n d sum m ary 427 3 2. The natural shape of spectral lines 438

example 431 t o n ia n s 447

Vol. 251. A. (Price 9s. ) 54 [Published 15 September 1959

[ctkA>stk'A'] = ^kk'^AA' (2')

A (x, t) -- H aexp { i( k .x - ti) } + c .c .] (3)

non-relativistic radiation problems. T he Green function for the electrodynamic potentials of

H = 2 2 ^ ( p(Z))2+ U ( q(Z)) + i - J ( | ^ | 2 + |^ |2 ) d r —J<^x . P d r + |P |2dr

. , [q»X JT (0)]«+.... (6)

2. C oulomb gauge in perturbation theory

2 1 . Discussion and elementary example

turbation theory or w ith reference to an interaction representation, using a suitable unper­

H x + U = A (xt) +g 2ot(2). A( x2) + ............| , (7 )

state propagators and the energy exchange at each vertex is Using

and Af 4A,(k) cjA,(k ) = (4 = (8)

the two m atrix elements combine into the expression

2 2. Propagationfunctions in Coulomb gauge

(k = (k,k„),kx -- k . x - * 0<). (15)

with the retarded boundary condition is

@ij{x) — 4 Jd4A: (17)

and satisfies □ ^ ^ ( x ) — —S(t) Æy(x). (18)

whereas Æjj(x) is a representation of its longitudinal p art (cf. Belinfante 1946).

sin 'cos krsin

= —i(27T)~3j d 4k e ikxS(k2) e(k) ( | k | 2 ^ . — = (27i)~4J d (24)

T he associated retarded propagator, which satisfies

3. T he electromagnetic field and the shape of spectral lines

3 1 . The electric dipolefield transition matrix

H = 2 (p < » -« A (q ® ))^ -Z ^ 2 + ^ J (Ex2(x) + H 2(x)) dr. (27)

« x ) L = 2 e [ s^*(q(1)jq(2), •••,q(Z))T*„(q(1)q(2), . . q(Z)) IIdq^T

277J | P 11(x) |2dr = ^ J | E 11(x) |2dr. (35)

<£ -(X>*) >«. = 5 K J <Pj>«n a P { l *7 (f~ ' 1} ~ %) + to, (38)

which is the result expected by the correspondence principle.

Y (£ ; 0) = {!"(£) \0) + 2j ~ ^ m (39)

3 2. The natural shape of spectral lines

w ith Y (0; 0)> = m0| > + 2 |

<T(0; 0) \E t( x ,t) \'¥ ( t) ) ~ [e x p { -i(£ -liD

<T(0; 0) |£ f(X ,t)|¥ (< )> ~ - , < 6»,>£«i(% -$ ,% ) exp{i(r-< ) ( L - j i l H - s t - r ) , (46)

JL _ ___ ?____ =* _______ !)-i-Q(g2)

photon m atrix elements of the conventional interaction H am iltonian

p {k) dk = — (A_ £ )2+ j r 2 (61)

m fact - 7(2**) <ft w m (82)

3 3. Resonant absorption and stimulated emission rates

of ^ij(k , k') into (cf. Dirac 1947)

4 * (k ) ~ <G; k> A a>'1 ‘;l G;k- — > (57)

Px,(hk') = — S(k—k') n(k) l<G ;k’ * I ^ M Æ ^0> N < £; 0 1 ^ 1 G y t ' , MW (58)

m LX- I<G; k, A I f l r ) 0>|= |< £; 0 |f l p - |

= 27, S { ^ k \ |<£ |q | (R ight). (59)

r-' - 2 E ) t& h |\<

{ } = 2 " / M § 6 Q ( L ) 2 KG; k,A 0>| ( 61 )

4. C anonical equivalence of H amiltonians

recalled in § 3 1 . O u r aim is to provide an approxim ation m ethod in the q u an tu m theory of

[p®-«A(q<0)]2+ E/(q®) + ^ / [ | E | 2+ |H|*] dr. ( 68 )

is the m ultipole developm ent of the longitudinal field, w here electric

q u ad rupole m om ent of the atom .

w here P 11is the longitudinal p a rt of the vector field P .

= 2 -J [|^ J -|2 + |H |2] d r - J . S ’-L.P d T + 2 ) r J |P |2dT. (73)

To see th a t this is equivalent w ith (72), recall

s - 12 ^ [ p ® - ^ ' 0)]2s = z ^ (p®)2- z i s w 0 x p®] -[ v x a ( o)]

COULOMB GAUGE IN NON-RELATIVISTIC QUANTUM ELECTRO

turbation theory or w ith reference to an interaction representation, using a suitable unper

« x ) L = 2 e [ s^(q(1)jq(2), •••,q(Z))T„(q(1)q(2), . . q(Z)) IIdq^T

<£ -(X>) >«. = 5 K J <Pj>«n a P { l 7 (f~ ' 1} ~ %) + to, (38)

JL _ _ ? =* _____ !)-i-Q(g2)

We thank Professor H. B. G. Casimir for a stim ulating communication. Helpful con