PHYSICAL REVIEW

VOLUM E

136,

NUM B ER 3 8

NOVEMEBR

1964

EleCtrOn Gaa*

InhOmOgeIIeouS
P.

HOHENBERGt

Ecole Xornzale Superzeure, I'aris, France

AND

W. KonNt
Ecole Xonnale Superieure, I'aris, Prance and I'aculte des Sciences, Orsay, France
and
University

of Calzfo&nia at San Diego, La Jolla, Calzfornia

(Received 18 June 1964)

This paper deals with the ground state of an interacting electron gas in an external potential v(r). It is
proved that there exists a universal functional of the density, Ft (r) g, independent of v(r), such that the ex= fs(r)n (r)dr+Ft (r) has as its minimum value the correct ground-state energy associated with
pression E
s(r). The functional FLn(r)j is then discussed for two situations: (1) n(r) @san(r), 8/ao((1, and
In both cases F can be expressed entirely in terms of the cor(2) a(r) = q (r/ra) with p arbitrary and 1'p
relation energy and linear and higher order electronic polarizabilities of a uniform electron gas. This approach
also sheds some light on generalized Thomas-Fermi methods and their limitations. Some new extensions of
these methods are presented.

I j

~ ~.

INTRODUCTION
'

'

&~ IJRING the last decade there has been considerable

the properties of a
progress in understanding
homogeneous interacting electron gas. ' The point of
view has been, in general, to regard the electrons as
similar to a collection of noninteracting
particles
with the important additional concept of collective

excitations.
On the other hand, there has been in existence since
the 7920's a different approach, represented by the
Thomas-Fermi method' and its re6nements, in which
the electronic density n(r) plays a central role and in
which the system of electrons is pictured more like a
classical liquid. This approach has been useful, up to
now, for simple though crude descriptions of inhomogeneous systems like atoms and impurities in nietals.
Lately there have been also some important advances
along this second line of approach, such as the work of
Kompaneets and Pavlovskii, ' Kirzhnits, ' Lewis, ' Baraff
and Borowitz, ' Bara6, ' and DuBois and Kivelson. ' The
present paper represents a contribution in the same area.
In Part I, we develop an exact formal variational
principle for the ground-state energy, in which the density tz(r) is the variable function. Into this principle
enters a universal functional PLtr(r)), which applies to
all electronic systems in their ground state no matter
what the external potential is. The main objective of
* Supported in part by the U. S. Once of Naval Research.

f NATO Post Doctoral Fellow.

Guggenheim Fellow.
'f For a review see, for example, D. Pines,

Elementary

E'.'xci tati

in Solids (W. A. Benjamin Inc. , New York, 1963).

ons

' For a review of work up to 1956, see N. H. March, Advan.

Phys. 6, 1 (1957).
A. S. Kompaneets and E. S. Pavlovskii, Zh. Eksperim. i.
Teor. Fiz. 51, 427 (1956) [English transl. : Soviet Phys. JETP
4, 328 (1957)
D. A. Kirzhnits, Zh. Eksperim. i. Teor. Fiz. 32, 115 (1957)
JETP 5, 64 (1957)
I English transl. : Soviet Phys.
' H. W. Lewis, Phys. Rev. 111,
1554 (1958).
' G. A. 13araff and S. Borowitz, Phys. Rev. 121, 1704 (1961).
7 G.
A. BaraG, Phys. Rev. 123, 2087 (1961).
'D. F. Du Bois and M. G. Kivelson, Phys. Rev. 127, 1182

j.

(1962).

j.

is a description
theoretical considerations
of this
functional. Once known, it is relatively easy to determine the ground-state
energy in a given external
potential.
In Part II, we obtain an expression for FLnj when tr
deviates only slightly from uniformity, i.e. , n(r)=1'cp
0; In this case FLej is entirely
+ts(r), with ts/tss
expressible in terms of the exact ground-state energy
and the exact electronic polarizability n(g) of a uniform
electron gas. This procedure will describe correctly
the long-range Friedel charge oscillations' set up by
a localized perturbation. All previous refinements of the
Thomas-Fermi method have failed to include these.
In Part III we consider the case of a slowly varying,
but +of necessarily almost constant density, tr (r)
= p(r/rs), rs &oo. For this case we derive an expansion
of F)trj in successive orders of rs ' or, equivalently of
the gradient operator V acting on e(r). The expansion
coeKcients are again expressible in terms of the exact
ground-state energy and the exact linear, quadratic,
etc. , electric response functions of a uniform electron
gas to an external potential w(r). In this way we recover,
quite simply, all previously developed refinements of
the Thomas-Fermi method and are able to carry them
somewhat further. Comparison of this case with the
nearly uniform one, discussed in Part II, also reveals
why the gradient expansion is intrinsically incapable
of properly describing the Friedel oscillations or the
radial oscillations of the electronic density in an atom
which reQect the electronic shell structure. A partial
summation of the gradient expansion can be carried
out (Sec. III.4), but its usefulness has not yet been
tested.

&

I. EXACT

GENERAL FORMULATION

I. The

Density as Basic Variable

Ke shall be considering a collection of an arbitrary
number of electrons, enclosed in a large box and moving

' J. Friedel,

Phil. Nag. 45, 155 (1952).

I N HOMOGENEOUS
under the influence of an external potential v(r) and
the mutual Coulomb repulsion. The Hamiltonian has
the form

H= T+V+U,

where'0

~~i*(r)~~i (r)dr,

ELECTRON GAS
where Pfn] is a universal functional, valid for any
number of particles" and any external potential. This
functional plays a central role in the present paper.
With its aid we define, for a given potential v(r), the
energy functional

(2)

Egn]=

(10)

P*(r)P*(r') (r') P (r) drdr'

We shall in all that follows assume for simplicity that
we are only dealing with situations in which the ground
state is nondegenerate. We denote the electronic density
in the ground state 0' by

which is clearly a functional of v(r).

We shall now show that conversely v(r) is a unique
functional of N(r), apart from a trivial additive constant.
The proof proceeds by reductio ad absurdum'. Assume that another potential v'(r), with ground state
4' gives rise to the same density N(r). Now clearly
(unless v'(r) v(r)=const] 0' cannot be equal to
since they satisfy different Schrodinger equations.
Hence, if we denote the Hamiltonian and ground-state
energies associated with 0' and 0' by H, B' and E, E',
we have by the minimal property of the ground state,

E'= (@',H'+') & (+,H'+) = (+, (H+ V'

(r) (r) dr+ F LN].

Clearly, for the correct is(r), Ege] equals the groundstate energy E.
We shall now show that E,ge] assumes its minimum
value for the correct n(r), if the admissible functions
are restricted by the condition

V= v(r)i(*(r)P(r)dr,

V)%'),

fm]

n (r) dr = cV.

It is v ell known that for a system of

energy functional of 4'

E particles,

the

(12)
has a minimum at the correct ground state 4, relative
to arbitrary variations of 0' in which the number of
particles is kept constant. In particular, let 4' be the
ground state associated with a diferent external potential v'(r). Then, by (12) and (9)

BL@']=

) 8,$+]=

(r) I'(r) dr+Fc ri'],

v(r)e(r)dr+FLri].

so that

E'&E+

$v'(r)

v(r)]e(r)dr.

Interchanging primed and unprimed quantities, we find

in exactly the same way that

E & E'+

$v (r)

v' (r)]ti

(r) dr.

Addition of (6) and (7) leads to the inconsistency

E+E & E+E~

~

Thus v (r) is (to within a constant) a unique functional

of e(r); since, in turn, v(r) fixes H we see that the full
many-particle ground state is a unique functional of
rs(r).

2. The Variational Principle

is a functional of n(r), so is evidently the

Since
kinetic and interaction energy. We therefore define

ro

At, oDllc url'its are- use

Thus the minimal property of (10) is established relative to all density functions I'(r) associated with some
other external potential v'(r).
If F(1) were a known and sufFiciently simple functional of n, the problem of determining the ground-state
energy and density in a given external potential would
be rather easy since it requires merely the minimization
of a functional of the three-dimensional density function. The major part of the complexities of the manyelectron problems are associated with the determination
of the universal functional FLn].

"

3. Transformation

of the Functional P/n]

Because of the long range of the Coulomb interaction,

it is for most purposes convenient to separate out from

'~ This is obvious since the number of particles is itself a simple
functional of n(r).
~ We cannot prove whether an arbitrary positive density distribution a'(r), which satisaes the condition J'e'(r)dr=integer, can
be realized by some external potential v'(r}. Clearly, to first order
in R(r), any distribution oi the form n'(r) =no+n(r) can be so
realized and we believe that in fact g, ll, except some patbologicaf
distributions, can be realized,

P. HOHEN BERG
F[n] the

classical Coulomb energy and write

1

.[n]

so that E,

(r) n (r')

iz

F[n]=

r'l
r

and

R(r)dr=0

drdr'+ G[n],

Here we clearly must have a formal expansion of the

following sort:

(r) n(r) dr+

n (r)n (r')

drdr'+G[n],

(15)

where G[n] is a universal functional like F[n].

Now from the definition of F[n], Eq. (9), and
Eq. (14), we see that

G[n],

G[n]=

(23)

(14)

becomes
1

E,[n]=

W. KOHN

AND

V,V, .n~(r, r')

r'l
r

l, , dr+

C, (r, r')

drdr'. (16)
r'l
r

G[n] = G[np]+

E(r r')R (r)R (r') drdr'

I(r, r', r") R(r)

R(r') R(r"} dr

dr'

dr"+ .

. (24)

ln this equation there is no term linear in R(r) since

by translational invariance the coefficient of R(r) would
be independent of r leading to zero, by (23). The kernel
r
appearing in the quadratic term is a functional of r
only and may therefore be written as
l

Here n, (r, r') is the one-particle density matrix; and

Cz(r, r') is the two-particle correlation function defined
in terms of the one- and two-particle density matrices as

Cz(r, r')=nz(r,

r'; r, r') nz(r, r)nz(r', r').

(17)

n(r).
Of course nz(r, r) =
From (16) we see that we can define an energy-density
functional
g p[n]

= z V~V~ 1zz(r)r )

C, (r r'/2; r+r'/2)

dr'

(18)

(25)

The higher order terms will not be further discussed

here.
One may also quite trivially introduce a density
function

g, [n]= gp(np)+

"' "'

It(r r')=(1/~l)Z It(q)e

IC(r')R(r+-,'r')R(r

'r')dr'+,
,

(26)

where gp(np) is the density function of a uniform gas of

electron density np (kinetic, exchange, and correlation

energy).

such that

G[n] =

2. Expression of the Kernel X in Terms of

g, [n]dr.

the Electronic Polarizability

The fact that g, [n] is a functional of n follows of course

from the fact that 4' and hence e~ and e2 are.
It should be remarked, that while G[n] is a unique
functional of n, g, [n] is of course not the only possible
energy-density functional. Clearly the functionals

We shall now see that the kernel IC appearing in

Eqs. (24) and (26) is completely and exactly expressible
in terms of the electronic polarizability n(q). The latter
is defined as follows: Consider an electron gas of mean
density eo in a background of uniform charge plus a
small additional positive external-charge

n.,(r) = (X/Q)g

i9

g, [n]=g, [n]yP

ts, &'&[n],

(20)

density

a(q) e-'q'.

(27)

Write the electronic density, to first order in X, as

where the h~') are entirely arbitrary, give equivalent
results when used in conjunction with (19).
The following sections deal with G[n] and g, [n] in
some simple cases.

n(r)

n(r) = np+R(r),
R(r)/n,

b, (q)e-'q'.

(29)

Let us now define the operator

Pq=g

Ck

(3o)

Ck,

where c~*, c~ are the usual creation and annihilation

operators. Then, by first-order perturbation theory,

(21)
(22)

(28)

= bz(a)/~(a).
~(V)

II. THE GAS OF ALMOST CONSTANT DENSITY

1. Form of the Functionals G[n] and g[n]
We consider here a gas whose density has the form

= np+ ()/Q)p

b~(q)

= (8~)~(v)

(oI pql

n)(nip-. o)
l

(31)

I~ HOMOGE~TI:OUS El

Ro
I C I R

GAS

ib

so that.
1.0

(32)
Next we express the change of energy in terms of ct
By second-order perturbation theory we have
li'(4z. )'

Ia(q) I'

jj= ji, s+-

(0I p, le)(~el

q .

sl0)

Fr.o. 1. Behavior
of the electronic polarizability n(q), as
function of q (electronic
density =4
&(10" cm ').

Rtq)

0.5

q4

li'2

= ~''()

~(q),

'

Ib

(q)l'

E=

n(r)ri(r)+
2

Ib (q)

I'

n (q) q'

fl

V27r

lb (q)

(i

'

l tl y, in
Equivaen

0:

K(q) = 2z.

&

q + 2kp.

I'

q'

dK/dq

&

(q) I'

(34)

(35)

+~:

[cs+ (css c4) q'+

++ ~;

=-2~

~ 2k'

'.

q +~:

q' e(q)

G[N7 = G[rrs7+

n(q)

76(r),

27r

cs 8 (r)'dr

~ oo

~ const/q

= [1+(q'/kp')S(q)7 '

V'n(r)

I'dr+,

(48)

(37)

(38)
(39)

One of the most significant features of K(q) is its

.' att q==2k . This is responsible for the longsingu l arity
'
range Friedel oscillations" in E(r),

(4o)

i
b y the randomThese general properties are exemp lified
phase approximation in which

n(q)

, ea s o

i.e, , a gradient expansion.

= 1+csq'+c4q'+ . .

de/dq

K q,

(36)

The polarizability u(q) has the following properties,

as function of q (see Fig. 1)
Q(q)

(46)

K(r) = 27r[ cs+ (css c4) V+

+(css c4)

Nature of the Kernel

&0:

(44)

(45)

+ constXq .
K(q)

At this point an important

.7;

n(q)

we may write

3. The

(43)

2k r

which in turn gives

e(q) =

E(q)

of the dielectric constant,

terrors

4k p2/

(See Fig. 2.)

The power-series expansion of

=-2'
q'

q+2kF

2q

of Eqs. (33) and (34) gives

E(q)

(42)

This gives for E(q), by (35),

+2 K(q)
Comparison

Eqs. (15), (24), (25),

m(r)e(r )
drdr'+ G[e7

r'I
Ir

li'4'

q' )
kr
'+
ln
1

5(q) =

On the other hand, combining

and (28) gives

and

a(q)q'

&

kg = (4k p)'i'
(33)

screening constan,

wheie h'y is th e Thomas-Fermi

q'

li'2

q/qF

(q)l'

=~o

(41)

~~:

E(r)

remark must be made.

const cos(2krr+ 8)/r'.

(49

These obviously lie outside the framewor r of the

power-series expansion (44) of E(q) and hence outside
e gr
er the original Thomas-Fermi met od which
w h yneieither
onl y thee first
for the present system reduces to keeping
in on
~44~~~ nor its eneralizations
by the addition of
gradient terms, have correctly yielded wave-mec anica
density osci ations, suc
atoms which correspond to shell structure, or the ne e
oscillations in alloys which are of the same general origin.
. S. Langer and S. H, Vosko, Phys. Chem. Solids 12, 196
(1960}.

P. HOHEN BERG

AN D

W. KOHN

the Thomas-Fermi

V'v;(r)

equation

= (2 &'/37r)f p
v, (r)5'&
v(r)

2. The Gradient Expansion

10FxG. 2. Behavior
of the kernel E'(q),
as a function of q

(electronic density
&10" cm 3).

=4

It is well known that one condition for the validity

of the Thomas-Fermi equation is that ri(r) must be a
slowly varying function of r. This suggests study of the
functional Gfej, where e has the form
N(r)
with

(58)

= y(r/rp),

(59)

ro~~ .

(60)

It is obvious

III. THE

GAS OF SLOWLY VARYING DENSITY

1. The Thomas-Fermi Equation

For a erst orientation we shall derive, from our general
variational principle, the elementary Thomas-Fermi
equation. For this purpose, we use the functional (18)
and in (16) we neglect exchange and correlation effects,
thus setting C2=0. We approximate the kinetic-energy
term by its form for a free-electron gas, i.e. ,

f&5= i'oft~
(~)]'~,

where the Fermi momentum

+Z

kl: is given by

&i(r)&p(r')

r'f
fr

drdr'

f~(r)]""(52)

+r'p (3~')'"

To determine e(r) we now set

8

Efe] e(r)dr =0,

&i

where p, is a Lagrange
equation

m(r')

v(r)+
/r

If we

r'f

parameter.

(53)

This results in the

dr'+-', (3 r')7'"fm(r)]'

v, (r)

(54) is equivalent
N(r)

(r')

dr',

){2'v(r) v, (r)5)'&'

VPv;(r)

= 4v 0(r) .

. . (61)

Here successive terms correspond to successive negative

r p. Quantities like
powers of the scale parameter
gp(e(r)), g;(n(r)) etc. , are functions (not functionals)
of N(r). No general proof of the existence of such an
expansion is known to us, although it can be formally
verified in special cases, e.g. , when Gfe(r) 5 can be expanded in powers of fe(r)
Npj. At. the same time,
we know that, for a finite r0, the series does not strictly
converge (see the discussion at the end of Sec. II.3),
but we may expect it to be useful (in the sense of asymptotic convergence) for suKciently large values of rp.
Now a good deal of progress can be made, using only
is a universal functional of n,
the fact that g,
independent of v(r). This requires g, fej to be invariant
under rotations about r. The coeKcients g, ;,
(n(r)),
being functions of the scalar e, are of course invariant
under rotations. Hence one 6nds by elementary considerations that g, fnj must have the form

flj

g, fnj= gp(n)+ fgp&'(e) V'm+gpt &(n)(VN Vn)5

+terms of order
(55)

to the pair of equations

= (1/3m

V, V, &i(r)]+

' &Ii=0
(54).

now introduce the "internal" potential

n

""(~(r)) V'~(r)V~(r)

Lg

+g;, &'&(n(r))

(51)

This results in

Zfe]= v(r)e(r)dr+-

g, f&i]=gp(N(r))+g g, (n(r)) Vps(r)

(50)

= (37r'e)'~'.

k p(n)

that this is quite a di6erent class of systems

than that considered in Part 11 (N=ep+n, 8/Np1),
since now we shall allow q to have substantial variations. On the other hand, whereas in Part II, rI, could
contain arbitrarily short wavelengths, these are here
ruled out as r0 becomes large.
We now make the basic assumption that for large r0,
the partial energy density g, fnj may be expanded in
the form

(56)
(57)

From (56) and (57) we can eliminate m(r) and arrive at

V~4.

(62)

A further simpli6cation results from the fact that we

may eliminate from g, fej an arbitrary divergence
Q, V,h, 'fN] (see the end of Sec. I.3). It is then elementary to show that g, fnj may be replaced by

g, f&r j=gp(e)+gp "&(N)Ve

V&p

+{g "&(e)(V'e)(V'I)+g

i'&(n)(V'&i)(VN VN)

+g4'4&(e) (VN

Ve)')+O(V P). (63)

EOUS F LECT RON GAS

I NHOMOGEN

Here the subscripts refer to the number of gradient

operators (or the order in 1/rp) and the superscripts to
the number of times that n appears to the right of
g &"&(n).
It may be worth recalling that while g[n] is an
admissible density function in the sense that

G[n] = g, [n]dr,

Now let us set

We shall now express the coefficients g&"&(n) appearing in Eq. (63) in terms of the expansion coef6cients, in powers of q, of the electronic polarizability
a(q), and similar higher order, nonlinear, response
functions.
We do this by applying our general expression (63) to
the case of a nearly uniform electron gas, considered
already in Sec. II.2. We go, however, beyond (28) and
write

P b((q)e

"'+P b, (q)e-"'+
0

go (no)

q&0,
~
b, (q) = 1+.
j

4~)

~qo+

2go

&'&

+g

(4~1

(o&-

q'+"

~(q)

2m.

f/I

(q) =E

q'+"

q').
~(q')~(q

8x

n(r)dr

=0.

(67)

go&'&'(Vn
)'

V (Von)+2g4(o& (VoVon)

( &" (V4n)4+2g "&Vn V'(V'n)'

2Vn V(Von) 2(V'n)')

3g4(4)'(V'n)' 4g &'&V'n(Vn)' 4g &4&Vn V(Vn)'
+ . -~=0 (68)

(73)

now expand the response functions in powers of q,

= 1+c,q'+c4q'+
~(q, q') = 2 2 C-'q'"q ",
n(q)

V'n+3g4&'&'(Von)'+2g4('&" (Vn)'V'n

+ 2g4(o&~Vn

)Q

pg=o.

"'j

(76)
(77)

we can identify the functions g&"). Thus

= co,
= ,' ( c4+ co'),
go &"/4'

(78)

gp /4'&I

/4=

g4

dr'+go'

(74)

If we

This gives

(r')

(73)

giving

(i (q(, qo) ~(q()~(qp),

F[n]p

r'/
r

b((q) = 0,

+2g4&2&q4+

Similarly, we obtain

Now let us compare these expressions with what one

obtains with the use of (63). We require that

"&q'

. (65)

etc.

v(r)+

(72)

Also clearly

01+q.2=%

8e

(71)

4m

bi(q) =~(q)~(q),

'

iio=0,

+gp"+2go

~(q)+
2

functions are then de6ned by the relations

(q) =

'

Collecting terms of order go l(i $2 we find

The linear- and second-, third-, etc. , order response

bo

(70)

"Pi+~ Po+ '

=go+

4x

Gradient Exyansion

]e-'4',

n= no+ Q @bi(q)+X'bo(q)+

3. Identi6cation of the CoeKcients of the

q'

(64)

it differs from the energy density function g, [n], Eq.

(18), by a divergence.

(69)

IJ

n(r)=np+

u(q)
4$'I

X44r

o ( co+ 2coc4

(79)

co ) .

(80)

Similarly all other coefficients g&'&(n) can be expressed

in terms of the expansion coe%cients cof the linear
polarizability o, (q) of an electron gas of density n.
ln an analogous manner we can express all g(3) in
terms of c((qi) and n(qi, qo); and generally g&"& in terms
of n(qi),
n(qi, qo,
q i).
On dimensional grounds we can see from (63) that
the gradient expansion requires

+g4('&(Vo(Vn)'

Vn ~/n&&k, (n)

V,V;ni/i

Vnik, (n).

(81)
(82)

P. HOHEN BERG
Both of these conditions are necessary. For while (81)
would admit the case of a nearly uniform gas with a
this and
small but short-wavelength
nonuniformity,
similar cases are excluded by (82), as they must be.

In the preceding section we have expressed the coefficient g(2& in terms of the expansion coefficient c, of
the polarizabilityn(q), Eq. (76). However, we may apply
the expression (63) to the special case of the gas of
almost constant density, discussed in Part II. This shows
that the leading term gp(n) and the subsequent subseries involving coeAicients g("(n) may be summed to
yield
A.

', r')
n(r) j
(,i(r')[n(r+

y [n(r r') n(r)]dr'+

-',

. ~7q r'
~

en(r)

r, is the radius of the Wigncr-Seitz sphere

(83)

s4vrr,

This expression is
At
only for r,
metals (2&r, &5),
have been proposed.

(1)

S. Approximate Expressions for the CoefBcients

in terms of properties of the uniform electron gas. We

now collect some results of existing calculations referring to the uniform electron gas which are useful for
our present purposes.

a., gp(n)
This is the sum of the kinetic+exchange+correlation
energy density of a uniform gas of density m. Here one
has available the high-density expansion of Gell-Mann
and Brueckner'4;

2.21

O. 91.6

+0.062 lnr, 0.096+0(r,) n,

(85)

rs
'4

0.916 0.88

n.
r.'
r, r, +7 8.

"

"

M. Gell-Mann and K. Brueckner, Phys. Rev. 106, 364 (1957).

" Nozieres

g"'(n)

These coefficients are all determined in terms of the

electronic polarizability, n(q). For this latter quantity
there is available, at present, a random-phase expression, Eq. (41), which gives
27(

kg.

' 1+kp

$(q)

(88)

and
('&

(89)

4a

24 kc'kI;2

g4(2)

4'

18O k'kI,

(90)

'

Inclusion of the erst of these in the energy expression

agrees with a correction to the Thomas-Fermi energy
functional derived by Kompaneets and Pavlovskii. '
An expression for n(q), allowing in an approximate
manner for exchange eff ects has been proposed by
Hubbard.
It is

"

In the previous section we have expressed the coefficients g("i appearing in the gradient expansion (63)

believed to be reasonably accurate

lower densities, such as occur in
various approximate
expressions
One is due to Wigner"

Other approximations are due to Hubbard,

and Pines and Gaskell

of the Gradient Expansion

gp(n)

(86)

2. 21

The form (83) of ghas the merit of being exact in both

limiting cases where either the density has everywhere
nearly the same value (see Part II) or is slowly varying.
Its quantitative value for calculating the electronic
structure of actual atomic, molecular, or solid-state
systems is at present uncertain but. is being exaniined.
However, it is already clear that if applied to an atom
it will, unlike the simple Thomas-Fermi theory, yield:
(1) a finite density at the nucleus, and (2) oscillations
in the charge density corresponding to shell structure.

s= 1/n.

gp(n)-

n(q)

(84)

defined

by

b.

apart possibly from terms of the form of a divergence

or of higher order in the superscript v of g ~'~. Here
1
2'
&.(.) (r') = 2 ,

where

KOHN

AV.

(1.

4. Partial Summation of Gradient Expansion

g, [n-t=gp(n(r))+

AND

n(q)
where

1+
2

q'+kg'

q2

kz'

5(q)

(91)

5(q) is defined in Eq. (43). This form yields

4x

24

kg 2kp2

k p'

(92)

For typical metallic densities this has the opposite sign

from the random-phase approximation expression (88).
Thus we see that the lowest nonvanishing gradient correction to the Thomas-Fermi theory depends quite
sensitively on refinements in the theory of the electronic
polarizability, u(q).

"E.P. Wigner,

Phys Rev. 40, 10.02 (1934).

Proc. Roy. Soc. (London) A243, 336 (1957).
z7 P. Nozieres and D.
Pines, Phys. Rev. 111, 442 (1958).
Gaskell, Proc. Phys. Soc. (London) 77, 1182 (1961); 80,
1091 (1962),

"J.Hubbard,

"T.

ELECTRON GAS

NHOMOGENEOUS

IV. CONCLUDING REMARKS

inhomogeneous
developments.

In the preceding sections we have developed a theory

of the electronic ground state which is exact in two
limiting cases: The case of a nearly constant density
(Is=np+rI(r), rI(r)/ep((1) and the case of a slowly
varying density. Actual electronic systems do not belong
to either of these two categories. The most promising
formulation of the theory at present appears to be that
obtained by partial summation of the gradient expansion (Sec. III.4). It has, however, not yet been tested
in actual physical problems. But regardless of the outcome of this test, it is hoped that the considerations of
this paper shed some new light on the problem of the

PHYSICAL REVIEW

VOLUME

electron gas and may suggest further

ACKNOWLEDGMENTS

This work was begun and, to a considerable extent,

carried out at the University of Paris. One of the
authors (P. Hohenberg) acknowledges with thanks a
NATO Postdoctoral Fellowship; the other author (W.
Kohn) a Guggenheim Fellowship. Both authors wish
to thank the faculties of the Ecole Normale Superieure,
Paris, and the Service de Physique des Solides, Orsay,
for their hospitality, and Professor A. Blandin, Professor
J. Friedel, Dr. R. Balian, and Dr. C. De Dominicis
for valuable discussions.

136,

NUM

BER

3B

9 iVOVEM B ER

Scattering of a High-Intensity, Low-Frequency Electromagnetic

by an Unbound Electron*

1964

Wave

ZOLTAN FRIED)
Ordnance Laboratory, Silver Spring, Maryland
und Univ' sity of California, Santa Barbara, California

U.

S. iVaval

AND

IosEPII H. EszRLvf.

U.

S. Naval

Ordnance Laboratory, Silver Spring, Maryland

(Received 15 June 1964)

"Thomson" scattering of a high-intensity, low-frequency, circularly-polarized electromagnetic wave by a

free electron is considered. We find that by neglecting radiative corrections and pair e6ects, the FeynmanDyson perturbation expansion is summable, and the sum can be analytically continued in the form of a sum
of continued fractions. By imposing the boundary conditions that at t = & ~ the photons and target electron
propagate as free particles, we obtain results which differ from those reported by Brown and Kibble and by
Goldman. In particular our results dier in two aspects. The 6rst difference is in the kinematics; namely, we
find no intensity-dependent
frequency shift in the scattered photon. The second difference is in the dynamics;
that is, we obtain a different expression for the scattering amplitude. Both of these changes originate in the
choice of boundary conditions. Instead of treating the asymptotic radiation 6eld classically, we choose our
states as linear combinations of occupation-number states. Finally, contact is made with the results of Brown
and Kibble and of Goldman using a mixed set of classical and quantum boundary values.

I. INTRODUCTION
'HE advent of masers and lasers has stimulated a
great deal of interest in the interaction of intense
electromagnetic 6elds with matter. This activity has
been focused on three different aspects of the subject.
First, a great deal of attention has been devoted to the
dynamics of production of high-intensity
light. A

*A preliminary version of this work was presented at the

Pasadena Meeting of the American Physical Society, Bull. Am.
Phys. Soc. 8, 615 (1963).
f Present address: Lowell Technological Institute, Lowell,
on leave from the U. S. Naval Ordnance
Massachusetts;
Laboratory.
$ National Academy of Sciences National Research Council
Postdoctoral Research Associate, 1962-64.
' J. R. Singer, %users (John Wiley R Sons, Inc. , New York,
1900); F. Schwabl and W. Thirring (to be published); W. E.
Lamb, Jr. , Lecture Notes, Enrico Fermi International School of
Physics, Varenna, 1963 (unpublished).

second area of concentration is the question of proper

description of the electromagnetic radiation emanating
from a laser; i.e. , questions of coherence and correlation. ' And finally, the problem of interaction of laser
light with matter has attracted considerable interest. '
It is this latter question to which we are devoting ourselves in this paper.
The particular problem of immediate interest is the
effect of the presence of the high-intensity field on the
Compton (Thomson) scattering amplitude. Recall that
the Thomson amplitude describes the scattering of a

' R. Glauber, Phys. Rev. 130, 2529 (1963); E. C. G. Sudarshan,

Phys. Rev. Letters 10, 277 (1963); E. Wolf, Proc. Phys. Soc.
(London) 80, 1269 (1962).
~
J. A. Armstrong, N. Bloembergen, J. Ducuing, and P. S.
Pershan, Phys. Rev. 127, 1918 (1962); Z. Fried s.nd W. M. Frank,
Nuovo Cimento 27, 218 (1963).