Ann. Rev. Phys. Cher. 1983.

34: 631-56
Copyri!ht 1983 by Annual Reviews Inc. All rights reserved
DENSITY FUNCTIONAL THEORY
Robert G. Parr
Department of Chemistry, University of North Carolina, Chapel Hill,
North Carolina 27514
INTRODUCTION
In writing this review I hope to alert the physical chemical community to
the promise and the charm of the density functional theory of electronic
structure of atoms and molecules.
Density functional theory was born in an extraordinary 1964 paper by
Hohenberg & Kohn ( 1), and its chief method of implementation in a 1965
paper y Kohn & Sham (2). And yet each of these papers has been
referenced only once in the Annual Review of Physical Chemistry, and then
only in passing (3). I believe that these papers have transcendent importance
for chemistry. See also the 1966 sequel (4).
To be sure, the so-called XI method (5) has received much attention, and
it has been twice reviewed in these pages (6, 7). However, it generally has
been presented as an independent, self-contained method, and only the
review elsewhere by Connolly (8) revealed it for what it is, an approximation
to exact density functional theory. As for reviews of density functional
theory itself, I should mention the one by Kohn & Vashishta (9, 10) and the
one by Rajagopal (11).
In the present review I shall survey the density functional theory as it
applies to systems with fewas opposed to infnitely many-electrons.
Fundamental aspects are emphasized, with specifc applications only
touched upon. First I sketch the original theory. Then I consider
refnements and extensions, problems within the theory, applications to the
phenomenological description of chemical phenomena, and future pros
pects. I also discuss connections with statistical mechanics and the
intriguing conclusion that the distinction between microscopic and macro
scopic systems is more blurred than one had thought.
Uncertainties abound both in density functional theory and in its
applications, and the literature of the subject is not free of errors.
631
0066-426X/83/1101-0631$02.00
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ANNUAL
REVIEWS
632 PARR
EXACT FORMULATIONS
Density Theory
There was an old model, the Thomas-Fermi model (12-15), from which
originated the idea of an "electron gas." In this model all properties of a
system turn out to be expressible in terms of the electron density p, the
number of electrons per unit volume, as it varies through space. This fails to
give an accurate description of electronic systems of chemical interest; for
example, it cannot account for chemical binding (16). But it is now known to
be but a frst approximation to an exact description of the ground state of
any system in terms of its density-the density functional description.
The density can be obtained by quadrature from the exact N-particle
wave function 1(12 N):
p(1) " N
JII1
2
d'2 d'3 ..
d
ON
dsl
. 1.
1/1 itself comes from solution of the Schrodinger equation, which can be
expressed as a stationary principle,
({<.II.>-E[<.I.>-I]} 0
,
where the energy E is a Lagrange multiplier and is the Hamiltonian,

Li(f) + LIV(f)+ L"<v(1lr,v)
Since p integrates to N,
N =
N[p] J
p(l) d
Vl = J
p d
r
,
2.
3.
4.
and the operators t and l/r Iv are universal, this procedure is a way to begin
with N and v and determine all properties, including p. The quantity p is of
course of much interest, being directly accessible experimentally and readily
visualizable-just the classical density of the electronic system. Four recent
reviews of the properties of p should be mentioned (17-20), as should be the
extraordinary work of Bader (21) and others (22), following Collard & Hall
(23), in which the whole of structural chemistry is addressed by applying
modern catastrophe theory to p and V p.
But our concern here is rather the remarkable facts proved by Hohenberg
& Kohn (1), that p determines v and hence everything, and a wrong p gives
an energy above the true energy. Functionals T[p], v.[p], E[p], and so on
therefore exist, and there is a stationary principle analogous to Eq. 2,
c{E[p]-J[N[p]-N]} O. 5.
Here J is the so-called chemical potential; T[p] and Ve[P] are functionals
that give for any ground-state density p the kinetic energy of the electrons
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DENSITY FUNCTIONAL THEORY 633
and the electron-electron repulsion energy. The Euler equation cor
responding to Eq. 5 is
f o
E/op
= v
+
oF/o
p
6.
where P[
p
]
" T[
p
]
+
v"e
[P]
. The right side of Eq. 6 varies from point to
point through the system unless the density is the true density for the
system, in which case the value is the same everywhere-the chemical
potential.
For a system of a given number of electrons (an important restriction),
Levy (24) has shown how to determine F
[p
]
:
F
[
p
]
min
<
tIT+ Velt).
7.
!=p
Compute for all antisymmetric t which give p the expectation value of
T + fe; the minimum of all these is F[
p
]
. This is not to say that the
determination of F
[
p
]
is easy; therein indeed lies much of the challenge, and
the charm, of density functional theory.
For a change from one ground state to another, one fnds (25) the
fundamental equation for the change in E
[
N, v
]
,
oE foN +
f
p(
l)ov
(
l) dVl'
Thus one has
f
(aE/aN)"
and
p(1)
[
oE
/
ov
(
l)h
8.
9.
10.
The analogy with macroscopic thermodynamics is clear, about which more
later.
That the chemical potential is no more no less than the electronegativity
concept of structural chemistry follows from Eq. 9 and the famous
electronegativity formula of Mulliken (26):
I+A
f = (aE/oN)" -
-
2
-=
X
M,
11.
where I and A are the ionization potential and electron afnity of the species
in question. Many properties of electronegativity follow (25, 27, 28).
The electronic energy functional may be resolved into components as
follows:
E
[p]
=
T[p
] + v.,
e
[P] + v"e
[
P]

v.e[P] +
F[p
],
1
2
.
where v.e[
P
] fv(l)p(l) dVl and
v"e[P] J[
p
]-K[
p
]; J[
p
]
=
(
1
/2
)
ffp(
l
)p(2
)
(I/rd
d
Vl
d
V2'
13.
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634
PARR
For a molecule, the nuclear-nuclear repulsion must be added to give the
total energy. K here is defned as J minus Ye; it includes correlation as well
as exchange efects.
Density Matrix Theory
If the density determines all properties, so does the frst-order density
matrix,
14.
A whole formal theory can be constructed, therefore, using functionals of Y
1
rather than of p = Yl(
l
, 1), and that has been done (25, 29-32). [Note that
this is not wave function theory restated as a problem in density matrices,
which is a whole big, separate story.]
The most general such theory uses an arbitrary representation OfYl and
has many interesting aspects (29-31). Here we concentrate on the more
compact theory (25) in which Yl is represented in terms of natural spin
orbitals and their occupation numbers (33):
Y
I
(1
'
, 1)
Lk
n
kl:(
l
')lk(I).
15.
One expects (34, 35), and this point is vital,
0<
nk
< 1, 16.
for a complete set of the I
k
' or at worst almost a complete set. Functionals
of p become functionals of the Ik and the nk.
The kinetic energy as a functional ofYl is known explicitly,
17.
while the electron-electron repulsion energy Ye[Yl] is not; the latter,
however, txists by the Hohenberg-Kohn theorem. Minimization of the
energy B[Yl] with respect to the nk and tk' subject to orthonormalization
conditions, then gives (25, 31)
18.
where J is the chemical potential of Eqs. 5 and 6. Also, the
tk
satisfy
equations of the form
F
tk =
Gktk,
19.
where the ek are eigenvalues, and also
) = eJnk' for all k. 20.
While these equations are not so easy to implement in practice (see
below), the formal results are highly interesting. They depend critically on
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DENSITY FUNCTIONAL THEORY 635
Eq. 16. The verbal statement is that all natural spin orbitals have the same
chemical potential or electronegativity.
Equation 19 is not the Lowdin equation
(
33) for natural spin orbitals, but
a density functional analogue thereof
(
32). The L6wdin equation in fact is
not diagonal in the natural spin orbitals, whereas Eq. 19 is.
Kohn-Sham Theory
Kohn & Sham
(
2) introduced a quite diferent method for evaluating
T[p
]
:
separate it into a major part that is known and a minor correction.
Specifcally, a noninteracting (Ye = 0) system with density p would have a
kinetic energy
N
T[
p
] L
<
kl-
(1/2)
V
21

k>
21
.
k
and one may then write, in place of Eq. 12,
E[
p
]

'[
p
] + Ye[P] +J[
p
] + Exc[
p
]
22.
where
Exc[p] = T[p] - T[
p
] -K[p]
. 23.
Also,
24.
The "Kohn-Sham orbitals"
k
have densities that sum to the exact density.
As far as the density is concerned, it is as if the wave function were a single
Slater determinant built from the
k
. The exact wave function is not this
determinant, however; the entire physical meaning of the k is contained in
Eq. 24.
Minimization of the energy now leads to the Kohn-Sham equations for
determining the orbitals
k
, namely N one-electron equations of the form
F KS

k B

k
Here
FKS
-(1/2)V2+
v
+
+(JExc
/J
p)
25.
26.
where is the classical electrostatic potential due to the whole electron
distribution. These equations must be solved self-consistently, since
F
KS
depends on p. The method is in principle exact, though in practice one must
resort to approximations for
Exc
. None of the eigenvalues e

s is expected
to have defnite physical signifcance except the highest, and even its
meaning is tricky to establish (9, 36).
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636 PARR
Extensions
SPIN DENSITY THEORY The density of Eq. 1 is spin free, but is of course a
sum of spin-I density and spin-{ density. For states other than
1
S states,
and indeed for practical purposes often even for
1
S states, it is necessary or
convenient to use a generalization of the original Hohenberg-Kohn-Sham
theory that invokes similar theorems for the separate density components
(37, 38); we have, for example, E
=
E[Pa
,
Ppl Corresponding "spin
polarized" versions have been developed of Kohn-Sham and XI methods
(2, 37-40). Of particular importance is the possibility within such methods
of incorporating self-energy corrections, which have been developed and
exploited recently (41-47).
EXCITED STATES Higher-energy solutions of Eq. 2 are automatically
orthogonal to the ground-state solution. No such wave function ortho
gonalities exist between higher-energy solutions of Eq. 5 to the ground
state solution (except where there are symmetry diferences). For this
reason, density functional theory for excited states (48) is more difcult than
wave function theory for them; there is no such simple theorem that P for an
excited state determines all of its properties. As has been said, "Density
Functional theory is primarily a ground state theory" (49). The ground
state density determines all excited state properties, however, and excited
states have in fact been variously computed by density functional methods.
Rigorous discussions of diferent possible procedures include those of
Theophilou (50), Valone & Capitani (51), and Katriel (52). More work is
needed in this area.
TIME-DEPENDENT PROCESSES Using an energy-minimization principle
based on the hydrodynamic formulation of quantum mechanics, Bartolotti
(53) recently has derived a variational density functional theory for a time
dependent ground state, and then (54) a corresponding Kohn-Sham
procedure. A comprehensive discussion of much the same ground has been
given by Deb & Ghosh (55, 56), who also give special attention to the
problem of calculation of the dynamic polarizability (56). See also the
review by Lundqvist (57). Such results will be essential as one sets out to
describe systematically chemical processes using density functional
concepts.
MOMENTUM SPACE Electron density for a ground state, p
(
r
)
, and momen
tum density for a ground state, p(p), are not simple Fourier transformations
of each other, and so there is not a trivial transcription of Hohenberg-Kohn
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DENSITY FUNCTIONAL THEORY 637
theory into momentum space. However, there is a corresponding theory in
momentum space, which has been given by Henderson (58).
NON-BORN-OPPENHEIMER THEORY Among the extensions of Hohenberg
Kohn theory to muiticomponent systems (9) is the extension to the
molecule considered as a system of several components: the electrons plus
nuclei of each different type of nucleus (e.g. H20 is a three-component
system). This theory has been written out (59). Each component has its own
chemical potential. Extensions to a phenomenological description of
chemical reactions should be forthcoming.
The Hartree-Fock Case
The Hartree-Fock energy functional is a functional of the frst-order density
matrix, and so the Hartree-Fock model can be viewed as an approximation
to the density matrix theory described above (31, 32). However, there are
two respects in which the usual Hartree-Fock theory falls short of being a
full implementatin of density functional ideas. First, Eq. 16 is not satisfed,
and so Eq. 18 does not hold. Second, N is not generally treated as a variable,
certainly not as a continuous variable.
Nevertheless, Hartree-Fock theory as a density functional theory is of
interest. The Hartree-Fock density (known to be very close to the true
density) determines the Hartree-Fock potential and all properties for the
ground state (including the true density) (60, 61).
Following up on this result, Payne (62, 63) has introduced difference
coordinltes in the Hartree-Fock density matrix, and produced an interest
ing Hartree-Fock calculational scheme focusing on the density.
In an important paper, Aashamar et al (64) have determined the exact
Kohn-Sham orbitals and efective potential for Hartree-Fock atoms having
Z : 54. The orbitals are very close to Hartree-Fock orbitals.
The Exact Thomas-Fermi Limit
A fundamental advance was made when Lieb & Simon (65) established that
in the limit of high Nand Z, atoms conform to the original Thomas-Fermi
model, in which
27.
and K[p] is negligible. This is important because it establishes all of the
properties of the exact Hohenberg-Kohn functional in one important
limiting situation. However, one should note that N and Z "high" in this
context means on the order of thousands, which rules out the possibility
that Thomas-Fermi theory will govern elements actually in nature. The
"hydrogenic" limit is much closer in realitythe ve = 0 model (66, 67).
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638 PARR
LOCAL APPROXIMATIONS
The Essence of Localization
We now come to a very important point about this subject, the understand
ing of which is essential for the appreciation of why formulas originally
derived for the uniform electron gas work so well for such nonuniform
systems as atoms and molecules.
Consider an arbitrary given functional of the density, Q[p]. It is a local
density functional if its functional derivative with respect to the density,
JQ/Jp, at a point, is a function only of the density at that point (and not its
derivatives or integrals) (68). Thus Jp dr is local; the integral J
V
p'
V
p dr is
nonlocal. The exact Hohenberg-Kohn functionals T[p] and F[p] are
nonlocal.
Even though a given functional Q[p] is nonlocal, a good approximation
to it often may be provided by a local functional: while a local formula
Q[p] " J
q(
p
)
dr may be incorrect, a formula
Q[p] J
q(
p
)
dr + corrections
28.
may be extremely useful. If, further, the particular Q is known to have
dimensions of kinetic energy or potential energy, the dependence of
q(
p
)
on
p is forced (69). Specifcally, we may write, without any error whatsoever,
T[p] = Cdp5/3 dr + corrections 29.
and
K[p] Cxafp4/3 dr + corrections.
\
30.
Note, however, that the Kahn-Sham "exchange-correlation" functional has
potential and kinetic parts and cannot be written (except roughly) in the
form ofEq. 30. Constants CF and CXa in these expressions can depend on N.
For a uniform electron gas, the "corrections" in the above equations are
zero and the constants are those of Thomas-Fermi-Dirac theory. For a
nonuniform gas, there is no reason not to hope to use these same equations,
with corrections as appropriate, and with N dependence in the coeffcients
as appropriate. What is needed only is that the functionals in question are
to a certain degree local, and that does not at all require
t
hat they be
"statistical." Small N or large N, it does not matter!
Gradient Expansions
The idea of a gradient expansion of a functional Q[p] is to write, exactly,
Q[p] " f
q
[p] dr, and to expand
q
[p] into a local part plus parts that
depend successively on
V
p,
V
2 p, etc,
q
[p]

q
o
(
p
) + q
l(P)V
p
+
q
2a(
p
)V2
p
+
q2b(P)V
p
' V P
+ . . . 31.
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DENSITY FUNCTIONAL THEORY 639
The coefcient functions qo(p), ql(P), + . . , may depend on the choice of a
reference situation and may or may not be easy to determine. The resultant
series for Q[pJ may or may not converge; it may be useful even if it is
divergent; a truncated form may give good numerical values of Q but poor
values of oQ/op.
KINETIC ENERGY Using Szasz' results (69), a gradient expansion of the
kinetic energy functional must take the form
fvpvp
T[pJ = COf p5/3 dr+C
2
p
dr
+ C
4af(V2p)2p -5
/3 d
r + C
4bf(V2p)(V p. V p)p -8/3 dT
+C4cf(V
pVp)2p-1l/3 dT
+
...
32.
where the coefcients Co, C
2
, etc, could in principle depend on N. The
natural zero-order term is the Thomas-Fermi result
33.
Perhaps the most natural second-order term is the correction suggested
long ago by von Weizsacker (70)_
.
Tw[pJ =
f V
p

vp
dr. 34.
Note that this gives the whole correct T for a one-electron system or a two
electron Hartree-Fock system. Note also that if included in a functional,
this confers (if not interfered with by other terms) on oT/op the correct
behavior near an atomic nucleus (cusp condition) and far from all atomic
nuclei (long-range behavior) (71-73). Macke (74) in fact derived
35.
but neglected a term of the same importance as Tw (12). This formula gives
too large values of T
.
Systematic empirical studies on both atoms and
molecules (75-78) give rather
36.
where f 0.20, a value which has very recently been theoretically justifed
(79). This equation gives oT/ip = (iTo/ip)+f(iTw/ip); it is reasonable
though generally impractical to treat f as a quantity that depends on
position (71, 80).
Using the Thomas-Fermi problem as reference, a gradient expansion of
the form of Eq. 32 has been given by Hodges (81) up to fourth order; the
sixth-order terms also have been obtained (82)= The second-order term
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640 PARR
turns out to be (1/9)Tw This does violence to JT/Jp for small and large
distances from a nucleus. Nevertheless, calculations of the total T for atoms
gives some truly remarkable results (83-86). If one inserts Hartree-Fock
densities, To is low for neutral atoms but no more than 10%, To + T2 is still
low but less than 1 %, and To + T2 + T4 is even better (85). T6 is infnite for an
atom (82).
Recently it has been argued from detailed ftting of considerable data on
atoms (73), that for atoms a better form than Eq. 36 is
37.
with C = 1.332 21/3. This formula also has been theoretically derived
(87-89). This accords with an analysis by Schwinger (90), to the efect that
when Tw is added to describe correctly inner shells, a piece of To must be
subtracted that incorrectly describes those shells. The derivative JT/Jp
obtained from Eq. 37 still is incapable of correctly giving shell structure for
many-electron atoms, however (91).
THE COULOMB ENRGY The direct classical Coulomb energy J[p] ofEq. 13
is not a local functional, since its functional derivative, the potential 4 due
to the electron distribution, is an integral over the entire electron
distribution. In fact it has been shown (68) that an attractive and compact
"completely local" model alternative to the Thomas-Fermi model exists, in
which J[p] is replaced by a local approximation to it,
h[p] = BN2/3Jp4/3 dr. 38.
The value of B that best fts Hartree-Fock J values for atoms and ions is
0.9299 (68, 92), and this value can be rationalized theoretically (68, 93). An
interesting corresponding theory in momentum space has also been given
(94).
A gradient correction for J also has been derived and discussed (92, 95).
There results the nonlocal formula
39.
with B " 1.2263 and C " 0.0027. Again the numerical values of the
coefcients can be rationalized.
EXCHANGE ENERGY AND OTHR ENERGY COMPONENTS In considering
gradient expansions of exchange and correlation components, it is
important to distinguish expansions ofthe quantity K[p] ofEq. 13, which is
pure potential energy, from expansions of the quantity
E
x
c
[p] of Eq. 23,
which comprises both potential energy and kinetic energy. There are many
papers on these expansions.
The classical formula for K[p] is the local functional of Thomas-Fermi-
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Dirac theory,
DENSITY FNCTIONAL THEORY 641
Ko[p]
=
CxJp4/3 d., Cx
=
(3/4)(3/n)1/3. 40.
If one lets the coefcient depend on N, one gets the exchange energy of XI
theory (5),
41.
where I = I(N). The best values of I for atoms probably are those of
Schwartz (96, 97).
From scaling properties, the frst gradient correction to K[p] is expected
to be an integral Jp -4/3V p' V p d . When this is given an arbitrary
coefcient and added to Kx,[p], this gives what is called the X,p method
(98). For atoms, however, Bartolotti (99) has gven persuasive theoretical
and calculational reasons to prefer a correction in which the integrand
depends on r as well as p. His formula is
42.
wherey
=
d In p/d In r,C(N)
=
Cx +C
2
N-2/\andD(N)
=
D
2
N-2/3, with
C2 and D2 chosen to give correct results for a one-electron atom.
Combining a gradient expansion for K[p] with one for T[p] gives a total
energy functional that reproduces atomic Hartree-Fock energies very well
on input of Hartree-Fock densities (100). Excellent results have been
obtained similarly in calculations of the surface energy of metals (101).
Successive terms in gradient expansions unfortunately tend to be propor
tional to one another; the gradient expansion for the Hartree-Fock K[p]
in fact diverges. Inequalities among successive terms have also been
established (102).
When it comes to Exc[p], matters are much more complicated. Just to use
the local formula
43.
clearly is an oversimplifcation; the scaling is not right. This is what is being
done in any simple XC calculation purporting to include correlation efects.
Contemporary calculations with the Kohn-Sham method use instead a
formula
44.
where exc(p} is the correlation energy per particle for a uniform electron gas
of density p. exc being a function of p, this equation defnes what is
conventionally called the local density approximation (LDA). There an:
various ways to handle exc (2, 4, 9, 103, 104); one generally employs
complicated, often numerical, nearly exact expressions for it (37). Gradient
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642 PARR
corrections can be added, but successes with this have been limited (9, 105).
For spin-density gradient expansions of impressive accuracy, see the recent
work of Oliver & Perdew (106).
ISSUES WITHIN THE THEORY
The Problems of N Representability and v Representabilit
y
The Hohenberg-Kohn functional F[p] " T[p] + Ye[P] will be diferent
for diferent statistics. Left implicit in the original statement of the theory
(1), this point has caused confusion (107) but has since been explicitly stated
(108).
There is a real related problem, however, called the N represent ability
problem. Consider a system of fermions. As we vary from one p to the next,
in Eq. 5, for a given N, may we assume that every trial p is acceptable in the
sense that it comes from an antisymmetric wave function? The answer in
fact is yes, as was frst proved by Gilbert (29). He showed by explicit
construction that for any p, there exists a single determinantal wave
function which gives that p. Another construction is due to Harriman (109).
Much more subtle is the problem of v representability, which is the
question of whether trial p's always may be assumed to be associated with
eigenfunctions of a Hamiltonian operator of the form of Eq. 3, with an
appropriate v. This was assumed by Hohenberg & Kohn, who verifed its
correctness for one limiting case (1, footnote on page B865).
In general, however, the answer is now known to be negative. Early
attempts to solve the problem were not conclusive (110), but recently the
answer has been obtained. In a paper with the apt title "Electron Densities
in Search of a Hamiltonian," Levy (111) gives a counterexample, as does
also Lieb (112, 113).
Fortunately, this result does not ruin the theory. Inserting even non-v
representable p's in the Levy prescription of Eq. 7 does not hurt, because
this functional achieves its absolute lower bound for a given system with the
true v-representable p. As a constraint, v represent ability may be regarded
as unnecessary (111).
The Problem of N as a Continuous Parameter
If the reason that local functionals of p for few-electron systems are useful is
accounted for by the Szasz argument outlined above (69), there still can be
raised another argument against use of density-functional theory for few
electron systems. Density functional equations generally treat the para
meter N as continuous, whereas actual atomic or molecular systems always
possess an integral number of electrons. Does this invalidate use of density
functional theory for such systems?
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DENSITY FNCTIONAL THEORY 643
No, for reasons that have been recently discussed in some detail (36, 114-
116). Data on properties as functions of N are generally smooth, which itself
justifes interpolation procedures and demands development of interpolat
ing theories. The earliest such interpolating theories were those of Thomas,
Fermi & Dirac (12-14). The extensions of Kohn-Sham procedures due to
Janak and others (117, 118) also qualify.
Perhaps the most attractive argument is provided by the statistical
mechanical view frst suggested by Gyftopoulos & Hatsopoulos (119). The
average situation in a grand canonical ensemble can easily conform to a
nonintegral number of electrons. This agrees with Valone's proposal that in
any case the original Kohn-Hohenberg conception should be regarded
from an ensemble viewpoint (120).
Perdew et al (36) have proved a remarkable result for an isolated atom or
molecule at 0 K: the energy E(N) as a function of the number of electrons
is a broken straight line. A similar result has been obtained by Phillips
& Davidson (121). More specifcally and completely, if k is an integer and
N k+
w
,
(k )
E(k +l)-E(k-l) '
f
lE(k + l)-E(k) if
J +
w =
2
1
E(k)-E(k-l) if
In more familiar terms, we will have
{-A
J
=
-!(I +A)
-I
for a slightly negative species
J
for the neutral species
for a slightly positive species
45.
46.
Note that Mulliken's formula of Eq. 11 is verifed. Another interesting result
is that for a combined species A B where A and B are noninteractirig,
47.
where the min and max are of the values for the separate species A and B.
Under other conditions, such as for T > 0 or such as for atoms in a
molecule, diferent results will be obtained, but always
=
A<J<

1 + 48.
There can be cases, in fact, in which the value of the chemical potential is
imposed "from outside," as the case of a molecule physisorbed on a surface.
Limits are imposed by Eq. 48, but otherwise there could be quite a change
from one situation to the next. This could have bearing on heterogeneous
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644 PARR
catalysis (R. G. Parr, unpublished; Princeton University Seminar,
December 13, 1982).
A device helpful for separating the efect of change in N from change in
density at constant N is to write (116)
p = Na, Sa dv = 1. 49.
The quantity a has been called a "shape factor." When this separation is
elucidated, it becomes clear that in general there is an essential diference
between functional derivatives of the type oQ/op for constant Nand oQ/op
unrestricted. In particular, in Eq. 6 it is not (bF /bp)N but bF /op which
enters-a matter that has caused confusion (122). The exact electron
density for the ground state of a system of interest is not sufcient
information to determine its chemical potential (116).
The Problem of Well-Behavedness of Functionals
Even if one accepts the existence and uniqueness of the Hohenberg-Kohn
functional F[p] and other functionals we have been dealing with [and I
believe one should (107, 108)], many questions remain that must be
answered. Are they diferentiable with respect to p? With respect to
parameters in v? Are they invertible? Do they need to be and are they
convex? And so on.
Early studies of highly rigorous character include those of Lieb & Simon
(15, 65) on the Thomas-Fermi theory and Percus (123) on the general N
fermion problem [anticipating in part the later work of Levy (24)]. But the
defnitive study on mathematical aspects of Hohenberg-Kohn theory for
Coulomb systems (which include atoms and molecules) is the new work by
Lieb (112, 113). Lieb comes to constructive conclusions on many points.
Support is provided for favoring Levy's principle of Eq. 7, over other
formally equivalent ways to state the central stationary principle of the
theory. One may remain cautiously optimistic about these mathematical
matters.
THREE COURSES OF THE THEORY
The Molecule as a Single Thermodynamic System
In this "nonhomogeneous electron gas" description of the electrons in a
molecule that we have been discussing, we have what well may be thought
of as a "thermodynamic" description; there are correct and useful analogies
with a classical thermodynamics of such a system. The most obvious
thermodynamic aspect is the chemical potential, which, as is stated above,
measures the escaping tendency of electrons in just the way the chemical
potential of Gibbs would do, for a macroscopic system with varying density
in an external feld.
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DENSITY FUNCTIONAL THEORY 645
An important diference with classical thermodynamics is that the energy
functional E[p] is not homogeneous of degree one in the number of
.particles. If it were we would have E " Nf, which in general is not correct.
There is a local pressure P that can be defned, however, as the negative
one third of the trace of a classical stress tensor for a system (124). In terms
of the Classical electrostatic potential due to electrons, (r), and a new
defned functional
X[p]
[Jp(tT/tp)
dr
-(5/3)T]-[
J
p(tK/tp)
dr
-(4/3)K], 50.
one then fnds, amohg other results,
E
[p] JPfo dr+ J
p
v dr+
(1/2)
J
p dr
-
JP dr
-X[p],
where 10 is the chemical potential in the absence of felds. Also,
3
JP
dr = 2T[p]-K[p].
51.
52.
Except for the term -X, Eq. 51 is completely classical; X measures the
deviations from complete localizability, in the sense of Eqs. 29 and 30, of the
functionals T[p] and K[p]. These results are for zero degrees K.
An explicitly thermodynamic theory results if one considers what
happens for a typical system in a grand canonical ensemble of identical
systems, in equilibrium at some T > O. A remarkable result follows: the
density again determines all properties, with a corresponding stationary
principle for the free energy. This was frst shown by Mermin (125), using a
basic inequality of Gibbs, and has since been generalized and used
elsewhere in macroscopic physics, especially in the theory of surface phases
(126-132). Even though the derivation is easy once Gibb's result is known, it
apparently escaped discovery until the Hohenberg-Kohn-Mermin work
(perhaps because of the lack of interest in nonhomogeneous systems). A
summary is that there exists an equation of state even for a nonhomo
geneous system: T and the local p everywhere determine all properties.
There is a wide range of interesting and sometimes important identities
and relations among partial derivatives (Maxwell relations), mandatory
signs of derivatives (stability conditions), and alternative choices of
independent variables (Legendre transformations) (133). These have been
enumerated and discussed, both for Born-Oppenheimer and non-Born
Oppenheimer systems (134-136). Many of the formulas are useful for
describing actual physical phenomena. They also are important for
assessing which of various possible stationary principles equivalent to Eq. 5
will be mathematically well behaved and computationally most feasible
( 112,113).
The Single Hypersurface that is Chemistry
Chemistry is what happens to atoms and molecules in the presence of
external felds X, as a function of t, and so chemistry can be thought of as the
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646 PARR
st4dy of functionals of the form P[Z., Zp, ... ;N., Np, ... ;N;X; f], where P
is some property of interest, Z., Z p, . . . , are atomic numbers (of all nuclei in
the periodic table!); N, N p, ... , are the numbers of the d
i
ferent nuclei
present; and N is the number of electrons present. For example, one
property of great interest is the total energy for all tire-independent
ground states in the absence of felds; this is the hyper surface
E
[Z.,Zp,.
'
.. ;N",Np, ... ;Nl This single function contains all of thermo-
chemis
t
ry (at 0 K).
"
There is good reason to imagine all of the variables in E
to be continuous
if needs be, and in any case to try to codify as much information as possible
by systematic exploitation of the calculus, or the fnite diference calculus, of
this fu' nction. Many interesting recent studies can be viewed in this light.
Particularly exciting is the success of Tal & Levy (137-141) in obtain
i
ng
to an amazing accuracy the energies of all of the neutral atoms in the
period
+
table by a one-parameter recursion procedure into which is input
onlyihe Bohr formula for the energy of a hydrogen-like atom. Furthermore
the parameter has a value that is theoretically justifable. Specifcally, what
they have done is rationalize the formula
EK EK-1 +so(K)-2/[so(K)EK_1]1/2, 53.
where c
o
CK) is the noninteracting energy for the atom of atomic number K
and P = 0.959906. The average percentage of error relative to Hartree
Fock values is only 0.21.
Other very recent studies in this general spirit include, for example, the
works of Essen (142), Laurenzi (143), Mezey (144, 145), and Tal, Bartolotti
& Bader (146-148). All studies of (l/Z) or (1/Nl/3)
e
xpansions are of this
kind (28, 149-152); they ofen emphasize the noninteracting (v
e
= 0) limit,
which
'
in future may well replace the N =

Z = C limit as the prime

reference point for the calculation of properties of real atoms (79, 153).
The type of formula that is useful in such c
o
nnections is exemplifed by
the formula for an atom (27)
(iE/i
Z
)N/Z
=
(iEji
N
}z + (iE/i
Z
)N
=
J+(Vne/
Z
).
54.
Note the appearance of the cheical potential and the use of the Hellmann
Feynman theorem.
Connecting Wave Function Theory with Density
Functional Theory
Hohenberg-Kohn theory can be no more than a transcription of the usual
Schrodinger theory, a renormalization of it so to speak (154). It therefore is
pertinent to try to fnd the functionals F[p], Ve[P], T[p] using wave
function calculations as appropriate, and to put to work on this problem
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DENSITY FUNCTIONAL THEORY 647
the tremendous know-how built up by the quantum chemists on how to
compute wave functions.
In the eforts so far on this problem many mistakes have been made, in
particular in confusing constant-N calculations with non-constant-N
calculations (see above).
The prescription or
'
Eq. 7 is a solution in principle for a given N (24). A
specifc procedure for implementing this has been given by Freed & Levy
(155).
An early attempt to get a density functional procedure from wave
functions was Macke's attempt (74) to take the high-N limit of Hartree
Fock theory; this limit should be looked at again using the circulant
transformation recently discovered (156).
A program for determination, from wave functions for test cases, of the
functional derivative Ex
c/

p
of Kohn-Sham theory has recently been
initiated (157, 158
)
.
One could hopeI to fnd a diferential equation for the Hartree-Fock
density at fnite N (159, 160
)
. A procedure very recently proposed (161
)
can
be considered to have achieved this. The result obtained is a set of coupled
diferential equations, one of which is for the density, but which can be
solved for the density starting only from a guessed density. For the (1sf(2s)2
ground-state of Be, replace the usual Is and 2s orbitals with circulant
transformations of them (156),

I
= (
p/
4)
1/
2
exp(
iO)
,
2
= (
p/
4)
1
1
2
exp
{ -iO).
The Hartree-Fock energy functional then takes the perspicuous fon
n
E[p,O]

(1/8) <Vp Vp/p) +
(1
/2) <pVO V8) -Z<p/r) + (3
/4)J[p]
-
(1/
2)
JJp
(
l
)
p{
2)
cos[2
0(1)-20(2)] d
'l d'2/rI2'
and the equations for determining
p
and 0 are the coupled equations
Vp
Vp
V
2
p
+ 4(r)+ VO V8
8
p
2
4 P r 4 2
-} f
p
(2) cos
[
20(1)-28(2)] dr
2/
r
1
2
=
fN+ f
c
cos
2
0
55.
56.
57.
1 John Platt once wrote (159): "We must . . . fnd an equation for . . . total electron density
without going through the individual orbitals . . . . My guess is that there is a 'collective wave-
density equation' in which the number of particles is only a parameter . . .
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648 PARR
and
!V
2
e
+
!(Vp/p)Ve-!
J
p(2) sin[2e(I)-2e(2)J dr/r1
2
Jc sin 2e, 58.
where JN and Jc are Lagrange multipliers. Guessing p, one may solve Eq. 58
for e, put the result in Eq. 57, and then determine a new p. Iterating, this is a
pure density functional procedure. This result admits of generalization to
arbitrary N (161).
An enticing additional possibility exists, to fnd the best single determin
autal wave function for a system such that all orbitals have the same
electron density. That such orbitals should exist follows from some work of
Harriman (109). They are not in general equivalent to Hartree-Fock
orbitals, but the known properties of the circulant transformations of
Hartree-Fock orbitals (156) suggest that they may be surprisingly close to
Hartree-Fock orbitals.
MISCELLANEOUS STUDIES
Without pretending to be comprehensive, I now list some recent basic
studies on various topics of interest.
The pioneers in the application of density functionals ideas and methods
to chemistry, exclusive of the XO practitioners, were Nikulin in Russia and
Gordon & Kim in the US. In a series of papers beginning in 1970, these
authors considered rare gas interactions, ion-ion interactions, and cor
responding three-body efects (162-169). The essential idea of this work
(which has since proved valuable elsewhere) is to take the electron density
as a superposition of Hartree-Fock atomic densities, and to include in the
total energy a contribution to the total energy of electron correlation,
computed from formulas for the correlation energy for a uniform electron
gas (as a function of density). Subsequent work has included calculation of
crystal binding energies (170-172) and various static and collisional
polarizabilities (173-181). Intermolecular forces also have been treated
(182, 183). Inclusion of gradient corrections has been considered (184), and
various diffculties with the theory (185-187). Wood & Pyper (185) conclude
that the most reliable version of the method is that of Lloyd & Pugh (188,
189).
Beginning with a calculation on H2 in 1976 (40), there have been a series
of impressive Kohn-Sham-type density functional calculations on mole
cules by Gunnarsson, Harris & Jones (190-197). True, arbitrary decisions
have had to be made on how to determine E
x
c
' but as the description of
E
x
c
has improved, so have the results. Note in particular the improvement
obtained (198) when the very recent Ceperley-Alder (199) accurate corre-
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.
DENSITY FUNCTIONAL THEORY 649
lation calculation for the uniform electron gas is incorporated. There seems
to be no reason such methods should not be regarded as becoming
competitive with traditional wave function methods for determining
ground-state molecular properties.
For calculations by the Xe method, the reader may refer to last year's
comprehensive review in these pages (7). The electron afnities of the
elements have recently been very successfully calculated (200) using the self
interaction correction to the local spin density approximation for exchange
and correlation.
A number of alternative variational principles featuring the density have
been given (201); these all require comparing the system of interest with
another system (as does Kohn-Sham theory). Hierarchical principles
involving density matrices have been derived, which ultimately should help
connect density functional theory with density matrix theories (202-205).
Also important for the future will be understanding of the geometry of
density matrices (33, 206-209).
There is need to fnd density matrix functional calculational methods
that conform with Eqs. 16 and 18. The frst attempt at this failed to achieve
the desired result (210).
Given that the pure correlation energy is a functional of the electron
density, plus the considerable, still advancing expertise of the quantum
chemists in computing the density and the correlation energy, one would
hope and expect that there would be much efort directed at fnding
E
corr[P]
for atoms and molecules. So far there have been some, but not many, such
studies (211-219), and the problem has not been solved.
It has been shown that if electron densities constrained to be piece-wise
(shell-wise) exponential are input into extremum principles of Thomas
Fermi-Dirac-Weizsacker type for atoms, remarkably good electron den
sities and energies can be obtained (220, 221), and other atomic properties
as well. That atomic densities are indeed close to piecewise exponential
(220) leads one to speculate that there is an information-theoretic approach
to densities; a study aimed in that direction has appeared (222).
There is no question more central to chemistry than the question of what
is an atom in a molecule, and so addressing this question from density
functional theory is important (25). If in molecule AB atoms A and B are in
states A * and B* (in general distorted from A and B in their ground states,
both with respect to energy and shape), we may require, and we should
obviously require,
59.
and
JAB J1 J.
60.
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.
650 PARR
Another condition is needed to fx A * and B* uniquely; we may take it to be
a minimum promotional energy condition (25). The frst calculation with
such a scheme has been carried out by Palke (223), the next is the elegant,
similar work by Guse (224).
Also of much interest in chemistry is the concept of electro negativity,
about which there is a rich literature. Among recent density-functional
studies of this quantity are studies of electro negativity equalization [a valid
principle (25)] (225, 226), systematic calculations of electro negativity by the
XI transition-state method (227-229) and by other density functional
methods (230-232), and development of a useful electrostatic model (233).
In one of these works (226), it was suggested that for an atom near
neutrality, an exponentially decaying form be used for the electronegativity,
X
(N) " x(Z) exp [ -yeN -Z)]. 61.
The value of y is surprisingly universal: y 2.3; to the extent that it is
universal a geometric mean principle of electronegativity equalization
follows.
In the local v
e
theory discussed above (68), the electron density turns out
to be a simple function of the bare-nuclear potential, p(v). This roughly
characterizes true molecular electron densities (234), and deserves intensive
further study. Payne (235) has outlined a density functional theory of
nonbonded interactions in molecules.
Among recent modifcations of the original Thomas-Fermi ideas, one
may mention the coreless Thomas-Fermi model of Ny den & Acharya (236),
related works of Schwinger (90, 237-239), a "radially restricted" model
(240), and an "orthogonality constrained" scheme of Nyden (241). The
Thomas-Fermi atom has been solved in n dimensions (242).
Insofar as the relativistic kinetic energy of a free electron gas can be
expressed in terms of the density p, one can formulate a relativistic Thomas
Fermi theory, and gradient-expansion improvements thereof. A key early
paper is the work of Tomishima (243). Relativistic versions of general
density functional theory and Kohn-Sham theory also exist, for which see
the review of Rajagopal (11).
There are many studies concerning the fact that energy components T,
Y
e, ve
almost always are close to universal constant multiples of each
other. Thomas-Fermi theory gives 7E = 3Vne " -21 ve. That the same
ratios hold more generally was frst observed by Fraga (244). The cause is
that the homogeneties in p represented in Eqs. 33 and 40 are generally good
approximations (25, 245, 246). There are corresponding interesting impli
cations for the electrostatic potentials at nuclei (247-250) and for the sums
of orbital energies )i (251). And there is a related homogeneity charac
teristic of molecular energies with respect to nuclear charges (252, 253).
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.
DENSITY FUNCTIONAL THEORY 651
There are other related contributions by March and collaborators (254,
255).
Of more purely theoretical interest, there has been the proof of a
Hohenberg-Kohn theorem for a subspace (256, 257) and the discovery of a
useful complementary variational principle for density functional theories
(258).
CONCLUSION
It is commonplace to suppose that the theory of the electronic structure of
molecules is fast becoming a closed subject, because of the magnifcent
successes of the quantum chemists in solving the Schrodinger equation
quantitatively (259, 260). The Hartree-Fock method sufces for most
purposes and can be improved upon (261), one says, and the necessary
computer programs are canned.
Elsewhere I have given some of the reasons that in my opinion this
attitude slights much of the subject (262, 263). The present review provides
more. There is an attractive whole alternative theory, the density functional
theory. And there are a whole set of alternative calculational schemes, of Xo
or Kohn-Sham type. Such schemes, at least potentially, ofer hope of the
same quantitative accuracy as the conventional schemes. And they promise
much more as well: a perspicuity, an economy of description, a simplicity of
interpretation, and a closeness to the classical ideas of structural chemistry.
Much research is needed to bring density functional theory to maturity, but
there will result a substantially broadened and more useful quantum
chemistry.
ACKNOWLEDGMENTS
I have profted from prolonged discussion on density functional theory with
my co-workers at the University of North Carolina, especially Dr. Libero
Bartolotti, and many others. I thank Professor Mel Levy of Tulane
University for helping me plan this review. Our research on this subject, and
the preparation of this review, have been aided by grants from the National
Institutes of Health and the National Science Foundation. The manuscript
was completed while I was in residence at the Institute for Theoretical
Physics, University of California at Santa Barbara.
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