16 December 1994

CHEMICAL
PHYSICS
LETTERS
ELSEVIEK Chemical Physics Letters 231 ( 1994) 4042

On the proof of the principle of maximum hardness

K.L. Sebastian
Deparlment ofApplied Chemistry, Cochin University ofScience and Technology, &chin 682022, India

Received 7 June 1994; in final form 6 October 1994

Abstract

It has been suggested that molecules arrange their electronic structure to be such that they have the maximum hardness, this
being referred to as the principle of maximum hardness. This principle has been claimed to have been proved rigorously. We
show that the proof is in error.

The concepts of softness and hardness have been Parr and Chattaraj (PC) make use of the grand ca-
of great utility to the chemist, as is evidenced by the nonical ensemble theory in their arguments. Their
variety of applications [ l-3 ]_ The concepts were starting point is the definition of softness in terms of
given a quantitative footing, by the definition of ensemble theory as
hardness as f (I-A) by Parr and Pearson 1.21,who
also gave definitions using density functional theory.
They suggest
(S)=
( )*
y u(r) ==P< (N- (1’) Y> . (2)

( ) indicates taking the average with respect to the

and S= -I-
v(r),T 2V.
In the above, q is the hardness and .S is the softness.
We follow the notations of Ref. [ 4 1. Pearson [ 1 ] also
suggested that ‘there seems to be a rule of nature that
molecules arrange themselves to be as hard as possi-
ble’, this being referred to as the principle of maxi-
mum hardness. Parr and Chattaraj [4] claimed to
have proved this principle. The proof has received
considerable attention. For example, see the review
by Pearson [ 5 ] himself, where the proof is discussed
in a fair amount of detail. This Letter shows that the
proposed proof is in error. It is the aim of this Letter
to bring this point to the attention of the scientific
community, with the view to persuading them to look
for an alternative definition/proof of this principle,
for which there exists considerable empirical
evidence.
(1) equilibrium grand canonical ensemble probability
distribution P%.i. In the first paragraph of their pa-
per, PC suggest that the hardness may be a maximum
under conditions of constant temperature and chem-
ical potential. However, the proof that they offer is
for the following. If PN,iis an arbitrary distribution
close to the equilibrium one, obtained by varying the
chemical potential ~1of the electrons and external po-
tential v(r) slightly, then the softness for the non-
equilibrium ensemble, defined by
N,i
is always greater than the softness for the equilibrium
ensemble, i.e. s-- (S) >/ 0. To test this suggestion, we
consider a simple model, due to Gyftopoulos and
Hatsopoulos [ 6 1, and used by Perdew et al. [ 7 1. This
consists of an atomic system, for which one considers

0~9-2414/94/$07.00 Q 1994 Eisevier Science B.V. All rights reserved

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 K.L. Sebastian/Chemical Physics Letters231 (1994) 40-42 41

only three levels for the grand canonical ensemble

(see the book by Parr and Yang [ 8 ] for details). In
this model, one thinks of an atom with N,, electrons
having a ground state energy E,, ionization potential
Z and electron affinity A. The three levels are then
E,-A, E. and E,+Z, having N,+ 1, N, and N,-- 1
electrons, respectively. For this, one can easily find
Pg,i and calculate the values of (N) and (S). We
consider other non-equilibrium ensembles at the same
temperature, obtained by replacing the equilibrium
chemical potential ,U with p. Thus the non-equilib-
rium distribution is given by

PN,i=exp[-B(E~,,-N~)l/3(~0, (4)
O.9
I.o -0.5
I 0.0
1 0.5
1 11
.o
where S(p) = CN,i exp [ - j?(EN,L- Nfl) 1, and is the
P(cL- !-t)
normalizing factor for the probabilities. For such a
Fig. 1. Plot of s/ (S) against p(p-p), for sodium and oxygen
non-equilibrium ensemble, it is quite straightfor-
atoms. Four of the curves are for sodium, for which we adopt a
ward to compute s. To consider a specific case, we three-level model, with I=5.14 eV, A=0.55 eV. Results for four
take Z= 5.14 eV, A= 0.55 eV (both correspond to so- different temperatures, (---) T= 10 K, (- - -) T= 3000 K,
dium) and all the three levels to be non-degenerate. (- - -) T= 5000 K and (- ... -) T= 10000 K are given. A plot for
T= 1000 K would be almost indistinguishable from the one for
In Fig. 1, we give plots of the dimensionless quantity
T= 10 K. For oxygen (- - - - - ) , we adopt a four-level model ( see
2?/ (S) against pd = /3( ,U- p) (also dimensionless) for text), and give results only for T= 300 K. In this case, we have
different values of T, and clearly, there is no mini- chosen the chemical potential P for the equilibrium ensemble in
mum at ,u~= 0, which is what one would have ex- such a fashion that (N) =Na. Note that in both cases,.?/(S) has
pected, if the result of PC were true. values less than unity, implying that (S) is not a minimum.
In Fig. 1, we also give results for a four-level model,
all the levels assumed to be non-degenerate and their
energies taken to correspond to the species O+, 0, semble, obtained by varying both ,u and V(Y).
O- and 02-. The required electron affinities and The above results imply that there is a fallacy in the
ionization potential were taken from the book by arguments of PC, and to understand which, we re-
Huheey, Keiter and Keiter [ 9 1. The calculation was trace their arguments. They make use of classical sta-
done at 300 K and we took the chemical potential for tistical mechanics for simplicity, and consider the
the equilibrium ensemble to have a value such that non-equilibrium distribution
(N) = N,. Fig. 1 shows that in this case also, (S) is
not a minimum. F(~*‘,P~~‘)=(A)-‘A(~,~‘,P~~‘)~(~*’,P~’) . (6)
The fact that there is no minimum, can also be
Here and in the following, A is any function of rN,ph
shown analytically. If one puts ,ri= ZL+ S,LL,then from
and is not to be confused with the electron affinity.
the definitions given above, one finds
They invoke linear response theory to argue that for
s-(S) =P’Spl( (N- (N) )‘> > such a non-equilibrium ensemble, the expectation
(5)
value of A, denoted by 2 satisfies
to terms linear in 6~. If the equilibrium softness were
a minimum, there would not have been any term lin- A-(A)=(A)-‘((A-(A))*). (7)
ear in 6,~. We have considered here non-equilibrium
ensembles obtained by changing ,u, keeping v(r) fixed We agree fully with this equation and note that it is
and even in this special case, there are ensembles for not necessary to use linear response theory to derive
which sis less than (S) . Therefore, the result of PC it. It can be obtained easily by calculating the left-
cannot be true for an arbitrary non-equilibrium en- hand side of Eq. (7) using the definition of F( rN,
42 K.L. Sebastian/ Chemical Physics Letters 231(1994) 40-42

p”). Now they put A=P(I?- (IV) )2, to find that [2] R.G. Parr and R.G. Pearson, J. Am. Chem. Sot. 105 (1983)
7512.
s- (S) > 0, which is also correct, provided the non-
[ 31A. Dal Pino, M. Galvan, T.A. Arias and J.D. Joanopoulos, J.
equilibrium ensemble is given by the distribution
Chem. Phys. 98 (1993) 1606.
((N-(N))2)-1(N-(N))2f(rN, pN). Thus for [ 41R.G. Parr and P.K. Chattaraj, J. Am. Chem. Sot. 113 ( 199 1)
this particular non-equilibrium ensemble, the soft- 1854.
ness is larger than the equilibrium one, but that does [ 51 R.G. Pearson, Accounts Chem. Res. 26 (1993) 250.
not move it to be so for anv other ensemble. [ 61 E.P. Gyftopoulos and G.N. Hastopoulos, Proc. Natl. Acad.
Sci. US 60 (1965) 786.
We conclude by noting that the interesting uses the
[ 71 J.P. Perdew, R.G. Parr, M. Levy and J.L. Balduz Jr., Phys.
concept of hardness has found recently [ 3 ] have still
Rev. Letters49 (1982) 1691.
to be considered as rather empirical, not yet having a [ 8 ] R.G. Parr and W. Yang, Density functional theory of atoms
rigorous justification from theory. and molecules (Oxford Univ. Press, Oxford, 1989) pp. 75-
81.
[ 91 J.E. Huheey, E.A. Keiter and R.L. Keiter, Inorganic chemistry
References
(Harper Collins College Publishers, New York, 1993).
[ 1 ] R.G. Pearson, J. Chem. Educ. 64 (1987) 561.