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Chemical hardnesses of atoms and molecules from frontier orbitals

Article  in  Chemical Physics Letters · September 1997

DOI: 10.1016/S0009-2614(97)00799-9

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 5 September 1997

CHEMICAL
PHYSICS
LETTERS
ELSEVIER Chemical Physics Letters 275 (1997) 527-532

Chemical hardnesses of atoms and molecules from frontier

orbitals
P. S e n e t 1
Max-Planck-lnstitut fiir Str6mungsforschung, Bunsenstrasse 10, 37073 Gi~ttingen, Germany
Received 3 February 1997; in final form 11 July 1997

Abstract

It is demonstrated that the chemical hardness of molecules is exactly the screened interaction energy of the electrons in
the frontier (HOMO, LUMO) orbitals, whereas the derivative of the Kohn-Sham potential relative to the electron number is
a screened local hardness measuring the local reactivity of molecules and solids. It is also shown that the hardness of two
interacting molecules involves the screened interaction between their respective HOMO and LUMO orbitals. The formula
are applied to the Thomas-Fermi model. © 1997 Published by Elsevier Science B.V.

1. Introduction of an atom relative to its charge have been consid-

Electronegativity and chemical hardness have been
popular concepts in chemistry for several decades
[1,2]. The former measures "the power of an atom
or group of atoms to attract electrons to itself' [3]
whereas the latter measures "the resistance of an
atom to a charge transfer" [4]. Indeed, charge trans-
fer between two atoms is driven by the difference of
their electronegativities which is equal in first-order
to the product of the charge transferred by the sum
of their hardnesses [4]. The inverse of hardness,
softness [4], can be interpreted as " t h e capacity of an
atom or group of atoms to receive electrons".
The first and second derivative of the total energy
i Present address: Laboratoire de Physique du Solide, Facultrs
Universitaires Notre-Dame de la Paix, 61 Rue de Bruxelles, 5000
Namur, Belgium.
ered, respectively, as an electronegativity and as an
important charge coefficient [5], which has been
shown later to be equivalent to the chemical hard-
ness [4]. Therefore, in a simple electrostatic model
[6], in which an ion is represented by a conducting
sphere of some characteristic radius R and charge
Qe, electronegativity and hardness are equal to the
potential energy at the surface of the sphere,
Qe2/47r%R, and to a quantity inversely propor-
tional to the electrostatic capacity of the sphere,
e2/47reoR, respectively. This crude model explains
why ions are more electronegative than the corre-
sponding neutral species, why large atoms are soft,
and why softness is proportional to polarizability. It
fails however to reproduce the electronegativity dif-
ferences of neutral atoms in the periodic table.
Only in recent years has density functional theory
(DF'I') [7,8] provided a sound conceptual framework
for these qualitative, empirical concepts [9]. In DFY,
electronegativity is the negative of the chemical po-

0009-2614/97/$17.00 © 1997 Published by Elsevier Science B.V. All rights reserved.

PII S 0 0 0 9 - 2 6 1 4 ( 9 7 ) 0 0 7 9 9 - 9
528 P. Senet / Chemical Physics Letters 275 (1997) 527-532
tential /x, i.e. the derivative of the electronic energy
E relative to the number of electrons N [10],
= , (1)
Vext
and the hardness r/ is the second derivative of the
energy, i.e. [4],
where the derivatives are carried out at constant
external potential Vext(r), equal to the electron-ion
potential plus any other potential applied to the
system. Whereas softness and hardness are global
properties of the system as a whole, a local hardness
rl(r) [11] and softness s(r) [12] may be defined
which discriminate the hard and soft regions of a
molecule. The local softness is defined by [91
s(r) = S[ Oo(r) ] , (3)
[ ON I~o,,
where S is the global softness (S = 1/7?) and the
derivative of the electronic density p(r) is called the
Fukui function f ( r ) [13]. The latter is closely related
to the HOMO and LUMO frontier orbitals [9] of the
electron frontier orbital theory [14] and to the density
of states at the Fermi level [15] in a solid. The local
hardness R(r) is related to these quantities by the
following integral on the entire space [9]
f dr, rl(r,) s(r,) = 1. (4)
The calculation of the hardnesses and softnesses
is of interest because they enter in two well-known
principles of modern chemistry: the hard-soft-acids-
bases principle [2] and the maximum-hardness prin-
ciple [16]. The former states that "hard (soft) Lewis
acids will prefer to interact with hard (soft) Lewis
bases" and more generally "hard (soft) regions of a
molecule will prefer to interact with hard (soft)
regions of a reagent" [2,17]. The latter states that the
minimum of the energy of a system corresponds also
to a maximum hardness [16]. Most of the calcula-
tions of these chemical atomic and molecular quanti-
ties have been at an empirical level [4,6], based on
DFT models [18,19] or based on finite difference
approximations of Eq. (3) [9]. On the other hand,
local softness has been formulated exactly in terms
of orbitals in the Kohn-Sham (KS) formulation of
DFT, making its ab initio calculation feasible [20,21].
Surprisingly, no similar exact orbital formulation
exists for the global hardness. It should be noted
however that recently in the KS formalism a hard-
ness matrix [22], which is only approximatively re-
lated to 77 [21], has been introduced.
In a recent paper [21], we derived an orbital
formulation of all the derivatives of the electronic
energy. In the present Letter, this formulation is
shown to provide simple physical interpretations of
both the global and local hardnesses and new practi-
cal schemes for their ab initio evaluation.
2. Derivation
In the KS formulation of DFT [8], the electronic
energy is given by [9]
E = 2 Ef~ei + E I ( p )
i
- fd,', [V,,s(,'l) - o(,'l), (5)
where E~ is the sum of the Hartree Coulomb repul-
sion energy and of the so-called exchange-correla-
tion energy. It is only a functional of the electronic
density
p(r) =2Y'.f~lOi(r)12=-2Y'.fipi(r), (6)
i i
where as in Eq. (5), f / a r e the occupation numbers (0
or 1) of the KS orbitals ~bi which in turn are
solutions of the following Schrrdinger equations
Hlq~i) = eilri). (7)
Here H is the ground-state one-electron KS Hamil-
tonian [8,9],
h2
/4 = - --v 2 + vKs(r), (8)
2m
where, as in Eq. (5), the self-consistent KS potential
vKS is defined by
6E~
VKS(r) = Vext(r) + 6p(r----~' (9)
in which the functional derivative is evaluated at the
ground-state value of the density.
 P. Senet/ Chemical PhysicsLetters 275 (1997) 527-532 529

The relation between the chemical potential and As will be shown next, the last two terms of Eq.
the HOMO and LUMO one-electron energies, the (10) exactly cancel each other, and thus the well-
so-called frontier eigenvalues EF, has been known known identification of the chemical potential with
for some time [23]. This result and the orbital expres- the frontier KS eigenvalues is recovered [23]. Indeed,
sion of the hardnesses can be obtained by direct the derivative of the KS SchriSdinger equations (7) is
derivation of Eq. (5) relative to the electron number (H- E,)I4,;) = V14,), (14)
N as shown below. It should be noted that for a
system with a HOMO-LUMO gap, such a derivative in which
is not well defined. Indeed, it may have different
values when evaluated to the left ( N - ) and to the
right (N +) of an integer value N of the number of Velt
electrons [23]. The corresponding chemical quantities and V is a perturbation given by the following
measure the response of the electrons to an elec- equation:
trophilic ( A N < 0 ) or to a nucleophilic ( A N > 0)
reagent, respectively [9]. The response to a radical V ~ ~i
- ON ,',, (16)
reagent ( A N = 0) is described by their average [9,20].
Carrying out these derivatives of the energy in Eq. Projection of Eq. (14) on the ith state yields the
(5) one obtains for the chemical potential result
OVKs
= eF + 2 ~f/r/i
i ~ i = < ~bi][ - - - ~ ] Cext](J~i>. (17)

From Eq. (13) it is found that

- fdrlfdr2 F(r,) hr(r,,r2) p(r2),
(10)
ON ~e~'=
where a = + or - and "qi and h~ are defined by (18)
_ [ Oei] ~ which defines what we call a screened local hardness
r/i '~ t-~],. , (11) ~(r). Using Eqs. (17) and (18) in Eq. (10) the
desired equality # = e F is obtained. In addition, the

h (r,,r2) = [ @ ( r ,a) @e'( , ' 2 ) ] . (12)

expression of the global hardness follows immedi-
ately from this result,

The first term of Eq. (10) arises because only the n = nV = f a r , OF(r,) ~ ( r , ) , (19)
occupation of the frontier orbital may change by
where PF is the frontier orbital density (see Eq. (6)).
addition (removal) of electrons to (from) the system
On the other hand, from Eqs. (4), (18) and (19) one
and the second is readily obtained by using the
obtains the following relation for the local hardness
following rule for the differentiation of an arbitrary
functional A ( p ) (20)
n(r) = fdr, hi(r,rl) PF(rl),
aA(p) _f6A(p) 0/9 (13) which may also be expressed as a sum of a Hartree
ON J 6p ON" Coulomb contribution and an exchange-correlation
Note that the h t kernel in Eq. (10) may have a part
different value if evaluated on the right or on the left e2 pF(rl)
of an integer number of electrons [23]. In the remain- n(r) = fdr
J41re o I r - r l [
der of the Letter, the indices a are dropped in order
to simplify the notation since this does not affect our
derivation.
+ fdr, hxc(r,r,) pF(r,). (21)
530 P. Senet / Chemical Physics Letters 275 (1997) 527-532
Eq. (21) may be found in Ref. [24] whereas Eqs. (18)
and (19) are new first-principles expressions for the
hardnesses. Their physical meaning and relations
with earlier work are discussed next.
3. Discussion
The simple electrostatic model described above is
used to define, by analogy, the radius R of a spheri-
cal atom via the following equation:
/z = VKs( R ) .
With this definition and Eq. (18), the atomic hard-
ness can be approximated as
r/= ~(R),
which implies from Eq. (19) that the electrons of the
frontier orbital are assumed to be "localized" at the
radius R
6(r-R)
pF(,) = 4,rrR2
By approximating E~ by the Hartree energy, Eq.
(22) becomes the well-known definition of the so-
called covalent atomic radius R c [19]. In this Hartree
approximation, Eq. (23) states that the hardness r/ is
the electrostatic potential at the covalent radius due
to the Fukui function. This relation has been justified
qualitatively and tested numerically [19] and is re-
covered here as a special case. It is worth noting that
~/(r) diverges at Re.
Eq. (19) for the hardness involves the Fukui
function f ( r ) which is related to the frontier orbital
by the exact relation [21,15]
f ( r ) = f dr, oF(r,) KC'(r,,,),
where K~-1 is the inverse linear potential response
function [21,15]
arKs(r) ] =
aVox,(r,).N ~ ( ' - ' 1 )
+ fdr2 h,(r,r2) xl(r2,rl),
in which X~ is the well-known linear density-density
response [25]. Therefore, in the Hartree approxima-
tion, /(1 1 represents exactly the inverse dielectric
function of the many-body screening theory [25,15].
The Fukui function is thus a screened frontier orbital
which is equal to PF only in the approximation of
unpolarizable electrons (X1 = 0) or in the approxi-
mation of noninteracting electrons (h I = 0). Using
Eq. (25), we find from Eq. (19)
~7= f d r , f d r 2 p F ( r , ) h ~ ( r , , r 2 ) p F ( r 2 ) , (27)
where h~¢ is a screened electron-electron interaction
kernel, i.e.,
(22)
h~C('l,r2) = fd,3 K l l ( ' l , ' 3 ) hi('3,'2 ). (28)
(23) Eqs. (27) and (28) imply that the hardness is
equal to the screened electron-electron interaction
energy between the frontier orbital densities. This
can be understood as follows. The finite difference
approximation of the derivative Eq. (2) gives [9]
77 = 1 - A, (29)
(24)
where I and A are respectively the ionization poten-
tial and the electronic affinity of the system. But
I - A is the energy cost of the disproportionation
reaction of a species S [9]
S+S#S++S "-, (30)
and thus should give a good approximation of the
electron-electron self-energy in the HOMO of S [9].
Approximation of the self repulsion integral by the
quantity I - A was first made by Pariser [26] in a
semi-empirical electronic method. It can be further
justified in DFT from Eqs. (27) and (29). The screen-
ing of the electron-electron interactions involved in
(25) rl explains also why the hardness is inversely propor-
tional to the dipolar polarizability in atoms [27].
Eq. (27) encompasses one of the keys of frontier
orbital theory: describe chemical reactions and hard-
ness/softness in terms of interactions between fron-
tier orbitals [ 14]. Indeed let us consider two molecules
A and B far apart from each other such that the
frontier orbital density of the entire AB system is the
(26) sum of frontier orbital densities of molecules A and
B
PF(r) = + (31)
 P. Senet/ ChemicalPhysicsLetters275(1997)527-532
From this partition of the frontier density one obtains
from Eq. (27)
ri = riAA 21_ riBB _~_2riAB, (32)
in which riAB is defined as
riAB = f drl f dr2 pA(rl ) h~(rl,r2) p~(r2),
(33)
and where riAA, riBB are in obvious notation. Ac-
cording to Eq. (33) the hardness of two interacting
molecules at large distances - i.e. at which the
frontier densities p# and P~ do not overlap signifi-
cantly - involves the screened interaction between
their respective H O M O and L U M O orbitals. Eq. (33)
holds also in principle at short AB separations though
in this region the sub-systems densities (Eq. (31))
cannot be defined in a unique way. Applications of
the above formula for polyatomic systems will be
explored in a further publication.
A one-electron orbital numerical evaluation of the
polarizability kernel X1 is feasible [25]. Use of this
quantity in Eq. (27) should give a better evaluation
of ri than earlier estimations based on a frozen-orbital
approximation (X~ = 0) [26]. Such a calculation is
however not simple and some insight can be gained
by using the Thomas-Fermi (TF) model for which
the dielectric function ~ ( I r - r 1I) in the wave-vector
space Q is simply [25]
efV(Q) = 1 + Q---S, (34)
where 1/Q~ is the so-called TF screening length. It
is readily found in this model from Eq. (27) and
using K 1 = I / E that
e2 1 pF(Q) 2
riTF_ 41re
__ ° 2,rr2
fdQ Q2
+ Q2 - (35)
riTV is positive which is related to the variational
principle of DFT. On the other hand, recalling that
Q~ is related to the density of states at the Fermi
level D ( £ ) (per volume unit) by Q~ = eZD(£)/eo,
one finds that the hardness increases when D ( £ )
decreases which in fact is a general property for
metals [ 12].
Global hardness Eq. (2) is not a relevant quantity
for a macroscopic solid or for a very large molecule
for which it always has a negligible value since such
531
systems are infinite reservoirs of electrons. There-
fore, the local properties ri(r) and s(r) must be
used. We believe however that this is the screened
local hardness ~ ( r ) which could be more relevant
for chemistry as exemplified by the success of the
approximation Eq. (23). On the other hand, in a
periodic solid ~/ can be expanded in a Fourier series
I
~/(r) = ~ E T / G e iGr, (36)
G
where G are the reciprocal lattice vectors and /2~ is
the volume of the crystal unit cell. It is readily
shown in the TF approximation that ~70 = 1/D(¢)
whereas rl0 diverges. ~/0 makes the link between
hardnesses of isolated atoms and of the same atoms
in a solid. These hardnesses are compared for alkali
atoms and metals in Table 1.
In this Letter, new first-principles formulae have
been derived for hardnesses which are consistent
with all known earlier results. The physical meaning
of hardnesses, including hardnesses of atoms in
solids, has been clarified. A model of ~ for insula-
tors is presently under investigations. Local softness
s(r) is equal to a screened local density of states at
the chemical potential energy [15]. Only a very
approximate measurement of it for metal surfaces
can be obtained by using scanning-tunneling-mi-
croscopy [28] in which the tunnel current is roughly
proportional to the local density of states at the
Fermi level, i.e. to the frozen core approximation of
the local softness. It would be of considerable inter-
est to find a technique which could directly measure
the screened local hardness ~/(r) or at least a linear
mapping of it. This would provide complementary
maps of the reactivity character of a surface in the
sense of Eq. (19).
Table 1
Hardnesses and polarizabilities of alkali atoms
cra 7/atomic b T/bulk metal ~
[,~31 [eVl [eVl
Li 22.0 4.8 2.1
Na 24.4 4.6 2.2
K 45.2 3.8 1.4
Rb 48.7 3.7 1.1
Cs 63.3 3.4
a Polarizabilities of isolated atoms from Ref. [29].
b 1-- A from Ref. [9].
c Calculated as r/0/[1~ with D( ~ )/2c from Ref. [30].
532 P. Senet / Chemical Physics Letters 275 (1997) 527-532
Acknowledgements
I thank Professor J.P. Toennies for his interest in
this work during my stay in G~ttingen and for his
remarks on the manuscript.
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