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A Quest for the Algorithm for Evaluating

the Molecular Hardness
AQ2 DULAL C. GHOSH, NAZMUL ISLAM
Department of Chemistry, University of Kalyani, Kalyani, West Bengal 741235, India

Received 5 August 2009; accepted 23 October 2009

Published online 00 Month 2009 in Wiley InterScience (www.interscience.wiley.com).
DOI 10.1002/qua.22499

ABSTRACT: In this work, we have basically launched a search whether the

molecular hardness, an important conceptual descriptor of chemistry and physics, can
be evaluated in terms of the atomic hardness values invoking various mathematical
algorithms for averaging or not. Starting from the semi-empirical radial dependent
formula of computing global hardness of atoms suggested by us, we have derived an
ansatz of the molecular hardness assuming that the hardness equalization principle is
operative and justifiably valid. In this work, we have attempted a validity test of our
ansatz for computing molecular hardness by application to real world. We have also
computed the hardness of considerable number of molecules through various
mathematical averaging techniques. We have also computed the hardness data of such
molecules by invoking ab initio quantum chemical method through the formula of Parr
and Pearson, (I  A)/2. Results demonstrate that the set of hardness data evaluated
through our suggested ansatz have very close agreement with the ab initio hardness
data compared to the sets of data obtained through the various averaging techniques. In
our next effort, by exploiting the suggestion of Gazquez, we have evaluated the reaction
energy of a number of hard–soft acid–base exchange reactions. On a comparative study,
it is found that (i) the arithmetic formula does not predict the reaction path at all, (ii)
other methods fail to explain all the reactions efficiently, and (iii) the molecular
hardness evaluated by the method suggested by us represent the reaction surface quite
reasonably. V C 2009 Wiley Periodicals, Inc. Int J Quantum Chem 000:000–000, 2009

Key words: HSAB principle; maximum hardness principle; hardness equalization

principle; electrostatic model of hardness; hardness difference and reaction energy

equivalent proportion they destroy each other. It

AQ3 Introduction is very difficult to define an acid and a base in
terms of their chemical composition or molecular

A cid and base are two diametrically opposite

concepts such that when they are mixed in
Correspondence to: D. C. Ghosh; e-mail: dcghosh1@rediffmail.
com
structure [1]. Many definitions and theories are
put forward to define acid and base, but the
Lewis [2] concept based on electronic structure
appears to be the most convincing and enduring
one. It is apparent that all other definitions of

International Journal of Quantum Chemistry, Vol. 000, 000–000 (2009)

V
C 2009 Wiley Periodicals, Inc.

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GHOSH AND ISLAM
acid and base can be substituted by a single defi-
nition of Lewis. Of the many efforts of systematiz-
ing and rationalizing the plethora of information
accumulated on acid base behavior, the HSAB
principle propounded by Pearson [3] is undoubt-
edly the most promising one. History shows that
the terms hard and soft are very old and were
originated with Mulliken [4] when he pointed out
that the ‘‘Hard’’ and ‘‘Soft’’ behavior of various
atoms, molecules, and ions can be conceived dur-
ing the acid–base chemical interaction. Thereafter,
Pearson [3] and Klopman [5] tried to systematize
and rationalize this intrinsic property of atoms
and molecules in terms of the electronic struc-
tures. Pearson [3] classified molecules, atoms, and
ions in three classes, hard, soft and borderline—
known as the HSAB principle. But the classifica-
tion was qualitative and its basis was empirical.
The hardness as conceived in chemistry signi-
fies the resistance toward the deformation of
charge cloud of the chemical systems under small
perturbation encountered during chemical proc-
esses. Thus, the general operational significance of
the hard–soft chemical species may be understood
in the following statement. If the electron cloud is
strongly held by the nucleus, the chemical species
is ‘‘hard,’’ but if the electron cloud is loosely held
by the nucleus, the system is ‘‘soft’’ [3, 5].
In chemical domain, there is extensive theoreti-
cal search to quantify chemical hardness. Klop-
man [5], in an attempt to theorize the HSAB prin-
ciple, had drawn link to Hard -Soft behavior with
the HOMO-LUMO gap of the frontier orbital
theory. The term hardness is also a very popular
term in condensed matter physics [6]. The me-
chanical hardness is linked with the ‘‘HOMO-
LUMO’’ gap evaluated from the band spectrum.
The significance of the term hardness to a physi-
cist is the resistance toward the distortion of
structure of the solid species. Such resistance is
offered by the screened nucleus on the electron
cloud of the species under distortive influence.
Thus, the hardness is one of the extremely useful
and indispensible conceptual constructs of the
present day theoretical chemistry and condensed
matter physics.
The word ‘‘hardness’’ has been used by both
physicists and chemists virtually in different con-
texts, and consequently, the same word ‘‘hard-
ness’’ has two different connotations—‘‘chemical
hardness’’ and ‘‘physical hardness.’’ But the two
different fundamental descriptors of physical
structure, the chemical hardness and the physical
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hardness, have fundamentally evolved with time
to converge to the one and single concept—the
hardness in general [7].
The concept of hardness and electronegativity
are two very important fundamental descriptors
extensively used in theoretical chemistry and con-
densed matter physics but none of them is physi-
cal observable. But it is the experience of chemists
and physicists that the appearance and signifi-
cance of heuristically developed concepts of elec-
tronegativity and hardness in chemistry and
physics resemble the unicorns of mythical saga
[8]. They occur in the domain of the hypothesis.
They exist but never seen. We may refer to the
opinion of Parr et al. [9] who seem to have con-
nected the reality of the hardness and the electro-
negativity with the noumenon of Kantian philoso-
phy. The noumenon is an object knowable by the
mind or intellect, not by the senses. Thus, the
hardness and/or electronegativity is an object of
purely intellectual intuition. We feel it pertinent
to recall the opinion of Ayers [10] that before any
algorithm of computing the hardness and the
electronegativity is developed, the reification of
abstract concept into things of the real world is
necessary.
Without the concept and operational signifi-
cance of hardness and electronegativity, chemistry
and many aspects of condensed matter physics
becomes chaotic, and the long-established unique
order in chemico-physical world will be disturbed
[7]. Thus, the hardness is a qualitative concept
par see and has to be evaluated qualitatively
goaded by physical and chemical experience. But
according to the rules of quantum mechanics nei-
ther the electronegativity nor the hardness has
any quantum mechanical operator to enable the
quantum mechanical evaluation of such descrip-
tors. However, within the scope of the new para-
digm of density functional theory [11–16], the
work of Parr and Pearson [16] clarified the con-
ceptual interpretation of the hardness and sug-
gested a quantitative definition for hardness, g as
follows:
g ¼ 1=2½@ l=@ Nv ¼ 1=2½ð@ 2 E=@ N2 Þv (1)
where, E and N are the total energy and the total
number of electrons, v is the external potential,
and l is the chemical potential having the defini-
tion:
l ¼ ½@ E=@ Nv (2)
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AQ1
The operational and approximate formula of
hardness invoking the calculus of finite difference
looks:
g ¼ ðI  AÞ=2
Where I and A are the first ionization potential
and electron affinity of the chemical species. Pear-
son [17] connected these DFT descriptors with the
Hartree-Fock SCF theory and proceeded further
to evaluate I and A in terms of orbital energies of
the highest occupied molecular orbital, HOMO,
and the lowest unoccupied molecular orbital,
LUMO, by invoking Koopmans’ theorem. The
modified formula for the computation of hardness
looks
g ¼ ðeHOMO þ eLUMO Þ=2
The density functional definitions of hardness
of Parr and Pearson [16] are now in the glossary
of chemistry. The quest for the theoretical basis of
the hard soft acid base behavior has given birth
of a new branch of density functional based theo-
retical chemistry known as ‘‘Conceptual Density
Functional Theory’’ [12, 18–23].
The conceptual density functional theory has
added (i) the maximum hardness principle [24],
(ii) the minimum polarizability principle [25], and
(iii) the electronegativity equalization principle
[26] to the list of the fundamental principles in
the chemical domain of the nature. The concep-
tual density functional theory has been success-
fully exploited in elucidating and correlating
many mechanistic aspects of chemico-physical
processes viz. regio-selectivity, catalysis, aromatic-
ity, intramolecualr rotation, inversion and isomer-
ization reaction, and the rationale of the reactive
proclivities [27–34].
Importance of the HOMO-LUMO
Gap in Solids
In solids, the HOMO-LUMO gap is also used
to evaluate the hardness, which describes its me-
chanical stability. The HOMO-LUMO gap also
determines the optical hardness of transparent
solids. Optical hardness is associated with the
electronic polarizability, which determines the re-
fractive index and is largely determined by the
HOMO-LUMO gap.
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ALGORITHM FOR EVALUATING THE MOLECULAR HARDNESS
The hardness has been identified as the cardi-
nal index of chemical reactivity and stability. But
question remains, are the Eqs. (1) and (3) can be
exploited to evaluate the hardness of atoms and
(3) molecules? Sen and Vinayagam [35] have demon-
strated that the computation of hardness by
invoking this equation is extremely difficult. Eval-
uation through the operational and approximate
formula of Parr and Pearson face some practical
difficulties. The ionization potential, I, for all the
atoms are known but that of electron affinity, A,
is not probably all known accurately. In case of
molecules, the problem of evaluation of hardness
through the Eq. (3) faces some obvious difficulties
that the I and A for every molecule is not known
both experimentally. Although the method of
photo-electronic spectroscopy can calculate I and
A for molecule. Also, we are here after to the de-
(4)
velopment of a semi-empirical algorithm for the
evaluation of hardness for molecule. In case of
atom, we previously developed a semi-empirical
model.
Evaluation of Molecular Hardness
from the Hardness of Its
Constituent Atoms: The Search
of Probable Algorithm of
Molecular Hardness
Now atoms merge into molecules under the
criteria of minimum energy principle, and the
supplementary to the minimum energy criteria is
the maximum hardness principle. The hardness of
a conglomeration of atoms, i.e., a molecule is
maximum at the equilibrium conformation.
Now, it is well known that the energy of a
cluster of atoms, i.e., molecule is less than the
sum of the energies of constituent atoms. Now
what is the relationship between the sum of
atomic hardnesses and the molecular hardness?
As we have already pointed above that the ap-
proximate working formulae of Parr and Pearson
[16] for the evaluation of hardness vide Eq. (3)
and Eq. (4), is not useful in evaluating the hard-
ness of molecule because of the fact that both the
ionization potential, I and the electron affinity, A
can not be known. Therefore, it is expedient and
necessary that some method must be developed
for the computation of molecular hardness. In the
literature, we find that there are efforts [36–39] of
computing molecular hardness in terms of
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GHOSH AND ISLAM
available atomic hardness through various mathe-
matical techniques. To explore the comparative ef-
ficacy of the mathematical averaging formulae of
computing molecular hardness, we have per-
formed a validity test. We have computed the
molecular hardness through the atomic hardness
data computed by us [40] invoking the available
mathematical averaging techniques.
METHOD OF GHOSH AND COWORKERS
Ghosh and coworkers [36] considered that the
hardness of a molecule is simply the arithmetic
mean of the softness of its composing fragments.
ð1=gAB Þ ¼ ð1=2Þfð1=gA Þ þ ð1=gB Þg
Where gA, gB, and gAB are the hardness value of
the atom A, B, and the molecule AB, respectively.
Rearranging the above equation, we get
gAB ¼ 2gA gB =ðgA þ gB Þ
This method implies that Ghosh and coworkers
[36] invoked harmonic mean of the hardness
value.
METHOD OF DUTTA
Dutta [37] proposed a model for the molecular
hardness relying upon the fact that hardness
and electronegativity are fundamentally propor-
tional to each other, and hence, there will be
hardness equalization analogues to the electrone-
gativity equalization. He proposed the formula
for the equalized molecular hardness for a dia-
tomic system simply by taking the geometrical
mean of the hardness values of the atoms.
gAB ¼ ðgA gB Þ1=2
ARITHMETIC MEAN FORMULA FOR
EVALUATING MOLECULAR HARDNESS
We venture to verify whether the arithmetic
mean the atomic hardness can be used as a tool
for the evaluation of the molecular hardness. The
arithmetic average hardness (AM) can be repre-
sented for a diatomic system as follows:
gAB ¼ ðgA þ gB Þ=2
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The entries in the above equations bear their
original meanings.
METHOD OF GHOSH
An alternative model, originally due to Ghosh
[38], uses the electron-transfer energy formula of
Parr and Pearson [16] to compute the response of
the molecular chemical potential to additional
electrons,
gAB ¼ ðg2A þ g2B þ 3 gA gB Þ=ðgA þ gB Þ (9)
But Chattaraj et al. [39] without any numerical
data made a comparative study of the efficacious-
ness of the model of Ghosh [38], and the arithme-
(5) tic mean formula of Ghosh and coworkers [36].
We want to explore the efficient algorithm for
computing the molecular hardness from the avail-
able atomic hardness data. We have already sug-
gested a new algorithm for computing molecular
hardness [41]. Now we explore the efficacy of the
(6) suggested algorithm in comparison vis-a-vis the
existing formulae.
Molecular Hardness as a Function
of Internuclear Distance—The
Present Method
In a recent work [40], we have relied upon the
fact that the atomic hardness is a function of the
absolute/most probable atomic radius, i.e., gAtom
¼ ƒ(r). We have computed the global hardness of
the 103 elements of the periodic table using the
radial dependent ansatz proposed by us. For
ready reference, the computed atomic hardnesses
are presented in Table I. Again in a recent com- T1
munication [41], relying upon the hardness equal-
ization principle, we have pointed out that the
(7) molecular hardness is a function of the internu-
clear distance of the atoms, i.e., gMolecule ¼ ƒ(rAB).
The necessary algorithm for evaluating the mo-
lecular hardness from the atomic hardness under
the operation of hardness equalization principle is
laid down in our previous report [41]. We again
mention here the salient points for the easy visu-
alization of the jargon of the trade. With the phys-
ical process of charge transfer during chemical
reaction leading to bond formation, the hardness
kernel of atoms change and in the process, it
would increase somewhere and decrease else-
(8) where ultimately the hardness values of the
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ALGORITHM FOR EVALUATING THE MOLECULAR HARDNESS

TABLE I
AQ6 Periodic chart of computed hardness values of 103 elements.

C
O
L
O
R

atomic fragments will equalize to some intermedi- and

ate values common to all. Let d be the amount of
charge transfer from atom B to A, during the for- =
gB ¼ Cðe  dÞ2 =2rB (11)
mation of the molecule, AB.
Thus, after the charge transfer the hardness of
atom A and B in the molecule AB becomes gA
= respectively.
=
and gB , respectively. The necessary formulae are Expanding and neglecting the d2 term we get:

= =
gA ¼ Cðe þ dÞ2 =2rA (10) gA ¼ Cðe2 þ 2edÞ=2rA (12)

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GHOSH AND ISLAM
and
= pendent on other factors such as electronegativ-
gB ¼ Cðe2  2edÞ=2rB
Then invoking the hardness equalization prin-
ciple and the approximation [42] r1  rA and r2 
rB, the molecular hardness can be shown as:
gAB  C½e2 =ðRAB Þ
The Eq. (14) computes hardness in esu, in elec-
tron volt the Eq. (14) looks:
gAB  Cð14:4=RAB Þ
where, the internuclear bond distance, RAB must
be expressed in the Angstrom unit, C is the con-
stant depending on the fundamental nature of
hardness e.g., the bond type and steric factors.
However, we have obtained a standardized value
of C ¼ 0.75 with the help of the Hyperchem 8.0
professional program [43].
The hardness of all of the molecules studied
here is computed by invoking an ab initio Har-
tree-Fock quantum mechanical method. To be
very specific, to compute the ab initio quantum
chemical hardnesses of the compounds, the geo-
metries of the corresponding molecules have been
optimized with minimal STO-3G basis set using
Hyperchem 8.0 professional program [43]. The
equilibrium hardnesses labeled as ab initio hard-
ness of the compounds are calculated using Pear-
son’s formula [17].
Verification of HSAB Rule
Let us consider the generalized acid base
exchange reaction as follows
AB þ A= B= ¼ AB= þ A= B
Now, HSAB principles suggest that if the reac-
tion follows the sequence
i. hs þ sh ¼ hh þ ss
the reaction is spontaneous (DE < 0) but if it
follows the reverse sequence, i.e.,
ii. hh þ ss ¼ hs þ sh
the reaction is not spontaneous (DE > 0).
Where A stands for acid, B stands for base and
‘‘h’’ and ‘‘s’’ denotes harder and softer, respectively.
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However, the spontaneity of the reaction is de-
(13) ities, sizes, orbital symmetry and overlaps, and
steric repulsions etc of the acids and bases
involved in the reactions, one should compare
them to the hardness values based on the maxi-
mum hardness principle [24].
The reaction hardness may be defined as the
(14) difference between the sum of the hardness of the
reactants and the products. The reaction hardness
for a hard/soft exchange reaction can be com-
puted by writing the exchange reactions [16] in
terms of fundamental acid–base reactions:
(15)
A þ B ! AB (17)
There are several models [36–39, 44] for com-
puting the reaction hardness for a hard/soft
exchange reaction. But none of these models have
included all the parameters that determine the
reaction to proceed. To examine the HSAB rule,
although it is impossible, we also assumed that
all the other factors remain constant.
Considering an exchange reaction between ‘‘n’’
number of reactants and ‘‘m’’ number of products,
we can simply calculate the hardness difference
of the reaction as taking difference of the sum of
the reactants hardness and that of the product
hardness
Xn Xm
Dg ¼ i¼1
ðgProduct Þi  j¼1
ðgreactant Þj (18)
Gázquez [45] provided a formula to estimate
the interaction energy or reaction energy (DEReac)
as well as the bond energies (BE) using the chem-
ical potentials and the hardnesses of the isolated
species and the hardness of each of the interact-
ing, say AB of the above exchange reaction spe-
cies, at the equilibrium position as follows
(16)
DEReac  ð1=2ÞfðlA  lB Þ2 =ðgA þ gB Þg
þ 1=2½NAB
2
fgAB  ðgA gB Þ=ðgA þ gB Þg ð19Þ
and
BE ¼ DEReac  ð1=2ÞfðlA  lB Þ2 =ðgA þ gB Þg
þ 1=2½NAB
2
fgAB  ðgA gB Þ=ðgA þ gB Þg ð20Þ
Where, l’s are chemical potentials, g’s are the
hardnesses, and N’s are the number of valence
electrons of the species in the molecule, AB.
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ALGORITHM FOR EVALUATING THE MOLECULAR HARDNESS

Gazquez [45] noted that, in general, the contri- A look on the Eqs. (18) and (24) reveal that the
bution from the first term on the right hand side of hardness difference is directly related to the reac-
Eq. (20), which has been associated with the charge tion energy of the acid/base exchange reactions.
transfer process, is almost negligible in comparison It may represented by
with the second term. However, this should not be
interpreted as if the charge transfer, in general, is Dg ¼ 2DEReac (25)
negligible, because the second term in Eq. (20)
may also include some of the charge transfer asso- Or, more precisely
ciated with the bond formation. It implies that the
change of energy associated with the second step,
Dg / DEReac (26)
at constant chemical potential, represents the main
contribution to the bond energy.
Now, let us consider the following type of It follows immediately that if the sum of the
reactions in which two bonds are broken and two hardness of the products is greater than the sum
new bonds are formed. of the hardness of the reactants, then DEReac < 0,
and if the opposite case occurs, then DEReac > 0.
ABþCD!ACþBD (21) These inequalities are in complete agreement
with the experimental evidence that the exchange
This process may be divided into the following
reaction almost always goes in the direction that
steps:
produces the hardest molecules [46, 47].
In the present effort, we try to evaluate the mo-
AB!AþB
lecular hardness using the (i) geometrical, (ii)
CD!CþD arithmetic, (iii) the harmonic average formula for
AC!AþC the hardness equalization principle of molecular
BþD!BD formation, and (iv) the ansatz of Ghosh [38]. We
have invoked the formulae above said to evaluate
Now applying Eq.19 to each one of these steps, equilibrium hardness of a number of diatomic
the reaction energy is derived by Gazquez as molecules. Thereafter, we have computed the
follows: hardness difference of some well-known acid/
base exchange reactions. Along with this, we have
DEReac ¼ ½ð1=2ÞfNAC
2
gAC þ NBD
2
gBD  NAB
2
gAB used our formula, Eq. (15) to compute the hard-
ness difference of some acid/base exchange reac-
 NCD
2
gCD g þ ½ð1=2ÞfNAC
2
fgA gC =ðgA þ gC Þ tions. We further evaluated the hardness differen-
þ NBD
2
fgB gD =ðgB þ gD Þ  NAB
2
fgA gB =ðgA þ gB Þ ces of some exchange reactions using their ab
initio quantum chemical hardness data.
 NCD
2
fgC gD =ðgC þ gD Þ  ½ð1=2ÞfðlA  lC Þ2 =ðgA
þ gC Þg þ fðlB  lD Þ2 =ðgB þ gD Þg  fðlA  lB Þ2 =ðgA
þ gB Þg  fðlC  lD Þ2 =ðgC þ gD Þg ð22Þ Results and Discussion

Then, Gazquez [45] proceeded to arrive at the We have reproduced the global hardness val-
final formula by assuming that N ¼ 1 in all cases ues of the atoms of the 103 elements of the peri-
and neglecting the second and third terms of odic table published by us [40] in Table I atomic
Eq. (22) hardness used to evaluate the average hardnesses
of the molecules brought under study is taken
DEReac  ½ð1=2ÞfðgAC þ gBD Þ  ðgAB þ gCD Þg from Table I.
(23) The different sets of hardness data computed
through different formulae discussed here in ear-
For a polyatomic molecule the interaction lier are presented in Table II. Table III present the T2 T3
energy thus can be written as ‘‘Standard Deviation’’ (SD) in % between the ab
initio molecular hardness values and that of the
DEReac hardness values computed through the five differ-
nXn Xm o
ent methods under reference. In Table IV, we T4
 ð1=2Þ ðgProduct Þi  ðgreactant Þj ð24Þ
i¼1 j¼1 made a comparative study of the hardness

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GHOSH AND ISLAM

TABLE II
Comparative study of the different sets hardness data evaluated through various averaging formulae,
the formula of Ghosh and that through the present work of selected molecules vis-a-vis their
ab initio counter parts (eV).

Molecule gAB (ab initio) g (Present work) gAB (GM) gAB (AM) gAB (HM) gAB (Ghosh )

LiF 6.15445 6.90591 4.65017 5.74053 3.76692 9.41739

LiCl 5.36037 5.34471 3.73226 4.12039 3.38069 8.45174
LiBr 5.01916 5.34259 3.74652 4.14284 3.38811 8.47028
LiI 4.60443 4.51516 3.64135 3.97924 3.33215 8.33038
NaF 8.03546 5.60757 4.71779 5.77531 3.85391 9.63477
NaCl 8.35535 4.57468 3.78653 4.15516 3.4506 8.62649
NaBr 7.73399 4.31643 3.801 4.17762 3.45832 8.64581
NaI 7.39956 4.51516 3.69429 4.01401 3.40004 8.50010
KF 4.42853 4.97356 4.60366 5.7169 3.7072 9.26799
KCl 4.93819 4.04998 3.69493 4.09675 3.33251 8.33128
KBr 4.54884 3.82869 3.70904 4.11921 3.33972 8.34930
KI 4.29956 3.54345 3.60492 3.9556 3.28534 8.21334
RbF 5.08598 4.75695 4.3943 5.61347 3.43992 8.59981
RbCl 5.88444 3.87546 3.5269 3.99332 3.11495 7.78738
RbBr 5.38427 3.66751 3.54037 4.01578 3.12125 7.80312
RbI 5.18921 3.39952 3.44099 3.85217 3.07369 7.68423
HF 14.326 11.7798 7.65207 7.76822 7.53767 18.8442
HCl 10.8576 8.47343 6.14161 6.14807 6.13515 15.3379
HBr 9.99803 7.63436 6.16507 6.17053 6.15962 15.3990
HI 8.6564 6.71171 5.99201 6.00692 5.97713 14.9428
AgF 5.38581 5.44574 5.56697 6.25484 4.95474 12.3869
AgCl 5.1632 4.73514 4.46808 4.63469 4.30747 10.7687
AgBr 5.18045 4.5129 4.48516 4.65715 4.31952 10.7988
AgI 5.17922 4.2442 4.35925 4.49354 4.22897 10.5724
NaH 7.90039 5.72458 3.96431 4.43705 3.54193 8.85482
LiNa 4.11604 3.7435 2.40911 2.40936 2.40886 6.02215
LiK 3.162 3.24139 2.35083 2.35095 2.35071 5.87679
LiRb 3.685 3.13316 2.24393 2.24752 2.24034 5.60085
NaK 4.51935 3.0866 2.38501 2.38573 2.3843 5.96075
NaRb 4.32766 2.96418 2.27655 2.2823 2.27082 5.67706
KRb 3.31265 2.65454 2.22148 2.22389 2.21908 5.54769
KCs — 2.52278 1.2607 1.50512 1.05597 2.63993
RbCs — 2.44432 1.20337 1.40169 1.03311 2.58277
LiCs — 2.9443 1.27344 1.52875 1.06076 2.65190
CsF — 4.6048 2.49378 4.8947 1.27055 3.17637
CsCl — 3.71606 2.00153 3.27455 1.22341 3.05852
CsI — 3.25769 1.95277 3.1334 1.21699 3.04248

differences of the products and the reactants with
reaction energy of some well known hard soft
exchange reactions.
In absence of any benchmark for the hardness,
we can assume that the quantum chemically eval-
uated hardness data is more reliable because such
calculations are done through the density func-
tional algorithm developed by Parr and Pearson
[16]. A deeper scrutiny of the results in Table II
reveals that, contrary to the observation of Chat-
taraj et al., [39] there is a very good correlation
between the sets of hardness data computed
through the quantum chemical method and the
algorithm of the present work, compared to the
sets of hardness data evaluated through various
averaging formulae and also the formula of
Ghosh [38]. It is further evident that the three dif-
ferent sets of hardness data computed through
the three different averaging formulae are closely
correlated. It is surprising to note that the set of

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ALGORITHM FOR EVALUATING THE MOLECULAR HARDNESS

TABLE III
Comparative study of the ‘‘Standard Deviation’’ (SD) in % between the ab initio hardness data and the
respective hardness data evaluated through different methods under reference.

Molecule SD (GM) SD (AM) SD (HM) SD (Ghosh) SD (Present Work)

LiF 24.44209 6.725524 38.79357 53.0161 12.21

LiCl 30.37308 23.13242 36.9317 57.6708 0.292219
LiBr 25.35562 17.45943 32.49643 68.7589 6.44393
LiI 20.9164 13.57808 27.6316 80.921 1.938872
NaF 41.28791 28.12722 52.03873 19.9032 30.21475
NaCl 54.6814 50.26942 58.70197 3.24508 45.24853
NaBr 50.85338 45.98363 55.2841 11.7898 44.18883
NaI 50.07414 45.75334 54.05078 14.8731 38.98075
KF 3.95453 29.0924 16.28831 109.279 12.3073
KCl 25.17651 17.0394 32.51549 68.7113 17.98665
KBr 18.46176 9.444853 26.58082 83.5479 15.83153
KI 16.15597 7.999831 23.58904 91.0274 17.58582
RbF 13.59968 10.3714 32.36457 69.0886 6.469294
RbCl 40.06401 32.1376 47.06461 32.3385 34.14061
RbBr 34.246 25.41646 42.03026 44.9244 31.88477
RbI 33.68956 25.76572 40.7676 48.081 34.48866
HF 46.58612 45.77541 47.3847 31.5382 17.77295
HCl 43.43497 43.37542 43.49445 41.2639 21.95849
HBr 38.33714 38.28257 38.39166 54.0208 23.64136
HI 30.77947 30.60717 30.95133 72.6217 22.46535
AgF 3.36358 16.1355 8.003726 129.991 1.11266
AgCl 13.46289 10.23608 16.5737 108.566 8.290572
AgBr 13.4215 10.10149 16.6189 108.453 12.88589
AgI 15.83194 13.23904 18.34733 104.132 18.05336
NaH 49.8214 43.83761 55.16764 12.0809 27.54049
LiNa 41.47013 41.46403 41.47622 46.3094 9.050911
LiK 25.65361 25.64984 25.65735 85.8566 2.51087
LiRb 39.10643 39.0089 39.20383 51.9904 14.97533
NaK 47.22661 47.21077 47.24243 31.8939 31.70265
NaRb 47.39527 47.26249 47.52769 31.1808 31.50611
KRb 32.93943 32.8668 33.01201 67.47 19.86654

hardness data evaluated through the formula of In strong support of our observation on the ba-
Ghosh [39] is consistently widely divergent from sis of Table II, we present the results in Table III.
all other sets of hardness data. It is transparent from Table III that the hardnesses

TABLE IV
Comparative study of the hardness differences evaluated through different methods under reference.
(R1 and R2 are the reactants and P1 and P2 are the products).

Dg Dg Dg DH
R1 R2 P1 P2 (ab initio) (Present work) Dg (GM) Dg (AM) Dg (HM) (Ghosh) (kcal/mol)

LiCl þ NaF ¼ LiF þ NaCl 1.11397 0.52831 0.0133 0 0.0171 0.4272 9.5
LiCl þ KF ¼ LiF þ KCl 1.30374 0.63762 0.00918 0.0225 0.01154 0.02885 10
LiBr þ KF ¼ LiF þ KBr 1.2556 0.41844 0.00904 0.16361 0.01133 0.028326 10.5
LiF þ HI ¼ LiI þ HF 4.11958 2.67739 0.65124 0 1.12577 2.81443 10.6
NaF þ HCl ¼ NaCl þ HF 3.78829 2.27452 0.57921 0 0.99921 2.498019 16.2
CsF þ HCl ¼ CsCl þ HF — 2.41767 1.01821 0 1.35538 3.388448 16.7
LiI þ CsF ¼ LiF þ CsI — 0.46782 0.46782 0 1.04364 0.953021 12.1

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GHOSH AND ISLAM
computed through our method have the closest
agreement with the ab initio results.
A look at the Table IV reveals that averaging
methods including the method of Ghosh [39] fail
to predict the reaction path presented in row 1.
But the present method and the quantum chemi-
cal method seem to predict the proper reaction
surface in row 1. But in all other cases under ref-
erence except the arithmetic mean method can
correlate the reaction surface reasonably well.
It is worth mentioning that the reaction enthal-
pies of all the reaction can be beautifully corre-
lated by the hardness difference data of evaluated
through the present venture. This proves unequivo-
cally that the averaging formulae compute hardness
values that can not correlate the driving forces of
chemical reactions. On the contrary, the present
method evaluates molecular hardness that can be
well applied to study the chemical reactions and
reaction surface.
Conclusions
Starting from the empirical radial dependent
formula of computing global hardness of atoms
suggested by us, we have derived an ansatz of
the molecular hardness assuming that hardness
equalization principle is operative and justifiably
valid in a previous work. In this work, we have
basically tried to perform a validity test of the
algorithm we have suggested for evaluating mo-
lecular hardness by application in the real field of
hard–soft acid–base reaction. We have also tried
to verify whether the various averaging formulae
can be invoked to compute molecular hardness
from the atomic hardness data. As hardness is not
an experimentally measurable property, there is
no benchmark to perform any validity test of our
computed data. Invoking an ab initio Hartree-
Fock quantum mechanical method, we have com-
puted the ab initio hardness data of the molecules
studied here using the formula of Parr and Pear-
son, (I  A)/2. To compute I and A, we have
invoked Koopmans’ theorem. It is found that the
set hardness data of a number of molecules eval-
uated through the ansatz suggested by us have
close agreement with the hardness value com-
puted through the ab initio quantum chemical
method. We have applied the internuclear dis-
tance dependent ansatz vis a vis the averaging
formulae to compute the hardness difference of
10 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
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some well known hard soft acid base exchange
reactions and found that the arithmetic formula
does not predict the reaction path at all, other
averaging methods also fail to explain all the
reactions efficiently whereas, the hardness data of
our suggested method can draw the exact picture
of the model of the chemical reaction surface.
Thus, we performed a validity test of the efficacy
of our suggested algorithm for the evaluation of
molecular hardness by application in the real
world when hardness is a hypothesis.
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