Absolute Electronegativity and Absolute Hardness Lewis Acids and Bases

J. Am. Chem. SOC.
1985, 107, 6801-6806 6801

Absolute Electronegativity and Absolute Hardness of Lewis
Acids and Bases
Ralph G. Pearson
Contribution f rom the Chemistry Department, University of California,
Santa Barbara, California 931 06. Received April 15, 1985
Abstract: The relationship of xo, the absolute electronegativity, and 7, the absolute hardness, to chemical bonding in Lewis
acid-base complexes is examined. This is done by using semiempirical MO theory in which the same experimental parameters
appear. The a priori electronegativity of a Lewis acid or base is shown to be ( I +A) / 2. For any two atoms, ions, or molecules,
the direction of net electron flow is determined by the difference in x o values. For a specific pair of reactants, the effective
value of x o can range from AA for a pure electron acceptor to I , for a pure electron donor. The most common situation will
have electron transfer in both directions (u plus B bonding). Then x o will be a weighted mean of I and A for both acid and
base. The absolute hardness, q =(I - A) / 2, determines the magnitude of the total electron transfer, both u and H. Small
values of v A and 7, lead to the greatest amount of covalent bonding. For neutral molecules and cations, values of I and A
for the species are used. For anions i t is both necessary and theoretically logical to use values of I and A for the corresponding
neutral atoms or radicals.
Recent work based on density functional theory has developed
the concepts of absolute electronegativity, x,] and absolute
hardness, 7. * The definitions are
Where E is the electronic energy of a molecule, atom, or ion, N
is the number of electrons, and Z is a fixed set of nuclear charges.
The absolute electronegativity is also equal to the electronic
chemical potential, k , with change in sign. The operational (and
approximate) definitions are
x =y2(Z +A) ; 7 =)'>(I - A) ( 2)
where Z is the ionization potential, and A is the electron affinity.
The absolute electronegativity is the same as the Mulliken value.
We assume that for small changes in N, we can write
w =wo +27AN
(3)
If we have two chemical species, A and B, which are allowed to
react, there will be a shift of electrons from the less electronegative
molecule, B, to the more electronegative molecule, A. The con-
dition of equilibrium is that the chemical potentials, pA and pB,
become equaL3 This leads to a shift in charge, AN, from B to
A.
( XOA - X OB )
A N =
2(?A -k 7B)
Electron transfer leads to an energy lowering, given by2
(4)
(5)
Note in (4) and (5) that electronegativity difference drive the
electron transfer, and the sum of hardness parameters inhibit it.
The hardness is the resistance of the chemical potential to change
in the number of electrons. That is, 27 =(aw/aN),.
The chemical potential and the absolute electronegativity are
molecular properties and not orbital properties. However, in
considering the transfer of electrons from B to A, it becomes
(1) Parr, R. G.; Donnelly, R. A, ; Levy, M.; Palke, W. E. J. Chem. Phys.
1978, 68, 3801. See also: Iczkowski, R. P.; Margrave, J . L. J. Am. Chem.
SOC. 1961, 83, 3547.
(2) Parr, R. G.; Pearson, R. G. J. Am. Chem. SOC. 1983, 105, 7512. See
also: Huheey, J . E. J . Phys. Chem. 1965, 85, 148.
(3) This condition was first given by Sanderson as the postulate of elec-
tronegativity equalization. Sanderson, R. T. Science (Washington, D. C. ) 1951,
114, 670. It is provable in density functional theory (ref 1).
necessary to consider the electrons as coming from definite oc-
cupied orbitals in B and going into definite empty orbitals in A.
This defines the relative orientations of A and B, to give the
greatest possible overlap between these frontier orbital^.^ Also
7 and x are state functions, and while ground states are most often
considered, sometimes it is useful to consider valence states or
excited states, particularly for the reactions of atoms.
Equations 4 and 5 are obviously incomplete. The chemical
potential is also a function of changing external fields, so that if
A (or B) is charged, this will affect wLB (or wA) as a function of
the distance between A and B.5 Also there is no indication of
the delocalization of electron density corresponding to covalent
bonding.
In spite of these shortcomings, eq 4 and 5 are very appealing.
They have the great virtue (and weakness) of trying to predict
chemical behavior with a minimum number of parameters. Values
of I are becoming available for more and more molecules.6 Values
of A are still few in number. In fact for most molecules, the
electron affinity cannot be detected. In such cases A is set equal
to zero, meaning that E is a minimum when the electron is at
infinity. Clearly this is inconsistent with the idea of electrons
transferring to definite orbitals. I t suggests instead negative values
of A, related to, but not equal to, the energy of appropriate empty
orbitals.'
The use of eq 4 and 5 actually predates the development of
density functional theory.* Attempts have also been made to
include the effects of Coulombic interactions (ionic bonding) and
of covalent bonding.' However, this earlier work considered only
atoms and radicals with one valence electron to contribute to a
bond. Also the interest was in estimating the percent of ionic
character in the bond, and the results are not convenient for bond
energies.
I n this paper we will consider the interaction of a Lewis acid
and a base:
( 6 )
A +:B - A:B
(4) Parr, R. G.; Yang, W. J . Am. Chem. SOC. 1984, 106, 4049.
( 5) Nalewajski, R. F. J . Am. Chem. SOC. 1984, 106, 944.
(6) Rosenstock, H. M. et al. J . Phys. Chem. ReJ Dura 1977, 6, suppl. no.
( 7) Lowe (Lowe, J . P. J . Am. Chem. SOC. 1977, 99, 5557) gives a useful
(8) Hinze, J .; Whitehead, M. A, ; J affe; H. H. J . Am. Chem. SOC. 1963,
(9) Iczkowski. R. P. J . Am. Chem. SOC. 1964. 86. 2329. Evans. R. S.:
1.
discussion of the electron affinities of small molecules.
85, 148.
Huheey, J . E. J.'Inorg. Nucl. Chem. 1970, 32. 373,' Reed, J . L. J. Phys.
Chem. 1981, 85, 148.
0002-7863/85/1507-6801$01.50/0 0 1985 American Chemical Society

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J. Am. Chem. SOC.

1985, 107, 6801-6806 6801

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