CHEMICAL PHYSICS LETTERS 1 (19681 529-531.

NOHTH- HOLLAND PUBLISHING COPANY, A&rSTERDAM

ON THE PROBLEM OF DEFINING THE CHARGE
ON AN ATOM IN A MOLECULE
L. Ch. CUSACHS
Riefuzrdson Chemistq- Laboratories, TuZcnte Uzziuersify,
New Orleans, Louisiana, USA
and
P. POLITZEIZ
Depurt?nent of Chemistry, Louisinna State University in Neru Orleans.
New Orleans, Louisiana. USA
Received 20 December 1967
It is shown that the Mulliken and the Liiwdin definitions of atomic charge lead to significantly different
are used as criteria of self-consistency in com- wave functions and physical interpretations. when they
_ _
_ I puting the wave functions.
The problem of defining a measure of the
charge associated with an atom in a molecule
is a particularly difficult one, being related as
it is to the very fundamental but very complex
question of how to describe an atom in a mole-
cule, if indeed it is still valid to speak of an
atom in such circumstances. An important
contribution along these lines was made by Mul-
liken Cl], when he suggested that, within the
framework of LCAO-molecular orbital theory,
the electronic charge (or population) on an
atom be defined as
&* = F Nk [x (dm + 23 Cknr%%n,)l ,
??l
s,n
where the kth molecular orbital is
kk= c c
Ynz km%z~
,
the subscripts wz and n refer to atomic orbitals
on atoms rand s, respectively, SBZn is the over-
lap integral between orbitals nz and n, and Nk
is the number of electrons in the kth molecular
orbital.
This definition is unrealistic in two respects:
First, it apportions the overlap charge equally
between the two atoms, which should in general
be true only if the atoms are identical, and sec-
ond, it allows the possibility of an atom having a
J anuary 1968
529
negative electronic population, for a given mole-
cular orbital, when the cross-terms are negative
and are sufficiently large. Despite these wezk-
nesses, the Mulliken definition has been very
useful, and has been widely adopted.
Another definition of the electronic charge on
an atom was proposed by Lliwdin [2], but has had
only limited usage. If the molecular wave func-
tion is written in terms of a basis set of orthogo-
nalized atomic orbitals,
then the electronic charge on atom T is defined
to be
(All overlap integrals S,,,, are zero.) This method
of defining the charge does not permit negative
populations, since only squared terms are in-
volved, but it has the disadvantage that by mixing,
at least to the extent needed to achieve wthogw
nality, orbitals from other atoms into those of
the atom being considered, one deIocaEizes to
that extent the charge which is being assigned to
that atom.
In computing semi-empirical molecular wave
functions, a technique that is coming to be widely
used is to make the Hamiltonian matrix elements
530
L. Ch. CUSACHS and P. POLITZER
Table 1
RlUl Description Input charges
Output charges
Liiwdin MuiIiken
Sum of eigenvaiues
(eV)
1 Not includinc
hydrogen 2pBrbitais
2 Not including
hydrogen 2p orbitals
3 Not including
hydrogen 2p orbitals
4 Including
hydrogen 2p orbital5
5 Including
hydrogen 2p orbit&
G Including
hydrogen 2p orbitals
B 0.000
Hbridging O-000
HterminaI O-000
B 0.146
Hbridging 0.021
Htermin& -0.0835
B 0.121
Hbridging O-045
HtsrminaI -0.083
B 0.000
Hbridging O.OGO
HterminaI O-000
B 0.018
Hbridging e-062
Hterminal -0.040
B 0.178
Hbridging G-005
Htermind -0.0915
0,551 0.8964
-0.034 -0.1716 -172.768
-0.258 -0.3624
0.033 0.1433
0.102 0.0276 -176.548
-0.068 -0.0855
0.125 0.2780
0.051 -0.0477 -175.679
-0.088 -0.1151
0.755 0.0538
-0.122 0.3744 -187.029
-0.316 -0.2141
0.718 0.0110
-0.223 0.0672 -186.809
-0.248 -0.0391
0.178 -0.9262
0.007 0.5107 -197 -039
-0.092 0.2078
dependent upon the charges of the atoms, and then
to iterate over these charges until consistency is
achieved between the values assumed and the
charges calculated from the resulting molecular
wave function [3,4]. The Muiliken definition of
charge has generally been used for this purpose
in the past. In a recent calculation on diborane,
however, it was decided to achieve self-consis-
tency in terms of both the Mu&ken and the Low-
din definitions, for purposes of comparison.
The results are shown in table 1. Runs 1, 2,
and 3 were carried out with a basis set of 2s and
2p overlap-matched atomic orbitais [S] on the
boron atoms, with orbital exponents of 0.820 and
0.720 respectively, and with 1s orbitals, 5 = 1.20,
on the hydrogens. The last three runs used the
same basis set, plus 2p orbitals on the h;rdrogens,
with c =0.60. In runs 1 and 4, the input charges
were zero, in order to see the effect of starting
with neutral atoms. In the second and third runs,
and again in the fifth and sixth, self-consistency
was attained in terms of the Mulliken and the
LCiwdin definitions, respectively. It was neces-
sary to do them separately; no single wave func-
tion could achieve balance with respect to both
of these criteria *.
The data in table 1 bring out several interest-
ing points. First, the inclusion of 2p orbitals on
the hydrogens definitely has a very significant
effect. This is seen, for instance, in comparing
runs 1 and 4, which had identical input charges;
the final charges, whether computed by the Low-
din or by the Mulliken schemes, change ccnsider-
ably when hydrogen Zp orbitais are included. The
sum of the eigenvalues also changes significantly.
Second, the wave function which one accepts
as the final result will be quite different if one
expression for the charge is used from what it
wouid be in terms of the other. Wave functions 5
and 6, for example, selfconsistent in terms of
the Muiliken and Ltiwdin charges, respectively,
are seen to differ markedly; the Muiliken charge
on the boron, for instance, is 0.011 in one case,
-0.926 in the other, which is certainly a drastic
change. Similar variations occur on the other
* As a matter of practical interest may be mentioned
the fact that the process of achieving charge self-con-
sistency was easier, in the present work, when the
Lawdin tiefinition was used. The output charges fiuc-
tuated less, and the values for the various atoms
were less intesdependent, so that they could to a
greater extent be balanced~separately.
DEFINING THE CHARGE CN AN ATCM IN A MCLECULE 531
atoms. Furthermore, the sums of the eigenvalues
differ by 10 eV. So one arrives at considerably
different final functions using these two criteria
of self -consistency.
Finally, there is the important question of the
physical significance of these numbers which are
being called the charges on the atoms [Z]. As-
suming, for the moment, that they may be inter-
preted literally, and considering the functions
without 2p orbitals on the hydrogens (runs 2 and
3; the former is self-consistent in terms of Mul-
liken charges, the latter in terms of L6wdin
charges), it is seen that si the first case, the
addition of hydrogen 2p orbitals leads to an ap-
parent removal of electronic charge from the
hydrogens (of both types) and addition of it to the
borons; in the second case, the effect of the hy-
drogen 2p orbitals is just the opposite - electron-
ic charge moves from the borons to the bridging
hydrogens, with the terminal hydrogens almost
unchanged.
purpose is, first, to point out that one does ob-
tain different final functions using these two
criteria of self-consistency, so that some basis
for preference will haveto be reached: and sec-
ond, to emphasize the uncertainty associated with
the physical interpretation of these quantities. It
may be that one of them does have a valid physical
interpretation - or it may be that neither does. It
is felt that these areisignificant questions, which
merit further study .
References
[l] R.S. liluliiken, J . Chem. Phys. 23 (1955) i833.
[2] P.-O.Lijwdin, J . Chem. Phys. 18 (1950) 365.
[3] D. G. Carroll, A.T. Armstrong and S. P. J fcGIynn,
J . Chsm. Phys. 44 (1966) 1865.
[4] R-Rein, N. Fukuda. H-Win, G.A.CIarke and F.E.
Harris, J . Chem. Phys. 45 (1966) 4743.
[5] L. C. Cusachs, D. G. Carroll, B. L. Trus and S. P.
McGlynn, Intern. J . Quantilm Chem. 1 (Slater Sym-
posium Issue, 1967) p. 159.
Obviously, these conclusions cannot both be
correct. And this in turn means that at least one
of these two definitions of charge has no direct
physical meaning; it cannot be interpreted as a
measure of the charge on an atom in a molecule.
It is not intended in this note to advocate one
definition or the other as being more meaninnful.
[6] M. Pollak and R. Rein, J . Chem. Phys. 47 (1967) 2045.
Further investigations will be-required before
* Several definitions of atomic charge have recently
any such conclusion can be reached. The present been discussed and compared by Pollak and Rein [S].