A New Class IV Charge Model for Extracting Accurate Partial Charges from Wave Functions

Li, J.; Zhu, T.; Cramer, C. J.; Truhlar, D. G.

* J. Phys. Chem. A*
**1998**, *102*, 1820.

We propose a new formalism, Charge Model 2 (CM2), to obtain accurate
partial atomic charges from a population analysis of wave functions by a
parameterized mapping procedure, so that the resulting charges reproduce
highly accurate charge-dependent observables. The new method, which
produces Class IV charges, is illustrated by developing CM2 mappings of
Loewdin charges obtained from semiempirical and *ab initio*
Hartree-Fock theory and density functional theory, in particular AM1, PM3,
HF/MIDI!, HF/6-31G*, HF/6-31+G*, BPW91/MIDI!, BPW91/6-31G*, B3LYP/MIDI!,
and BPW91/DZVP calculations. The CM2 partial charges reproduce experimental
dipole moments with root-mean-square errors that are typically a factor of
7 better than dipole moments computed from Mulliken population analysis, a
factor of 3 better than dipole moments computed by Loewdin analysis, and
even a factor of 2 better than dipole moments computed from the continuous
electron density. At the HF/6-31G* and B3LYP/MIDI! levels, the new charge
model yields root-mean-square errors of 0.19 D and 0.18 D, respectively,
for the dipole moments of 211 polar molecules containing a diverse range of
structures and organic functional groups and the elements H, C, N, O, F,
Si, P, S, Cl, Br, and I. A comparison shows that the new charge model
predicts dipole moments more accurately than MP2/cc-pVDZ calculations,
which are considerably more expensive. The quality of the results is
similarly good for electrostatic potentials and for the other
parameterizations as well.

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