Computational analysis shows that neighbor atom potentials dictate charge distribution in heteronuclear molecules, indicating the need for electrostatic corrections in semiempirical modeling.
Three methods of approximating the diagonal elements of the one-electron Hamiltonian matrix for semiempirical MO calculations are discussed: employing the orbital energy of the free atom, correcting it for charge migration (net charge), and also correcting it for neighbor atom potentials. An analytic method for estimating the neighbor atom potentials is suggested, and it is employed to estimate the change in the diagonal Hamiltonian elements due to neighboring atoms. The results from calculating molecular properties employing the three approximations for the Hii elements are presented. It is found that charge distribution is quite sensitive to the approximation employed, and that in order to achieve good predictions of molecular properties it is necessary to take into account the electrostatic potentials due to neighboring atoms.
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Corrington et al. (2009) studied this question.
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