Selection of Molecular Matrix Elements from Atomic Data

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Abstract
A simple internally consistent recipe for obtaining atomic orbital matrix elements (Hii) from atomic spectral data agrees with values obtained from empirical molecular ionization potentials via molecular orbital calculation. Regularities observed lead to very simple expressions useful for adjustment of parameters for charge transfer. Various assumed relations between atomic valence-state quantities and orbital matrix elements are compared with the observed data for selected atoms. In the cases studied, valence-state ionization potentials depend quadratically on the degree of ionization, but can be satisfactorily approximated by linear functions for net charges between −1 and +1. In the linear approximation, the second term is the same for both occupancies of both s and p orbitals.