Atomic multipoles and perpendicular electrostatic forces in diatomic and planar molecules

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Abstract

Current methods for assigning atomic multipoles focus on reproduction of the molecular electrostatic potential. Another aspect of electrostatic interaction, which is usually overlooked, is the forces that an external electric field exerts on the nuclei of a molecule. In a self‐consistent theory, both the electrostatic potential and force should be accounted for. However, in general it is not easy to meet this requirement for the force. For planar molecules, though, a formal solution is available in terms of atomic multipoles that are extracted from the molecular multipolar tensors. These Force‐Related (FR) atomic multipoles are discussed in detail for some typical diatomics and planar polyatomics, and are shown to provide a solid uniform framework for treating both aspects of the electrostatics. In contrast, the commonly used potential‐derived charges (i.e., the atomic charges obtained by fitting the electrostatic potential) can yield large deviations with respect to electrostatic forces on the nuclei, even when the electrostatic potential is very well reproduced.

Original languageEnglish
Pages (from-to)469-486
Number of pages18
JournalJournal of Computational Chemistry
Volume12
Issue number4
DOIs
StatePublished - 1 Jan 1991

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