Theoretical and Computational Chemistry

Mulliken-Dipole Population Analysis

José Ortega Universidad Autónoma de Madrid

Abstract

Atomic charge is one of the most important concepts in Chemistry. Mulliken population analysis is historically the most important method to calculate atomic charges and is still widely used. One basic hypothesis of this method is the half-and-half partition of the overlap populations, Q(μ, v), into equal charges in orbitals μ and v. This partition preserves the monopole moment of the overlap density but, other than that, is arbitrary. In this work we derive a new population analysis (which we designate Mulliken-Dipole population analysis) based on the conservation of both the monopole moment and the dipole moment along the bond direction. Test calculations show that the Mulliken-Dipole atomic charges are in accord to the chemical intuition; also they are very different from the Mulliken ones, being quite similar to the Hirshfeld atomic charges. Mulliken-Dipole atomic charges are conceptually appealing and very easy to calculate. In a further step, we also show how this Mulliken-Dipole population analysis can be used to derive atomic charges for atomistic simulations that reproduce the total dipole moment of the molecule, yielding at the same time a good description of the local charges and dipole moments for the molecular fragments.

Content

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Supplementary material

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Supporting-Information