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Partial atomic multipoles for internally consistent microelectrostatic calculations
Author(s) -
Snamina Mateusz,
Mazur Grzegorz,
Petelenz Piotr
Publication year - 2017
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24903
Subject(s) - polarizability , partial charge , quadrupole , charge (physics) , symmetry (geometry) , atomic physics , electric field , chemistry , molecule , molecular physics , physics , statistical physics , quantum mechanics , mathematics , geometry
An extension of the extant microelectrostatic methodologies, based on the concept of distributed generalized polarizability matrix derived from the Coupled Perturbed Hartree–Fock (CPHF) equations, is proposed for self‐consistent calculation of charge carrier and charge‐transfer (CT) state electrostatic energies in molecular solids, including the doped, defected and disordered ones. The CPHF equations are solved only once and the generalized molecular polarizability they yield enables low cost iterations that mutually adjust the molecular electronic distributions and the local electric field in which the molecules are immersed. The approach offers a precise picture of molecular charge densities, accounting for atomic partial multipoles up to order 2, which allows one to reproduce the recently reported large charge‐quadrupole contributions to CT state energies in low‐symmetry local environments. It is particularly well suited for repetitive calculations for large clusters (up to 300,000 atoms), and may potentially be useful for describing electrostatic solvent effects. © 2017 Wiley Periodicals, Inc.