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Electric field‐derived point charges to mimic the electrostatics in molecular crystals
Author(s) -
Whitten Andrew E.,
McKin Joshua J.,
Spackman Mark A.
Publication year - 2006
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.20419
Subject(s) - electrostatics , electric field , point particle , point (geometry) , static electricity , chemical physics , field (mathematics) , charge (physics) , computational chemistry , materials science , chemistry , physics , classical mechanics , mathematics , quantum mechanics , geometry , pure mathematics
Because of the way the electrostatic potential is defined in a crystal, it is not possible to determine potential‐derived charges for atoms in a crystal. To overcome this limitation, we present a novel method for determining atomic charges for a molecule in a crystal based on a fit to the electric field at points on a surface around the molecule. Examples of fits to the electric field at points on a Hirshfeld surface, using crystal Hartree–Fock electron densities computed with a DZP basis set are presented for several organic molecular crystals. The field‐derived charges for common functional groups are transferable, and reflect chemical functionality as well as the subtle effects of intermolecular interactions. The charges also yield an excellent approximation to the electric field surrounding a molecule in a crystal for use in cluster calculations on molecules in solids. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1063–1070, 2006