Electrostatic energy in the effective fragment potential method: Theory and application to benzene dimer

TitleElectrostatic energy in the effective fragment potential method: Theory and application to benzene dimer
Publication TypeJournal Article
Year of Publication2007
AuthorsSlipchenko LV, Gordon MS
Journal TitleJournal of Computational Chemistry
Volume28
Pages276-291
Date PublishedJan
Type of ArticleArticle
ISBN Number0192-8651
Accession NumberISI:000243171300024
KeywordsAPPROXIMATION, BASIS-SETS, benzene-benzene, BINDING-ENERGIES, CHARGE PENETRATION, chemistry, dispersion, DISTRIBUTED MULTIPOLE ANALYSIS, EFP, electrostatic screening, molecular-orbital methods, SCHEME, surface, wave-functions
Abstract

Evaluation of the electrostatic energy within the effective fragment potential (EFP) method is presented. The performance of two variants of the distributed multipole analysis (DMA) together with two different models for estimating the charge penetration energies was studied using six homonuclear dimers. The importance of damping the higher order multipole terms, i.e. charge dipole, was also investigated. Damping corrections recover more than 70% of the charge penetration energy in all dimers, whereas higher order damping introduces only minor improvement. Electrostatic energies calculated by the numerical DMA are less accurate than those calculated by the analytic DMA. Analysis of bonding in the benzene dimer shows that EFP with inclusion of the electrostatic damping term performs very well compared to the high-level coupled cluster singles, doubles, and perturbative triples method. The largest error of 0.4 kcal/mol occurs for the sandwich dimer configuration. This error is about half the size of the corresponding error in second order perturbation theory. Thus, EFP in the current implementation is an accurate and computationally inexpensive method for calculating interaction energies in weakly bonded molecular complexes. (C) 2006 Wiley Periodicals, Inc.

DOI10.1002/jcc.20520
Alternate JournalJ. Comput. Chem.