Reliable prediction of threebody intermolecular interactions using dispersioncorrected secondorder MøllerPlesset perturbation theory
Abstract
Threebody and higher intermolecular interactions can play an important role in molecular condensed phases. Recent benchmark calculations found problematic behavior for many widely used density functional approximations in treating 3body intermolecular interactions. Here, we demonstrate that the combination of secondorder MøllerPlesset (MP2) perturbation theory plus shortrange damped AxilrodTellerMuto (ATM) dispersion accurately describes 3body interactions with reasonable computational cost. The empirical damping function used in the ATM dispersion term compensates both for the absence of higherorder dispersion contributions beyond the tripledipole ATM term and nonadditive shortrange exchange terms which arise in thirdorder perturbation theory and beyond. Empirical damping enables this simple model to outperform a nonexpanded coupled KohnSham dispersion correction for 3body intermolecular dispersion. The MP2 plus ATM dispersion model approaches the accuracy of O(N{sup 6}) methods like MP2.5 or even spincomponentscaled coupled cluster models for 3body intermolecular interactions with only O(N{sup 5}) computational cost.
 Authors:

 Department of Chemistry, University of California, Riverside, California 92521 (United States)
 Publication Date:
 OSTI Identifier:
 22493447
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 143; Journal Issue: 4; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 00219606
 Country of Publication:
 United States
 Language:
 English
 Subject:
 74 ATOMIC AND MOLECULAR PHYSICS; ACCURACY; APPROXIMATIONS; BENCHMARKS; CORRECTIONS; DAMPING; DENSITY FUNCTIONAL METHOD; DIPOLES; INTERACTION RANGE; INTERMOLECULAR FORCES; PERTURBATION THEORY; SPIN; THREEBODY PROBLEM
Citation Formats
Huang, Yuanhang, and Beran, Gregory J. O.,. Reliable prediction of threebody intermolecular interactions using dispersioncorrected secondorder MøllerPlesset perturbation theory. United States: N. p., 2015.
Web. doi:10.1063/1.4927304.
Huang, Yuanhang, & Beran, Gregory J. O.,. Reliable prediction of threebody intermolecular interactions using dispersioncorrected secondorder MøllerPlesset perturbation theory. United States. doi:10.1063/1.4927304.
Huang, Yuanhang, and Beran, Gregory J. O.,. Tue .
"Reliable prediction of threebody intermolecular interactions using dispersioncorrected secondorder MøllerPlesset perturbation theory". United States. doi:10.1063/1.4927304.
@article{osti_22493447,
title = {Reliable prediction of threebody intermolecular interactions using dispersioncorrected secondorder MøllerPlesset perturbation theory},
author = {Huang, Yuanhang and Beran, Gregory J. O.,},
abstractNote = {Threebody and higher intermolecular interactions can play an important role in molecular condensed phases. Recent benchmark calculations found problematic behavior for many widely used density functional approximations in treating 3body intermolecular interactions. Here, we demonstrate that the combination of secondorder MøllerPlesset (MP2) perturbation theory plus shortrange damped AxilrodTellerMuto (ATM) dispersion accurately describes 3body interactions with reasonable computational cost. The empirical damping function used in the ATM dispersion term compensates both for the absence of higherorder dispersion contributions beyond the tripledipole ATM term and nonadditive shortrange exchange terms which arise in thirdorder perturbation theory and beyond. Empirical damping enables this simple model to outperform a nonexpanded coupled KohnSham dispersion correction for 3body intermolecular dispersion. The MP2 plus ATM dispersion model approaches the accuracy of O(N{sup 6}) methods like MP2.5 or even spincomponentscaled coupled cluster models for 3body intermolecular interactions with only O(N{sup 5}) computational cost.},
doi = {10.1063/1.4927304},
journal = {Journal of Chemical Physics},
issn = {00219606},
number = 4,
volume = 143,
place = {United States},
year = {2015},
month = {7}
}