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Title: An energy decomposition analysis for second-order Møller–Plesset perturbation theory based on absolutely localized molecular orbitals

Abstract

An energy decomposition analysis (EDA) of intermolecular interactions is proposed for second-order Møller–Plesset perturbation theory (MP2) based on absolutely localized molecular orbitals (ALMOs), as an extension to a previous ALMO-based EDA for self-consistent field methods. It decomposes the canonical MP2 binding energy by dividing the double excitations that contribute to the MP2 wave function into classes based on how the excitations involve different molecules. The MP2 contribution to the binding energy is decomposed into four components: frozen interaction, polarization, charge transfer, and dispersion. Charge transfer is defined by excitations that change the number of electrons on a molecule, dispersion by intermolecular excitations that do not transfer charge, and polarization and frozen interactions by intra-molecular excitations. The final two are separated by evaluations of the frozen, isolated wave functions in the presence of the other molecules, with adjustments for orbital response. Unlike previous EDAs for electron correlation methods, this one includes components for the electrostatics, which is vital as adjustment to the electrostatic behavior of the system is in some cases the dominant effect of the treatment of electron correlation. The proposed EDA is then applied to a variety of different systems to demonstrate that all proposed components behave correctly. Thismore » includes systems with one molecule and an external electric perturbation to test the separation between polarization and frozen interactions and various bimolecular systems in the equilibrium range and beyond to test the rest of the EDA. We find that it performs well on these tests. We then apply the EDA to a halogen bonded system to investigate the nature of the halogen bond.« less

Authors:
;  [1]
  1. Department of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry, University of California, Berkeley, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22493571
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 8; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BINDING ENERGY; DECOMPOSITION; ELECTRON CORRELATION; ELECTRONS; ELECTROSTATICS; EQUILIBRIUM; EVALUATION; EXCITATION; HALOGENS; MOLECULES; PERTURBATION THEORY; POLARIZATION; SELF-CONSISTENT FIELD; WAVE FUNCTIONS

Citation Formats

Thirman, Jonathan, and Head-Gordon, Martin. An energy decomposition analysis for second-order Møller–Plesset perturbation theory based on absolutely localized molecular orbitals. United States: N. p., 2015. Web. doi:10.1063/1.4929479.
Thirman, Jonathan, & Head-Gordon, Martin. An energy decomposition analysis for second-order Møller–Plesset perturbation theory based on absolutely localized molecular orbitals. United States. https://doi.org/10.1063/1.4929479
Thirman, Jonathan, and Head-Gordon, Martin. 2015. "An energy decomposition analysis for second-order Møller–Plesset perturbation theory based on absolutely localized molecular orbitals". United States. https://doi.org/10.1063/1.4929479.
@article{osti_22493571,
title = {An energy decomposition analysis for second-order Møller–Plesset perturbation theory based on absolutely localized molecular orbitals},
author = {Thirman, Jonathan and Head-Gordon, Martin},
abstractNote = {An energy decomposition analysis (EDA) of intermolecular interactions is proposed for second-order Møller–Plesset perturbation theory (MP2) based on absolutely localized molecular orbitals (ALMOs), as an extension to a previous ALMO-based EDA for self-consistent field methods. It decomposes the canonical MP2 binding energy by dividing the double excitations that contribute to the MP2 wave function into classes based on how the excitations involve different molecules. The MP2 contribution to the binding energy is decomposed into four components: frozen interaction, polarization, charge transfer, and dispersion. Charge transfer is defined by excitations that change the number of electrons on a molecule, dispersion by intermolecular excitations that do not transfer charge, and polarization and frozen interactions by intra-molecular excitations. The final two are separated by evaluations of the frozen, isolated wave functions in the presence of the other molecules, with adjustments for orbital response. Unlike previous EDAs for electron correlation methods, this one includes components for the electrostatics, which is vital as adjustment to the electrostatic behavior of the system is in some cases the dominant effect of the treatment of electron correlation. The proposed EDA is then applied to a variety of different systems to demonstrate that all proposed components behave correctly. This includes systems with one molecule and an external electric perturbation to test the separation between polarization and frozen interactions and various bimolecular systems in the equilibrium range and beyond to test the rest of the EDA. We find that it performs well on these tests. We then apply the EDA to a halogen bonded system to investigate the nature of the halogen bond.},
doi = {10.1063/1.4929479},
url = {https://www.osti.gov/biblio/22493571}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 8,
volume = 143,
place = {United States},
year = {Fri Aug 28 00:00:00 EDT 2015},
month = {Fri Aug 28 00:00:00 EDT 2015}
}