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Title: Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions

Abstract

Your correspondents develop and apply fully nonorthogonal, local-reference perturbation theories describing non-covalent interactions. Our formulations are based on a Löwdin partitioning of the similarity-transformed Hamiltonian into a zeroth-order intramonomer piece (taking local CCSD solutions as its zeroth-order eigenfunction) plus a first-order piece coupling the fragments. If considerations are limited to a single molecule, the proposed intermolecular similarity-transformed perturbation theory represents a frozen-orbital variant of the “(2)”-type theories shown to be competitive with CCSD(T) and of similar cost if all terms are retained. Different restrictions on the zeroth- and first-order amplitudes are explored in the context of large-computation tractability and elucidation of non-local effects in the space of singles and doubles. To accurately approximate CCSD intermolecular interaction energies, a quadratically growing number of variables must be included at zeroth-order.

Authors:
;  [1]
  1. Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22415855
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 20; 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:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; AMPLITUDES; APPROXIMATIONS; COUPLING; COVALENCE; EIGENFUNCTIONS; HAMILTONIANS; INTERMOLECULAR FORCES; MATHEMATICAL SOLUTIONS; MOLECULES; PARTITION; PERTURBATION THEORY; SPACE

Citation Formats

Azar, Richard Julian, E-mail: julianazar2323@berkeley.edu, and Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu. Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions. United States: N. p., 2015. Web. doi:10.1063/1.4921377.
Azar, Richard Julian, E-mail: julianazar2323@berkeley.edu, & Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu. Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions. United States. doi:10.1063/1.4921377.
Azar, Richard Julian, E-mail: julianazar2323@berkeley.edu, and Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu. Thu . "Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions". United States. doi:10.1063/1.4921377.
@article{osti_22415855,
title = {Similarity-transformed perturbation theory on top of truncated local coupled cluster solutions: Theory and applications to intermolecular interactions},
author = {Azar, Richard Julian, E-mail: julianazar2323@berkeley.edu and Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu},
abstractNote = {Your correspondents develop and apply fully nonorthogonal, local-reference perturbation theories describing non-covalent interactions. Our formulations are based on a Löwdin partitioning of the similarity-transformed Hamiltonian into a zeroth-order intramonomer piece (taking local CCSD solutions as its zeroth-order eigenfunction) plus a first-order piece coupling the fragments. If considerations are limited to a single molecule, the proposed intermolecular similarity-transformed perturbation theory represents a frozen-orbital variant of the “(2)”-type theories shown to be competitive with CCSD(T) and of similar cost if all terms are retained. Different restrictions on the zeroth- and first-order amplitudes are explored in the context of large-computation tractability and elucidation of non-local effects in the space of singles and doubles. To accurately approximate CCSD intermolecular interaction energies, a quadratically growing number of variables must be included at zeroth-order.},
doi = {10.1063/1.4921377},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 20,
volume = 142,
place = {United States},
year = {2015},
month = {5}
}