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Title: Orbital-optimized density cumulant functional theory

Abstract

In density cumulant functional theory (DCFT) the electronic energy is evaluated from the one-particle density matrix and two-particle density cumulant, circumventing the computation of the wavefunction. To achieve this, the one-particle density matrix is decomposed exactly into the mean-field (idempotent) and correlation components. While the latter can be entirely derived from the density cumulant, the former must be obtained by choosing a specific set of orbitals. In the original DCFT formulation [W. Kutzelnigg, J. Chem. Phys. 125, 171101 (2006)] the orbitals were determined by diagonalizing the effective Fock operator, which introduces partial orbital relaxation. Here we present a new orbital-optimized formulation of DCFT where the energy is variationally minimized with respect to orbital rotations. This introduces important energy contributions and significantly improves the description of the dynamic correlation. In addition, it greatly simplifies the computation of analytic gradients, for which expressions are also presented. We offer a perturbative analysis of the new orbital stationarity conditions and benchmark their performance for a variety of chemical systems.

Authors:
;  [1]
  1. Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602 (United States)
Publication Date:
OSTI Identifier:
22251325
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 20; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 97 MATHEMATICAL METHODS AND COMPUTING; DENSITY; DENSITY MATRIX; PARTICLES; RELAXATION; WAVE FUNCTIONS

Citation Formats

Sokolov, Alexander Yu., E-mail: asokolov@uga.edu, and Schaefer, Henry F. Orbital-optimized density cumulant functional theory. United States: N. p., 2013. Web. doi:10.1063/1.4833138.
Sokolov, Alexander Yu., E-mail: asokolov@uga.edu, & Schaefer, Henry F. Orbital-optimized density cumulant functional theory. United States. doi:10.1063/1.4833138.
Sokolov, Alexander Yu., E-mail: asokolov@uga.edu, and Schaefer, Henry F. Thu . "Orbital-optimized density cumulant functional theory". United States. doi:10.1063/1.4833138.
@article{osti_22251325,
title = {Orbital-optimized density cumulant functional theory},
author = {Sokolov, Alexander Yu., E-mail: asokolov@uga.edu and Schaefer, Henry F.},
abstractNote = {In density cumulant functional theory (DCFT) the electronic energy is evaluated from the one-particle density matrix and two-particle density cumulant, circumventing the computation of the wavefunction. To achieve this, the one-particle density matrix is decomposed exactly into the mean-field (idempotent) and correlation components. While the latter can be entirely derived from the density cumulant, the former must be obtained by choosing a specific set of orbitals. In the original DCFT formulation [W. Kutzelnigg, J. Chem. Phys. 125, 171101 (2006)] the orbitals were determined by diagonalizing the effective Fock operator, which introduces partial orbital relaxation. Here we present a new orbital-optimized formulation of DCFT where the energy is variationally minimized with respect to orbital rotations. This introduces important energy contributions and significantly improves the description of the dynamic correlation. In addition, it greatly simplifies the computation of analytic gradients, for which expressions are also presented. We offer a perturbative analysis of the new orbital stationarity conditions and benchmark their performance for a variety of chemical systems.},
doi = {10.1063/1.4833138},
journal = {Journal of Chemical Physics},
number = 20,
volume = 139,
place = {United States},
year = {Thu Nov 28 00:00:00 EST 2013},
month = {Thu Nov 28 00:00:00 EST 2013}
}
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