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Title: FDE-vdW: A van der Waals inclusive subsystem density-functional theory

Abstract

We present a formally exact van der Waals inclusive electronic structure theory, called FDE-vdW, based on the Frozen Density Embedding formulation of subsystem Density-Functional Theory. In subsystem DFT, the energy functional is composed of subsystem additive and non-additive terms. We show that an appropriate definition of the long-range correlation energy is given by the value of the non-additive correlation functional. This functional is evaluated using the fluctuation–dissipation theorem aided by a formally exact decomposition of the response functions into subsystem contributions. FDE-vdW is derived in detail and several approximate schemes are proposed, which lead to practical implementations of the method. We show that FDE-vdW is Casimir-Polder consistent, i.e., it reduces to the generalized Casimir-Polder formula for asymptotic inter-subsystems separations. Pilot calculations of binding energies of 13 weakly bound complexes singled out from the S22 set show a dramatic improvement upon semilocal subsystem DFT, provided that an appropriate exchange functional is employed. The convergence of FDE-vdW with basis set size is discussed, as well as its dependence on the choice of associated density functional approximant.

Authors:
;  [1];  [2]
  1. Department of Chemistry, Rutgers University, Newark, New Jersey 07102 (United States)
  2. Department of Chemistry and Biochemistry, Montclair State University, Montclair, New Jersey 07043 (United States)
Publication Date:
OSTI Identifier:
22419928
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 4; Other Information: (c) 2014 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; ADDITIVES; BINDING ENERGY; DECOMPOSITION; DENSITY; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; VAN DER WAALS FORCES

Citation Formats

Kevorkyants, Ruslan, Pavanello, Michele, E-mail: m.pavanello@rutgers.edu, and Eshuis, Henk. FDE-vdW: A van der Waals inclusive subsystem density-functional theory. United States: N. p., 2014. Web. doi:10.1063/1.4890839.
Kevorkyants, Ruslan, Pavanello, Michele, E-mail: m.pavanello@rutgers.edu, & Eshuis, Henk. FDE-vdW: A van der Waals inclusive subsystem density-functional theory. United States. doi:10.1063/1.4890839.
Kevorkyants, Ruslan, Pavanello, Michele, E-mail: m.pavanello@rutgers.edu, and Eshuis, Henk. Mon . "FDE-vdW: A van der Waals inclusive subsystem density-functional theory". United States. doi:10.1063/1.4890839.
@article{osti_22419928,
title = {FDE-vdW: A van der Waals inclusive subsystem density-functional theory},
author = {Kevorkyants, Ruslan and Pavanello, Michele, E-mail: m.pavanello@rutgers.edu and Eshuis, Henk},
abstractNote = {We present a formally exact van der Waals inclusive electronic structure theory, called FDE-vdW, based on the Frozen Density Embedding formulation of subsystem Density-Functional Theory. In subsystem DFT, the energy functional is composed of subsystem additive and non-additive terms. We show that an appropriate definition of the long-range correlation energy is given by the value of the non-additive correlation functional. This functional is evaluated using the fluctuation–dissipation theorem aided by a formally exact decomposition of the response functions into subsystem contributions. FDE-vdW is derived in detail and several approximate schemes are proposed, which lead to practical implementations of the method. We show that FDE-vdW is Casimir-Polder consistent, i.e., it reduces to the generalized Casimir-Polder formula for asymptotic inter-subsystems separations. Pilot calculations of binding energies of 13 weakly bound complexes singled out from the S22 set show a dramatic improvement upon semilocal subsystem DFT, provided that an appropriate exchange functional is employed. The convergence of FDE-vdW with basis set size is discussed, as well as its dependence on the choice of associated density functional approximant.},
doi = {10.1063/1.4890839},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 4,
volume = 141,
place = {United States},
year = {2014},
month = {7}
}