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Title: Non-additive non-interacting kinetic energy of rare gas dimers

Abstract

We show approximations of the non-additive non-interacting kinetic energy (NAKE) as an explicit functional of the density are the basis of several electronic structure methods that provide improved computational efficiency over standard Kohn-Sham calculations. However, within most fragment-based formalisms, there is no unique exact NAKE, making it difficult to develop general, robust approximations for it. When adjustments are made to the embedding formalisms to guarantee uniqueness, approximate functionals may be more meaningfully compared to the exact unique NAKE. We use numerically accurate inversions to study the exact NAKE of several rare-gas dimers within partition density functional theory, a method that provides the uniqueness for the exact NAKE. We find that the NAKE decreases nearly exponentially with atomic separation for the rare-gas dimers. We compute the logarithmic derivative of the NAKE with respect to the bond length for our numerically accurate inversions as well as for several approximate NAKE functionals. We show that standard approximate NAKE functionals do not reproduce the correct behavior for this logarithmic derivative and propose two new NAKE functionals that do. The first of these is based on a re-parametrization of a conjoint Perdew-Burke-Ernzerhof (PBE) functional. The second is a simple, physically motivated non-decomposable NAKE functional thatmore » matches the asymptotic decay constant without fitting.« less

Authors:
ORCiD logo [1];  [1];  [2]
  1. Purdue Univ., West Lafayette, IN (United States). Dept. of Physics and Astronomy
  2. Purdue Univ., West Lafayette, IN (United States). Dept. of Physics and Astronomy, and Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1540150
Alternate Identifier(s):
OSTI ID: 1426015
Grant/Contract Number:  
SC0005291; FG02-10ER16191
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 10; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Jiang, Kaili, Nafziger, Jonathan, and Wasserman, Adam. Non-additive non-interacting kinetic energy of rare gas dimers. United States: N. p., 2018. Web. doi:10.1063/1.5016308.
Jiang, Kaili, Nafziger, Jonathan, & Wasserman, Adam. Non-additive non-interacting kinetic energy of rare gas dimers. United States. doi:10.1063/1.5016308.
Jiang, Kaili, Nafziger, Jonathan, and Wasserman, Adam. Wed . "Non-additive non-interacting kinetic energy of rare gas dimers". United States. doi:10.1063/1.5016308. https://www.osti.gov/servlets/purl/1540150.
@article{osti_1540150,
title = {Non-additive non-interacting kinetic energy of rare gas dimers},
author = {Jiang, Kaili and Nafziger, Jonathan and Wasserman, Adam},
abstractNote = {We show approximations of the non-additive non-interacting kinetic energy (NAKE) as an explicit functional of the density are the basis of several electronic structure methods that provide improved computational efficiency over standard Kohn-Sham calculations. However, within most fragment-based formalisms, there is no unique exact NAKE, making it difficult to develop general, robust approximations for it. When adjustments are made to the embedding formalisms to guarantee uniqueness, approximate functionals may be more meaningfully compared to the exact unique NAKE. We use numerically accurate inversions to study the exact NAKE of several rare-gas dimers within partition density functional theory, a method that provides the uniqueness for the exact NAKE. We find that the NAKE decreases nearly exponentially with atomic separation for the rare-gas dimers. We compute the logarithmic derivative of the NAKE with respect to the bond length for our numerically accurate inversions as well as for several approximate NAKE functionals. We show that standard approximate NAKE functionals do not reproduce the correct behavior for this logarithmic derivative and propose two new NAKE functionals that do. The first of these is based on a re-parametrization of a conjoint Perdew-Burke-Ernzerhof (PBE) functional. The second is a simple, physically motivated non-decomposable NAKE functional that matches the asymptotic decay constant without fitting.},
doi = {10.1063/1.5016308},
journal = {Journal of Chemical Physics},
number = 10,
volume = 148,
place = {United States},
year = {2018},
month = {3}
}

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