期刊
JOURNAL OF CHEMICAL PHYSICS
卷 148, 期 10, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.5016308
关键词
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资金
- Office of Basic Energy Sciences, US Department of Basic Energy Sciences [DE-FG02-10ER16191]
- US National Science Foundation CAREER program [CHE-1149968]
- Camille Dreyfus Teacher-Scholar Awards Program
- Office of Basic Energy Sciences, US Department of Energy (DOE) [DE-FG02-10ER16191]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1149968] Funding Source: National Science Foundation
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. Published by AIP Publishing.
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