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Title: On the piecewise convex or concave nature of ground state energy as a function of fractional number of electrons for approximate density functionals

Abstract

In this paper, we provide a rigorous proof that the Hartree Fock energy, as a function of the fractional electron number, E(N), is piecewise concave. Moreover, for semi-local density functionals, we show that the piecewise convexity of the E(N) curve, as stated in the literature, is not generally true for all fractions. By an analysis based on exchange-only local density approximation and careful examination of the E(N) curve, we find for some systems, there exists a very small concave region, corresponding to adding a small fraction of electrons to the integer system, while the remaining E(N) curve is convex. Several numerical examples are provided as verification. Although the E(N) curve is not convex everywhere in these systems, the previous conclusions on the consequence of the delocalization error in the commonly used density functional approximations, in particular, the underestimation of ionization potential, and the overestimation of electron affinity, and other related issues, remain unchanged. Finally, this suggests that instead of using the term convexity, a modified and more rigorous description for the delocalization error is that the E(N) curve lies below the straight line segment across the neighboring integer points for these approximate functionals.

Authors:
ORCiD logo [1];  [2]
+ Show Author Affiliations
  1. Duke Univ., Durham, NC (United States). Dept. of Chemistry
  2. Duke Univ., Durham, NC (United States). Dept. of Chemistry; South China Normal Univ., Guangzhou (China). Key Lab. of Theoretical Chemistry of Environment. School of Chemistry and Environment
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1465680
Alternate Identifier(s):
OSTI ID: 1361757
Grant/Contract Number:  
SC0012575; CHE-13-62927
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; protons; Hilbert space; electron affinities; band gap; ground states; local density approximations; electron densities of states; many electron systems

Citation Formats

Li, Chen, and Yang, Weitao. On the piecewise convex or concave nature of ground state energy as a function of fractional number of electrons for approximate density functionals. United States: N. p., 2017. Web. doi:10.1063/1.4974988.
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Li, Chen, & Yang, Weitao. On the piecewise convex or concave nature of ground state energy as a function of fractional number of electrons for approximate density functionals. United States. https://doi.org/10.1063/1.4974988
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Li, Chen, and Yang, Weitao. Tue . "On the piecewise convex or concave nature of ground state energy as a function of fractional number of electrons for approximate density functionals". United States. https://doi.org/10.1063/1.4974988. https://www.osti.gov/servlets/purl/1465680.
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@article{osti_1465680,
title = {On the piecewise convex or concave nature of ground state energy as a function of fractional number of electrons for approximate density functionals},
author = {Li, Chen and Yang, Weitao},
abstractNote = {In this paper, we provide a rigorous proof that the Hartree Fock energy, as a function of the fractional electron number, E(N), is piecewise concave. Moreover, for semi-local density functionals, we show that the piecewise convexity of the E(N) curve, as stated in the literature, is not generally true for all fractions. By an analysis based on exchange-only local density approximation and careful examination of the E(N) curve, we find for some systems, there exists a very small concave region, corresponding to adding a small fraction of electrons to the integer system, while the remaining E(N) curve is convex. Several numerical examples are provided as verification. Although the E(N) curve is not convex everywhere in these systems, the previous conclusions on the consequence of the delocalization error in the commonly used density functional approximations, in particular, the underestimation of ionization potential, and the overestimation of electron affinity, and other related issues, remain unchanged. Finally, this suggests that instead of using the term convexity, a modified and more rigorous description for the delocalization error is that the E(N) curve lies below the straight line segment across the neighboring integer points for these approximate functionals.},
doi = {10.1063/1.4974988},
journal = {Journal of Chemical Physics},
number = 7,
volume = 146,
place = {United States},
year = {2017},
month = {2}
}
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