Calculation and interpretation of classical turning surfaces in solids

Kaplan, Aaron D.; Clark, Stewart J.; Burke, Kieron; Perdew, John P.

doi:10.1038/s41524-020-00479-0

Calculation and interpretation of classical turning surfaces in solids

Journal Article · Mon Feb 01 00:00:00 EST 2021 · npj Computational Materials

DOI:https://doi.org/10.1038/s41524-020-00479-0· OSTI ID:1763828

; ; ; Perdew, John P.

Abstract

Classical turning surfaces of Kohn–Sham potentials separate classically allowed regions (CARs) from classically forbidden regions (CFRs). They are useful for understanding many chemical properties of molecules but need not exist in solids, where the density never decays to zero. At equilibrium geometries, we find that CFRs are absent in perfect metals, rare in covalent semiconductors at equilibrium, but common in ionic and molecular crystals. In all materials, CFRs appear or grow as the internuclear distances are uniformly expanded. They can also appear at a monovacancy in a metal. Calculations with several approximate density functionals and codes confirm these behaviors. A classical picture of conduction suggests that CARs should be connected in metals, and disconnected in wide-gap insulators, and is confirmed in the limits of extreme compression and expansion. Surprisingly, many semiconductors have no CFR at equilibrium, a key finding for density functional construction. Nonetheless, a strong correlation with insulating behavior can still be inferred. Moreover, equilibrium bond lengths for all cases can be estimated from the bond type and the sum of the classical turning radii of the free atoms or ions.

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Research Organization:: Univ. of California, Irvine, CA (United States)

Sponsoring Organization:: National Science Foundation; Physical Sciences Research Council; Temple University; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-08ER46496; SC0012575

OSTI ID:: 1763828

Alternate ID(s):: OSTI ID: 1849873
OSTI ID: 1866800

Journal Information:: npj Computational Materials, Journal Name: npj Computational Materials Journal Issue: 1 Vol. 7; ISSN 2057-3960

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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