Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Calculation and interpretation of classical turning surfaces in solids

Journal Article · · npj Computational Materials
; ; ;

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.

Research Organization:
Univ. of California, Irvine, CA (United States); Temple Univ., Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
FG02-08ER46496; SC0012575
OSTI ID:
1849873
Journal Information:
npj Computational Materials, Vol. 7, Issue 1; ISSN 2057-3960
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English

References (58)

Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Visualizing atomic sizes and molecular shapes with the classical turning surface of the Kohn–Sham potential journal November 2018
Generalized Gradient Approximation Made Simple journal October 1996
Why semilocal functionals work: Accuracy of the on-top pair density and importance of system averaging journal September 1998
On-top pair-density interpretation of spin density functional theory, with applications to magnetism journal January 1997
Assessing the SCAN functional for itinerant electron ferromagnets journal September 2018
Density functional methods for the magnetism of transition metals: SCAN in relation to other functionals journal July 2019
Semilocal density functional obeying a strongly tightened bound for exchange journal January 2015
Hybrid functionals based on a screened Coulomb potential journal May 2003
Accurate critical pressures for structural phase transitions of group IV, III-V, and II-VI compounds from the SCAN density functional journal March 2018
Efficient first-principles prediction of solid stability: Towards chemical accuracy journal March 2018
Self-consistent hybrid functional for condensed systems journal May 2014
Theory of the Insulating State journal January 1964
Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy journal December 1982
From explicit to implicit density functionals journal January 1999
Improved method for generating exchange-correlation potentials from electronic wave functions journal February 2017
Evaluation of a characteristic atomic radius by an ab initio method journal January 1997
A characteristic molecular contour evaluated by a theoretical method journal August 1998
Locality of correlation in density functional theory journal August 2016
What do we learn from the classical turning surface of the Kohn–Sham potential as electron number is varied continuously? journal February 2020
Quantum Density Oscillations in an Inhomogeneous Electron Gas journal March 1965
What do the Kohn-Sham Orbital Energies Mean? How do Atoms Dissociate? book
Density functionals from many-body perturbation theory: The band gap for semiconductors and insulators journal April 2006
Understanding band gaps of solids in generalized Kohn–Sham theory journal March 2017
Step structure in the atomic Kohn-Sham potential journal December 1995
How Interatomic Steps in the Exact Kohn–Sham Potential Relate to Derivative Discontinuities of the Energy journal December 2017
A simple measure of electron localization in atomic and molecular systems journal May 1990
Many-Body Interactions in Ice journal March 2017
Equation of state for solid neon from quantum theory journal August 2009
First-principle study of solid neon under high compression journal October 2010
Transparent dense sodium journal March 2009
Liquid-drop model for crystalline metals: Vacancy-formation, cohesive, and face-dependent surface energies journal January 1991
Vacancies in Metals: From First-Principles Calculations to Experimental Data journal October 2000
High-Level Correlated Approach to the Jellium Surface Energy, without Uniform-Gas Input journal January 2008
Communication: Ionization potentials in the limit of large atomic number journal December 2010
Interpretations of ground-state symmetry breaking and strong correlation in wavefunction and density functional theories journal January 2021
Tests of a ladder of density functionals for bulk solids and surfaces journal February 2004
Charge transfer in time-dependent density-functional theory via spin-symmetry breaking journal April 2011
An Approximate Quantum Theory of the Antiferromagnetic Ground State journal June 1952
Localized Magnetic States in Metals journal October 1961
Energetic stability and magnetic properties of MnO in the rocksalt, wurtzite, and zinc-blende structures: Influence of exchange and correlation journal October 2010
Synergy of van der Waals and self-interaction corrections in transition metal monoxides journal September 2017
Accurate and Numerically Efficient r 2 SCAN Meta-Generalized Gradient Approximation journal September 2020
Meta-GGA performance in solids at almost GGA cost journal September 2020
Ab initiomolecular dynamics for liquid metals journal January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium journal May 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
First-principles simulation: ideas, illustrations and the CASTEP code journal March 2002
Finite basis set corrections to total energy pseudopotential calculations journal May 1990
Reproducibility in density functional theory calculations of solids journal March 2016
Band structure of MoS 2 , MoSe 2 , and α − MoTe 2 : Angle-resolved photoelectron spectroscopy and ab initio calculations journal November 2001
Self-consistent meta-generalized gradient approximation within the projector-augmented-wave method journal July 2011
Calculation of the lattice constant of solids with semilocal functionals journal February 2009
X-ray diffraction data for graphite to 20 GPa journal July 1989
Structure of graphite by neutron diffraction journal November 1975
Calculation and interpretation of classical turning surfaces in solids dataset January 2020
Interpretations of ground-state symmetry breaking and strong correlation in wavefunction and density functional theories dataset January 2020

Similar Records

Related Subjects

Chemistry
Materials Science