Visualizing Atomic Sizes and Molecular Shapes with the Classical Turning Surface of the Kohn-Sham Potential

Overview

Journal Proc Natl Acad Sci U S A

Specialty Science

Date 2018 Nov 23

PMID 30463943

Citations 3

Authors

Egor Ospadov

Jianmin Tao

Viktor N Staroverov

John P Perdew

Affiliations

Soon will be listed here.

Abstract

The Kohn-Sham potential [Formula: see text] is the effective multiplicative operator in a noninteracting Schrödinger equation that reproduces the ground-state density of a real (interacting) system. The sizes and shapes of atoms, molecules, and solids can be defined in terms of Kohn-Sham potentials in a nonarbitrary way that accords with chemical intuition and can be implemented efficiently, permitting a natural pictorial representation for chemistry and condensed-matter physics. Let [Formula: see text] be the maximum occupied orbital energy of the noninteracting electrons. Then the equation [Formula: see text] defines the surface at which classical electrons with energy [Formula: see text] would be turned back and thus determines the surface of any electronic object. Atomic and ionic radii defined in this manner agree well with empirical estimates, show regular chemical trends, and allow one to identify the type of chemical bonding between two given atoms by comparing the actual internuclear distance to the sum of atomic radii. The molecular surfaces can be fused (for a covalent bond), seamed (ionic bond), necked (hydrogen bond), or divided (van der Waals bond). This contribution extends the pioneering work of Z.-Z. Yang et al. [Yang ZZ, Davidson ER (1997) 62:47-53; Zhao DX, et al. (2018) 116:969-977] by our consideration of the Kohn-Sham potential, protomolecules, doubly negative atomic ions, a bond-type parameter, seamed and necked molecular surfaces, and a more extensive table of atomic and ionic radii that are fully consistent with expected periodic trends.

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