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Title: Visualizing atomic sizes and molecular shapes with the classical turning surface of the Kohn–Sham potential

The Kohn–Sham potentialveff(r)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. Letϵmaxbe the maximum occupied orbital energy of the noninteracting electrons. Then the equationveff(r)=ϵmaxdefines the surface at which classical electrons with energyϵϵmaxwould 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)Int J Quantum Chem62:47–53; Zhao DX, et al. (2018)Mol Phys116:969–977] 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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NSF-PAR ID:
10080024
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
Proceedings of the National Academy of Sciences
Date Published:
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
115
Issue:
50
ISSN:
0027-8424
Page Range / eLocation ID:
p. E11578-E11585
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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