Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 115, Issue 50, Pages E11578-E11585Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1814300115
Keywords
atomic radius; molecular surface; Kohn-Sham potential; chemical bonding; classical turning point
Categories
Funding
- National Science Foundation [DMR 1607868, CHE-1640584]
- Natural Sciences and Engineering Research Council of Canada [RGPIN-2015-04814, RGPAS 477791-2015]
- Temple University
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The Kohn-Sham potential v(eff)(r) is the effective multiplicative operator in a noninteracting Schrodinger 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 epsilon(max) be the maximum occupied orbital energy of the noninteracting electrons. Then the equation v(eff()r) = epsilon(max) defines the surface at which classical electrons with energy epsilon <= epsilon(max) 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) Int J Quantum Chem 62: 47-53; Zhao DX, et al. (2018) Mol Phys 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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