Eliminating symmetry problems in electronegativity equalization and correcting self-interaction errors in conceptual DFT

Journal of Computational Chemistry
László von Szentpály

Abstract

The chemical potential is by definition constant in molecules, and electronic charge is in principle equilibrated by bonding. Does electronegativity offer the best scale to unify these principles? According to conceptual density functional theory (c-DFT), the electronegativity equalization (ENE) and chemical potential equalization (CPE) principles seem rigorous and identical. However, the operational formulations of CPE and ENE fail to validate this claim, and frequently dramatic deviations from equalization are reported. We here eliminate the deviations to a very large extent. The problems originate from (i) c-DFT's exclusive reference to ground states and violations of the Wigner-Witmer symmetry constraints for bonding, (ii) electron self-interaction and delocalization errors. The problems are solved, and much more accurate ENE and bond polarities are obtained by replacing the ground-state electronegativity (χGS ) by the valence-state electronegativity (χVS ) and its generalization, the valence-pair-affinity (VPA, αVP ). The VPA is a charge dependent pair-sharing potential connected to Ruedenberg's bond theory that emphasizes the role of electron pair-density. The performances of the valence-pair equilibration (VPEq) and c-DF...Continue Reading

References

May 15, 2003·Chemical Reviews·P GeerlingsW Langenaeker
Jul 1, 1968·Proceedings of the National Academy of Sciences of the United States of America·E P Gyftopoulos, G N Hatsopoulos
Sep 14, 2006·Journal of the American Chemical Society·Leslie Glasser, László von Szentpály
Apr 14, 2007·The Journal of Chemical Physics·Muneaki Kamiya, So Hirata
Jan 15, 2008·The Journal of Chemical Physics·Tânia S AlmeidaSylvio Canuto
Jan 1, 1978·Annual Review of Physical Chemistry·R S Mulliken
Jan 26, 2010·The Journal of Chemical Physics·Apostolos KalemosAristides Mavridis
Apr 23, 2010·Journal of Molecular Modeling·Peter PolitzerFelipe A Bulat
Aug 24, 2010·The Journal of Chemical Physics·Ivan O AntonovMichael C Heaven
Sep 18, 2010·The Journal of Physical Chemistry. a·László von Szentpály
Oct 14, 2011·The Journal of Chemical Physics·Apostolos Kalemos, Aristides Mavridis
Dec 24, 2011·Chemical Reviews·Aron J CohenWeitao Yang
Aug 24, 2013·Journal of Chemical Information and Modeling·Crina-Maria IonescuJaroslav Koča
Jul 21, 2015·Journal of the American Chemical Society·Martin Rahm, Roald Hoffmann
Sep 9, 2014·Journal of Chemical Theory and Computation·Giovanni Li ManniLaura Gagliardi
Feb 8, 2011·Journal of Chemical Theory and Computation·Peter PolitzerJane S Murray
Jun 14, 2011·Journal of Chemical Theory and Computation·T VerstraelenM Waroquier
Jan 11, 2011·Journal of Chemical Theory and Computation·Peifeng SuPhilippe C Hiberty
Jan 9, 2016·Chemistry : a European Journal·Wenli Zou, Dieter Cremer
Jan 13, 2016·Chemistry : a European Journal·Markus Hermann, Gernot Frenking
Feb 26, 2016·The Journal of Physical Chemistry. a·Matteo Barborini
Jan 7, 2017·Science·Michael G MedvedevKonstantin A Lyssenko
Jan 31, 2017·The Journal of Physical Chemistry. a·Aaron C WestKlaus Ruedenberg
Jun 22, 2017·The Journal of Physical Chemistry. a·Andrew M JamesJohn Morrison Galbraith
Aug 12, 2017·The Journal of Chemical Physics·Apostolos Kalemos
Nov 2, 2017·The Journal of Physical Chemistry Letters·Junwei Lucas BaoDonald G Truhlar

❮ Previous
Next ❯

Citations

Oct 8, 2020·Physical Chemistry Chemical Physics : PCCP·J Luis Casals-SainzA Martín Pendás
Dec 11, 2020·The Journal of Physical Chemistry. a·László von SzentpályNihat Karakuş
Oct 21, 2021·Chemistry : a European Journal·Stefano Racioppi, Martin Rahm

❮ Previous
Next ❯

Related Concepts

Related Feeds

Basal Ganglia

Basal Ganglia are a group of subcortical nuclei in the brain associated with control of voluntary motor movements, procedural and habit learning, emotion, and cognition. Here is the latest research.