Non-Nuclear maxima and the universality of Bright Wilson's justification of the first Hohenberg Kohn theorem revisited

被引：5

作者：

Anderson, James S. M. ^{[1
]}

Massa, Lou ^{[2
,3
]}

Matta, Cherif F. ^{[4
,5
,6
,7
]}

机构：

[1] Univ Nacl Autonoma Mexico, Inst Quim, Edif D,Cubiculo 8,Univ 300,Ciudad Univ, Ciudad De Mexico 04510, Mexico

[2] CUNY, Dept Chem Hunter Coll, New York, NY 10065 USA

[3] CUNY, PhD Program Grad Ctr, New York, NY 10065 USA

[4] Mt St Vincent Univ, Dept Chem & Phys, Halifax, NS B3M 2J6, Canada

[5] Dalhousie Univ, Halifax, NS B3H 4J3, Canada

[6] St Marys Univ, Halifax, NS B3H 3C3, Canada

[7] Univ Laval, Dept Chim, Quebec City, PQ G1V 0A6, Canada

来源：

CHEMICAL PHYSICS LETTERS | 2021年 / 780卷

基金：

加拿大创新基金会; 加拿大自然科学与工程研究理事会;

关键词：

ELECTRON-DENSITY; ATTRACTORS; EXISTENCE; BOND;

D O I：

10.1016/j.cplett.2021.138940

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The Kato cusp condition involves a spherically-averaged derivative of the electron density with respect to distance from a given nucleus weighted by the electron density at that nucleus. This "Kato ratio" is shown analytically to vanish at all points of the electron density (and of the underlying external potential) that do not exhibit a singularity including non-nuclear maxima/attractors (NNM/NNAs). Using prototypical test cases, the analytical result is confirmed numerically. This result, while quite simply demonstrated and possibly tacitly known, could not be located in the literature to the best of the authors' efforts. Since the Kato ratio is zero at a NNM/NNA, this saves the DFT plausibility argument of E. Bright Wilson. The consideration of these ideas in excited electronic states is discussed.

引用

页数：6