Strongly separated pairs of core electrons in computed ground states of small molecules

被引：4

作者：

Gottlieb, Alex D. ^{[1
]}

Weishaeupl, Rada M. ^{[2
]}

机构：

[1] Wolfgang Pauli Inst, A-1090 Vienna, Austria

[2] Univ Vienna, Fac Math, A-1090 Vienna, Austria

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2013年 / 1007卷

基金：

奥地利科学基金会;

关键词：

Separated electron pairs; APSG; Orbital domains; Natural molecular shell; GEMINAL MODEL CHEMISTRY; DIATOMIC MOLECULES; DENSITY-MATRICES; APPROXIMATION; SYSTEMS; CONVERGENCE; ORBITALS; BORON; LIMIT; ATOM;

D O I：

10.1016/j.comptc.2012.11.024

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：

We have performed full configuration interaction computations of the ground states of the molecules Be, BeH2, Li, LiH, B, and BH and verified that the core electrons constitute "separated electron pairs." These separated pairs of core electrons have nontrivial structure; the core pair does not simply occupy a single spatial orbital. Our method of establishing the presence of separated electron pairs is direct and conclusive. We do not fit a separated pair model; we work with the wavefunctions of interest directly. To establish that a given group of spin-orbitals contains a quasi-separated pair, we verify by direct computation that the quantum state of the electrons that occupy those spin-orbitals is nearly a pure 2-electron state. (c) 2012 Elsevier B.V. All rights reserved.

引用

页码：82 / 89

页数：8