一种测试自旋对称性破缺波函数中共线性的简单方法：一般理论及其在广义哈特里 - 福克中的应用

A simple way to test for collinearity in spin symmetry broken wave functions: general theory and application to generalized Hartree Fock.

作者信息

Small David W, Sundstrom Eric J, Head-Gordon Martin

机构信息

Department of Chemistry, University of California, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.

出版信息

J Chem Phys. 2015 Mar 7;142(9):094112. doi: 10.1063/1.4913740.

DOI:10.1063/1.4913740

PMID:25747066

Abstract

We introduce a necessary and sufficient condition for an arbitrary wavefunction to be collinear, i.e., its spin is quantized along some axis. It may be used to obtain a cheap and simple computational procedure to test for collinearity in electronic structure theory calculations. We adapt the procedure for Generalized Hartree Fock (GHF), and use it to study two dissociation pathways in CO2. For these dissociation processes, the GHF wave functions transform from low-spin Unrestricted Hartree Fock (UHF) type states to noncollinear GHF states and on to high-spin UHF type states, phenomena that are succinctly illustrated by the constituents of the collinearity test. This complements earlier GHF work on this molecule.

摘要

我们引入了一个任意波函数共线的充要条件，即其自旋沿某一轴量子化。它可用于获得一种廉价且简单的计算程序，以在电子结构理论计算中测试共线性。我们将该程序应用于广义哈特里 - 福克（GHF）方法，并用于研究二氧化碳中的两条解离途径。对于这些解离过程，GHF波函数从低自旋无限制哈特里 - 福克（UHF）型态转变为非共线GHF态，再转变为高自旋UHF型态，共线性测试的组成部分简洁地说明了这些现象。这补充了早期关于该分子的GHF研究工作。