Symmetry Breaking in Spin-Restricted, Open-Shell Hartree-Fock Wave Functions

被引：10

作者：

Li, Xiangzhu ^{[1
]}

Paldus, Josef ^{[1
,2
,3
]}

机构：

[1] Univ Waterloo, Dept Appl Math, Quantum Theory Grp, Waterloo, ON N2L 3G1, Canada

[2] Univ Waterloo, Dept Chem, Waterloo, ON N2L 3G1, Canada

[3] Univ Waterloo, GWC2, Waterloo, ON N2L 3G1, Canada

来源：

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY | 2009年 / 109卷 / 08期

关键词：

Hartree-Fock stability conditions; broken-symmetry solutions; oxygen and boron molecule ground state; symmetry-breaking; UNITARY-GROUP-APPROACH; ELECTRON CORRELATION-PROBLEM; COUPLED-CLUSTER APPROACH; INDEPENDENT-PARTICLE MODEL; STABILITY CONDITIONS; MOLECULAR-SYSTEMS; EQUATIONS; POLYENES;

D O I：

10.1002/qua.22098

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：

Relying on a unitary group approach (UGA) to coupled-cluster (CC) theory for open-shell systems we formulate a spin-free analogue of Thouless' theorem and derive stability conditions for spin-restricted, open-shell Hartree-Fock (ROHF) The formalism is illustrated on the ground states of the oxygen and boron molecules. For the O-2 molecule, the broken-space-symmetry solution appears already for a slightly stretched O-O bond. For the B-2 molecule we find a broken-symmetry solution even at the equilibrium geometry and, in fact, in almost an entire region of intermolecular separations. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 109: 1756-1765, 2009

引用

页码：1756 / 1765

页数：10

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