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An efficient algorithm for complete active space valence bond self-consistent field calculation

Authors

  • Jinshuai Song,

    1. The State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China
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  • Zhenhua Chen,

    Corresponding author
    1. Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202
    • The State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China
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  • Sason Shaik,

    1. Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904, Israel
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  • Wei Wu

    Corresponding author
    1. The State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China
    • The State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China
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Abstract

This article describes a novel algorithm for the optimization of valence bond self-consistent field (VBSCF) wave function for a complete active space (CAS), so-called VBSCF(CAS). This was achieved by applying the strategies adopted in the optimization of CASSCF wave functions to VBSCF(CAS) wave functions, using an auxiliary orthogonal orbital set that generates the same configuration space as the original nonorthogonal orbital set. Theoretical analyses and test calculations show that the VBSCF(CAS) method shares the same computational scaling as CASSCF. The test calculations show the current capability of VBSCF method, which involves millions of VB structures. © 2012 Wiley Periodicals, Inc.

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