DFVB: A Density-Functional-Based Valence Bond Method

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• 作者：Fuming Ying ; Peifeng Su ; Zhenhua Chen ; Sason Shaik ; Wei Wu
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2012
• 出版时间：May 8, 2012
• 年：2012
• 卷：8
• 期：5
• 页码：1608-1615
• 全文大小：318K
• 年卷期：v.8,no.5(May 8, 2012)
• ISSN：1549-9626

文摘

A new ab initio valence bond method with density-functional-based correlation correction, so-called DFVB, is presented. In the DFVB method, the dynamic correlation energy is taken into account by use of density correlation functional(s), while the static correlation energy is covered by the VBSCF wave function. Owing to incorporation of DFT methods, DFVB provides an economic route to improving the accuracy of ab initio VB theory. Various tests of the method are presented, including the spectroscopic parameters of a series of diatomic molecules, the dipole moments of the NF molecule for different electronic states, and the singlet鈥搕riplet gaps of the diradical species, chemical reactions barriers, and total charge-shift resonance energies. These tests show that DFVB is capable of providing high accuracy with relatively low computational cost by comparison to the currently existing post-VBSCF methods.