我室吴玮教授、苏培峰副教授在JCTC上发表题为“A Hamiltonian matrix correction based density functional valence bond method”的研究论文。

文章链接：http://pubs.acs.org/doi/abs/10.1021/acs.jctc.6b01144

摘要：

In this work, a valence bond type multi-reference density functional theory (MRDFT) method, called Hamiltonian matrix correction based density functional valence bond method (hc-DFVB), is presented. In hc-DFVB, the static electronic correlation is considered by the valence bond self-consistent field (VBSCF) strategy, while the dynamic correlation energy is taken into account by Kohn-Sham density functional theory (KS-DFT). Different from our previous version of DFVB (J. Chem. Theory Comput. 2012, 8, 1608), hc-DFVB corrects the dynamic correlation energy with a Hamiltonian correction matrix, improving the functional adaptability and computational accuracy. The method was tested for various physical and chemical properties, including spectroscopic constants, bond dissociation energies, reaction barriers, and the singlet-triplet gaps. The accuracy of hc-DFVB matches KS-DFT and high level molecular orbital (MO) methods quite well. Furthermore, hc-DFVB keeps the advantages of VB methods, which are able to provide clear interpretations and chemical insights with compact wave functions.