title: Hamiltonian Matrix Correction Based Density Functional Valence Bond Method.
abstract: In this work, a valence bond type multireference density functional theory (MRDFT) method, called the 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 singlet-triplet gaps. The accuracy of hc-DFVB matches that of 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.
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and College of Chemistry and Chemical Engineering, Xiamen University , Xiamen, Fujian 361005, China.
authors.forename: Chen
authors.initials: C
authors.lastname: Zhou
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and College of Chemistry and Chemical Engineering, Xiamen University , Xiamen, Fujian 361005, China.
authors.forename: Yang
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and College of Chemistry and Chemical Engineering, Xiamen University , Xiamen, Fujian 361005, China.
authors.forename: Xiping
authors.initials: X
authors.lastname: Gong
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and College of Chemistry and Chemical Engineering, Xiamen University , Xiamen, Fujian 361005, China.
authors.forename: Fuming
authors.initials: F
authors.lastname: Ying
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and College of Chemistry and Chemical Engineering, Xiamen University , Xiamen, Fujian 361005, China.
authors.forename: Peifeng
authors.identifier: http://orcid.org/0000-0003-4398-6888
authors.initials: P
authors.lastname: Su
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and College of Chemistry and Chemical Engineering, Xiamen University , Xiamen, Fujian 361005, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Wu