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.

Diabatization around Conical Intersections with a New Phase-Corrected Valence-Bond-Based Compression Approach

“…Among various classical VB methods, VBSCF, , which optimizes structure coefficients and orbitals simultaneously, is the elementary method of ab initio classical VB theory. If required, extra dynamic correlation can be introduced afterward for better numerical accuracy, for example upon using the hc-DFVB method, which is a valence-bond-based multireference density functional theory method.…”

λ-Density Functional Valence Bond: A Valence Bond-Based Multiconfigurational Density Functional Theory With a Single Variable Hybrid Parameter

“…The geometry of Fe(II)–porphyrin is optimized at the B3LYP level. The geometries of TMM, carbene, and the reactants and the transition states for the D-A reaction and the Menshutkin reaction are taken from previous papers (Ying et al, 2012; Huang et al, 2014; Zhou et al, 2017).…”

“…Thus, the development of the multireference wave function-based DFT (MRDFT) method, in which the dynamic correlation is considered by DFT functionals and the static correlation is covered by a multiconfigurational wave function method, is promising because of its economical computational cost. Since the 1990s, many MRDFT schemes have been proposed (Lie and Clementi, 1974; Miehlich and Stoll, 1997; Filatov and Shaik, 1999; Gräfenstein and Cremer, 2000; Grafenstein and Cremer, 2005; Head-Gordon, 2003; Gusarov et al, 2004; Pérez-Jiménez et al, 2004; Yamanaka et al, 2006; Wu et al, 2007; Cembran et al, 2009; Kurzweil et al, 2009; Rapacioli et al, 2010; Sharkas et al, 2012; Ying et al, 2012; Manni et al, 2014; Zhou et al, 2017), most of which use the MCSCF/ complete active space self-consistent field (CASSCF) as the multireference wave function. Recently, two valence bond wave function-based MRDFT (DFVB) methods are presented: the first one is the dynamic correlation-corrected density functional valence bond (dc-DFVB) method (Ying et al, 2012), and the second one is the Hamiltonian matrix correction-based density functional valence bond (hc-DFVB) method (Zhou et al, 2017).…”

A Valence-Bond-Based Multiconfigurational Density Functional Theory: The λ-DFVB Method Revisited

“…In a similar fashion, the strategy of hybrid VB theory with DFT has been implemented, such as VBDFT(s) [35][36][37][38], VB-DFT [39], and DFVB [40][41][42]. Recently, a newly developed MRDFT scheme based on the valence bond wave function, namely the λ-density functional valence bond (λ-DFVB) method [42], was presented.…”