AUTHOR=Ying Fuming , Zhou Chen , Zheng Peikun , Luan Jiamin , Su Peifeng , Wu Wei TITLE=λ-Density Functional Valence Bond: A Valence Bond-Based Multiconfigurational Density Functional Theory With a Single Variable Hybrid Parameter JOURNAL=Frontiers in Chemistry VOLUME=7 YEAR=2019 URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2019.00225 DOI=10.3389/fchem.2019.00225 ISSN=2296-2646 ABSTRACT=

A new valence bond (VB)-based multireference density functional theory (MRDFT) method, named λ-DFVB, is presented in this paper. The method follows the idea of the hybrid multireference density functional method theory proposed by Sharkas et al. (2012). λ-DFVB combines the valence bond self-consistent field (VBSCF) method with Kohn–Sham density functional theory (KS-DFT) by decomposing the electron–electron interactions with a hybrid parameter λ. Different from the Toulouse's scheme, the hybrid parameter λ in λ-DFVB is variable, defined as a function of a multireference character of a molecular system. Furthermore, the EC correlation energy of a leading determinant is introduced to ensure size consistency at the dissociation limit. Satisfactory results of test calculations, including potential energy surfaces, bond dissociation energies, reaction barriers, and singlet–triplet energy gaps, show the potential capability of λ-DFVB for molecular systems with strong correlation.