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

ABSTRACT: A new valence bond (VB)-based multireference density functional theory (MRDFT) method, named ?-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). ?-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 ?. Different from the Toulouse's scheme, the hybrid parameter ? in ?-DFVB is variable, defined as a function of a multireference character of a molecular system. Furthermore, the E C 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 ?-DFVB for molecular systems with strong correlation.

SUBMITTER: Ying F 

PROVIDER: S-EPMC6476929 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature