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

Molecules

Peikun Zheng¹  Fuming Ying¹  Chenru Ji¹  Peifeng Su¹  Wei Wu¹ 

[1] Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, The State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China;

关键词: valence bond theory;    density functional theory;    electron correlation;    multireference;   

DOI  :  10.3390/molecules26030521

来源: DOAJ

【 摘 要 】

A recently developed valence-bond-based multireference density functional theory, named λ-DFVB, is revisited in this paper. λ-DFVB remedies the double-counting error of electron correlation by decomposing the electron–electron interactions into the wave function term and density functional term with a variable parameter λ. The λ value is defined as a function of the free valence index in our previous scheme, denoted as λ-DFVB(K) in this paper. Here we revisit the λ-DFVB method and present a new scheme based on natural orbital occupation numbers (NOONs) for parameter λ, named λ-DFVB(IS), to simplify the process of λ-DFVB calculation. In λ-DFVB(IS), the parameter λ is defined as a function of NOONs, which are straightforwardly determined from the many-electron wave function of the molecule. Furthermore, λ-DFVB(IS) does not involve further self-consistent field calculation after performing the valence bond self-consistent field (VBSCF) calculation, and thus, the computational effort in λ-DFVB(IS) is approximately the same as the VBSCF method, greatly reduced from λ-DFVB(K). The performance of λ-DFVB(IS) was investigated on a broader range of molecular properties, including equilibrium bond lengths and dissociation energies, atomization energies, atomic excitation energies, and chemical reaction barriers. The computational results show that λ-DFVB(IS) is more robust without losing accuracy and comparable in accuracy to high-level multireference wave function methods, such as CASPT2.

【 授权许可】

Unknown