Compact and accurate ab initio valence bond wave functions for electron transfer: The classic but challenging covalent-ionic interaction in LiF

Mingxing Ren; Xin Liu; Lina Zhang; Xuhui Lin; Wei Wu; Zhenhua Chen

doi:10.1063/5.0097614

Compact and accurate ab initio valence bond wave functions for electron transfer: The classic but challenging covalent-ionic interaction in LiF

J Chem Phys. 2022 Aug 28;157(8):084106. doi: 10.1063/5.0097614.

Authors

Mingxing Ren¹, Xin Liu¹, Lina Zhang¹, Xuhui Lin¹, Wei Wu¹, Zhenhua Chen¹

Affiliation

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

PMID: 36049989
DOI: 10.1063/5.0097614

Abstract

This paper combines the valence bond block diabatization approach with the idea of orbital breathing. With highly compact wave functions, the breathing orbital valence bond (BOVB) method is applied to investigate several atomic and molecular properties, including the electron affinity of F, the adiabatic and diabatic potential energy curves and the dipole moment curves of the two lowest-lying ¹Σ⁺ states, the electronic coupling curve and the crossing distance of the two diabatic states, and the spectroscopic constants of the ground states for LiF. The configuration selection scheme proposed in this work is quite general, requiring only the selection of several de-excitation and excitation orbitals in a sense like the restricted active space self-consistent field method. Practically, this is also the first time that BOVB results are extrapolated to complete basis set limit. Armed with the chemical intuition provided by valence bond theory, the classic but challenging covalent-ionic interaction in the title molecule is not only conceptually interpreted but also accurately computed.