Implementation of molecular symmetry in valence bond calculation

Abstract

AbstractA novel strategy for the construction of many‐electron symmetry‐adapted wave function is proposed for ab initio valence bond (VB) calculations and is implemented for valence bond self‐consistent filed (VBSCF) and breathing orbital valence bond (BOVB) methods with various orbital optimization algorithms. Symmetry‐adapted VB functions are constructed by the projection operator of symmetry group. The many‐electron symmetry‐adapted wave function is expressed in terms of symmetry‐adapted VB functions, and thus the VB calculations can be performed with the molecular symmetry restriction. Test results show that molecular symmetry reduces the computational cost of both the iteration numbers and CPU time. Furthermore, excited states with specific symmetry can be conveniently obtained in VB calculations by using symmetry‐adapted VB functions.