Hybrid Density Functional Valence Bond Method with Multistate Treatment

Abstract

Recently, a hybrid density functional valence bond (VB) method, λ-DFVB(U), has been proposed and shown to give accuracy that is comparable to that of CASPT2 in calculations of atomization energies, atomic excitation energies, and reaction barriers, while its computational cost is approximately the same as the valence bond self-consistent-field (VBSCF) method. However, the interaction between electronic states is not included in λ-DFVB(U) since the last step of λ-DFVB(U) is not a diagonalization of the Hamiltonian matrix on the electronic state basis. Therefore, λ-DFVB(U) gives the wrong topology of the potential energy surfaces (PESs) near the conical intersection region. In the present paper, we propose a novel hybrid density functional VB method with multistate treatment, named λ-DFVB(MS), in which an effective Hamiltonian matrix is constructed on the basis of the diabatic states obtained by the valence-bond-based compression approach for the diabatization scheme, and the interaction between electronic states can be included through the diagonalization of the effective Hamiltonian matrix. Test calculations show that λ-DFVB(MS) gives the correct topology of the PESs near the conical intersection region. We also show that the VBSCF wave function with selected VB structures can be applied as a reference in λ-DFVB(MS).