Parametrization of Linear Vibronic Coupling Models for Degenerate Electronic States.

ABSTRACT: Linear vibronic coupling (LVC) models have proven to be effective in describing coupled excited-state potential energy surfaces of rigid molecules. However, obtaining the LVC parameters in molecules with many degrees of freedom and a large number of, possibly (near-)degenerate, electronic states can be challenging. In this paper, we discuss how the linear intra- and interstate couplings can be computed correctly using a numerical differentiation scheme, requiring a phase correction and sufficient numerical precision in the involved electronic structure calculations. The numerical scheme is applied to three test systems with symmetry-induced state degeneracies: SO₃, [PtBr₆]^2-, and [Ru(bpy)₃]²⁺. The first two systems are employed to vali

SUBMITTER: Farkhutdinova D 

PROVIDER: S-EPMC11912485 | biostudies-literature | 2025 Mar

REPOSITORIES: biostudies-literature