Optical potential coupled to discrete variable representation for calculations of quasibound states: Application to the CO(B 1Σ+–D′1 Σ+) predissociating interaction

Abstract

The optical potential method initially proposed by Jolicard and Austin in the context of the stabilization method is reviewed here and used with the accurate and the efficient discrete variable representation method to obtain the energies and the widths (respectively, the real and the imaginary part of the resonance energies) of rovibrational predissociated states of diatomic molecules. In this method the resonances for an n coupled states problem are obtained by a direct diagonalization of the Hamiltonian matrix in the diabatic representation. This Hamiltonian matrix is directly evaluated in the discrete variable representation using the Fourier grid Hamiltonian method proposed by Marston and Balint‐Kurti. In this approach, two optical potentials are tested and used here to impose the asymptotic behaviors of the boundary conditions which are compatible with the resonance states. The method is exemplified for the B ¹Σ⁺–D’¹ Σ⁺ Rydberg–valence predissociating interaction in the CO molecule.