A MS-CASPT2 study of the low-lying electronic excited states of CH 2BrCl

Abstract

The low-lying singlet excited states of CH 2BrCl have been calculated using multiconfigurational CASSCF, second-order perturbation theory CASPT2 and its multistate extension MS-CASPT2. The CASSCF method shows spurious valence–Rydberg mixing and a wrong order of states. Inclusion of dynamical correlation by single root CASPT2 lowers dramatically the energy of the valences states but does not lead to a complete separation between valence and Rydberg states. This situation is improved by the MS-CASPT2 calculations, which gives two valence states for both A ′ and A″ symmetries below the lowest Rydberg state, corresponding to n(Br)→σ *(C–Br) and n(Cl)→σ *(C–Cl) transitions at 6.1 eV (203 nm) and 7.2 eV (173 nm), and being repulsive along C–Br and C–Cl coordinates.