Conical intersections and low-lying electronic states of tetrafluoroethylene.

Abstract

The low-lying electronic states of tetrafluoroethylene (C2 F4 ) are characterized theoretically for the first time using equation-of-motion coupled cluster theory (EOM-CCSD), and complete active space self-consistent field (CASSCF) and second-order perturbation theory (CASPT2). Computations are performed for vertical excitation energies, equilibrium geometries, minimum-energy conical intersections, and potential energy curves along three geometric coordinates: 1) twisting of the FCCF dihedral angle, 2) pyramidalization of the CF2 group, and 3) migration of a fluorine atom resulting in an ethylidene-like (CF3 CF) structure. The results suggest two relaxation pathways from the Rydberg-3s excited electronic state to the ground state. These relaxation pathways are discussed in conjunction with the femtosecond photoionization spectroscopy results of Trushin et al. [ChemPhysChem- 2004, 5, 1389].