Vibronic coupling in the excited cationic states of ethylene: Simulation of the photoelectron spectrum between 12 and 18 eV

The effect of vibronic coupling on structure and spectroscopy is investigated in the excited cationic states of ethylene. It is found from equation of motion coupled cluster singles and doubles method for ionization potential electronic structure calculations in a triple-zeta plus double polarization basis set that ethylene in its third (B (2)A(g)) and fourth (C B-2(2u)) ionized states does not have a stable minimum-energy geometry. The potential-energy surfaces of these states are energetically distinct and well separated at the ground-state geometry of ethylene, but in a geometry optimization as the structure of the ion relaxes, these surfaces end up in conical intersections and finally in the stable equilibrium geometry of the second ionized state (A B-2(3g)). The topology of the potential-energy surfaces can be clearly understood using a vibronic model Hamiltonian. Furthermore, by diagonalizing this model Hamiltonian, the photoelectron spectrum of ethylene corresponding to the second, third, and fourth ionized states (12-18 eV) is simulated. Spectra from vibronic simulations including up to quartic coupling constants and using various normal-mode basis sets are compared to those from vertical Franck-Condon simulations to understand the importance of vibronic coupling and nonadiabatic effects and to examine the influence of individual normal modes on the spectrum. (c) 2005 American Institute of Physics.