Multistate vibronic interactions in difluorobenzene radical cations. II. Quantum dynamical simulations

Abstract

The multistate vibronic dynamics in the X-D electronic states of all three difluorobenzene radical cations are investigated theoretically by an ab initio quantum dynamical approach. The vibronic coupling scheme and the ab initio values of the system parameters are adopted from Paper I [S. Faraji and H. Koppel, J. Chem. Phys. 129, 074310 (2008)]. Extensive calculations by wave-packet propagation have been performed with the aid of the multiconfiguration time-dependent Hartree method. Five coupled electronic potential energy surfaces and 10 (11 in the case of the orthoisomer) vibrational degrees of freedom have been included in these calculations. The nonadiabatic interactions lead to the restructuring of the photoelectron spectral envelopes. Ultrafast internal conversion processes within the electronic manifolds in question demonstrate the strength of the nonadiabatic coupling effects and complement the analogous findings for the electronic spectra. The internal conversion dynamics is characterized by a stepwise transfer of the electronic population to the lowest electronic state on a time scale of femtoseconds to picoseconds. A difference between the three isomers is found to be related to the weaker interaction between the sets of X-A and B-C-D states (with high-energy conical intersections) in the meta isomer, as compared to the other isomers. The implications of these findings for the qualitative understanding of the fluorescence dynamics of fluorinated benzene radical cations are discussed.