Photoionization dynamics from : a one-electron model

Quantum dynamics of photoionization from Cl 2 - is investigated by constructing a purely one-electron model Hamiltonian of the anion calibrated with the help of ab initio theoretical calculations at the MRSD-CI level. A mean-field time-dependent Fourier grid Hamiltonian method is used to investigate the modulation of the dynamics of photoionization from Cl 2 - caused by the coupling of electronic and nuclear motions. Vibrational quenching at low coupling strength is predicted to turn into vibrational enhancement of ionization at higher strengths of coupling.