Photophysics of fluorinated benzene. II. Quantum dynamics

Abstract

Nuclear dynamics in the coupled electronic states of mono-, di-(ortho and meta), and pentafluorobenzene molecules is investigated here. Attempts are specifically made to understand the complexity and broadening of the recorded gas phase electronic absorption spectra of these molecules. Justification is also provided for the low quantum yield of fluorescence emission with increasing number of fluorine substitutions. The nuclear dynamics is simulated from first principles both by time-independent and time-dependent quantum mechanical methods. Potential energy surfaces of the low-lying excited electronic states of these molecules constructed in Paper I [Mondal and Mahapatra, J. Chem. Phys.133, 084304 (2010)] are employed for the purpose. Theoretical results presented in this paper are compared with the available experimental data and the agreement between the two is found to be excellent. While structured electronic absorption bands are observed for the S1 state of mono- and difluorobenzene molecules, the same for the pentafluorobenzene is broad and structureless. Occurrence of S1-S2 conical intersections in pentafluorobenzene leads to a nonradiative internal conversion of the S1 state in ∼165 fs and contributes to the broadening of the S1←S0absorption band and a biexponential decay of its fluorescence emission.