Intramolecular vibrational dynamics in S1 p-fluorotoluene. I. Direct observation of doorway states

Picosecond time-resolved photoelectron spectroscopy is used to investigate intramolecular vibrational redistribution (IVR) following excitation of S-1 18a(1) in p-fluorotoluene (pFT) at an internal energy of 845 cm(-1), where nu(18a) is a ring bending vibrational mode. Characteristic oscillations with periods of 8 ps and 5 ps are observed in the photoelectron signal and attributed to coupling between the initially excited zero-order bright state and two doorway states. Values for the coupling coefficients connecting these three vibrational states have been determined. In addition, an exponential change in photoelectron signal with a lifetime of 17 ps is attributed to weaker couplings with a bath of dark states that play a more significant role during the latter stages of IVR. A tier model has been used to assign the most strongly coupled doorway state to S-1 17a(1) 6a'(2), where nu(17a) is a CH out-of-plane vibrational mode and 6a'(2) is a methyl torsional level. This assignment signifies that a torsion-vibration coupling mechanism mediates the observed dynamics, thus demonstrating the important role played by the methyl torsional mode in accelerating IVR. (C) 2011 American Institute of Physics. [doi:10.1063/1.3638689]