Time-resolved photoelectron imaging of excited state relaxation dynamics in phenol, catechol, resorcinol, and hydroquinone

Time-resolved photoelectron imaging was used to investigate the dynamical evolution of the initially prepared S-1 (pi pi*) excited state of phenol (hydroxybenzene), catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), and hydroquinone (1,4-dihydroxybenzene) following excitation at 267 nm. Our analysis was supported by ab initio calculations at the coupled-cluster and CASSCF levels of theory. In all cases, we observe rapid (<1 ps) intramolecular vibrational redistribution on the S1 potential surface. In catechol, the overall S-1 state lifetime was observed to be 12.1 ps, which is 1-2 orders of magnitude shorter than in the other three molecules studied. This may be attributed to differences in the H atom tunnelling rate under the barrier formed by a conical intersection between the S1 state and the close lying S-2 (pi sigma*) state, which is dissociative along the O-H stretching coordinate. Further evidence of this S-1/S-2 interaction is also seen in the time-dependent anisotropy of the photoelectron angular distributions we have observed. Our data analysis was assisted by a matrix inversion method for processing photoelectron images that is significantly faster than most other previously reported approaches and is extremely quick and easy to implement. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4765104]