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

Livingstone, Ruth A.
Thompson, James O. F.
Iljina, Marija
Donaldson, Ross J.
Sussman, Benjamin J.
Paterson, Martin J.
Townsend, Dave

Publication date

November 2012

DOI

Abstract

Time-resolved photoelectron imaging was used to investigate the dynamical evolution of the initially prepared S1 (\u3c0\u3c0*) 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 S1potential surface. In catechol, the overall S1 state lifetime was observed to be 12.1 ps, which is 1\u20132 orders of magnitude shorter than in the other three molecules studied. This may be attributed to differences in the H atom tunnelling rate...