Probing Rotational Motion in 4-tert-Butylcatechol through H Atom Photofragmentation: Deviations from Axial Recoil

The time-resolved photofragmentation dynamics of 4-tert-butylcatechol were studied following one photon excitation to the S1 (11ππ*) state with ultraviolet radiation in the range 260 ≤ λ ≤ 286 nm. The preparation of an aligned molecular ensemble via photoexcitation leads to anisotropy in the H atom photofragments. These H atoms originate from the decay of the S1 state through coupling onto the S2 (1πσ*) state, which is dissociative along the nonintramolecular hydrogen bonded “free” O–H bond. The degree of anisotropy of these photogenerated H atoms decreases with increasing pump–probe time delay. This is attributed to rotational dephasing of the initially aligned molecular ensemble. The measured dephasing occurs on a time scale akin to the appearance time of these H atoms, which likely places an intrinsic lower bound on the dephasing lifetime. The present work demonstrates how a careful balance between the appearance time of the H atoms, determined by the S1 lifetime, and the rotational dephasing in 4-tert-butylcatechol provides an opportune window to probe rotational motion in real time.