Collision-Induced Electronic Relaxation of Thiophosgene (S₁)

Fluorescence from the electronically excited thiophosgene (Cl2CS) in its first excited singlet state (S1) is efficiently quenched by collision. Rates of the collision-induced electronic relaxation were obtained for various vibrational levels in the S1 state by measuring the fluorescence lifetimes. We found that the relaxation process is strongly energy-dependent; the rate consistently increases by a factor of ~40 with the increase of vibrational energy from 0 to 1450 cm-1. Collision-induced intersystem crossing from the S1 to the first triplet state (T1) is attributed to the major process responsible for the electronic relaxation.