Intersystem crossing in tunneling regime: T1 → S0 relaxation in thiophosgene

Abstract

The T₁ excited state relaxation in thiophosgene has attracted much attention as a relatively simple model for the intersystem crossing (ISC) transitions in polyatomic molecules. The very short (20–40 ps) T₁ lifetime predicted in several theoretical studies strongly disagrees with the experimental values (∼20 ns) indicating that the kinetics of T₁ → S₀ ISC is not well understood. We use the nonadiabatic transition state theory (NA-TST) with the Zhu–Nakamura transition probability and the multireference perturbation theory (CASPT2) to show that the T₁ → S₀ ISC occurs in the quantum tunneling regime. We also introduce a new zero-point vibrational energy correction scheme that improves the accuracy of the predicted ISC rate constants at low internal energies. The predicted lifetimes of the T₁ vibrational states are between one and two orders of magnitude larger than the experimental values. This overestimation is attributed to the multidimensional nature of quantum tunneling that facilitates ISC transitions along the non-minimum energy path and is not accounted for in the one-dimensional NA-TST.