Surface hopping dynamics reveal ultrafast triplet generation promoted by S1–T2–T1 spin-vibronic coupling in 2-mercaptobenzothiazole

Abstract

We investigate the T₁ formation upon populating the optically “bright” S₂ in 2-mercaptobenzothiazole to interpret the underlying relaxation pathways associated with the experimental decay constants reported by D. Koyama and A. J. Orr-Ewing, Phys. Chem. Chem. Phys., 2016, 18, 26224–26235. Energetics, electronic populations and geometries of various stationary points of low-lying electronic states are computed using the semi-classical ab initio surface hopping dynamics simulations. Estimated decay constants of S₂–S₁ internal conversion (IC) and S₁–T₂ intersystem crossing (ISC) are in excellent agreement with the experiment. The observed ultrafast ISC is analyzed based on the S₁–T₂–T₁ spin-vibronic coupling mechanism. In contrast to the previous assignment of 6 ps to the T₂–T₁ IC, our findings enable us to attribute this decay constant to the combined events of T₂–T₁ IC followed by relaxation of vibrationally hot T₁.