Vibronic structures and dynamics of the predissociating dimethyl sulfide and its isotopomers (CH3SCH3, CD3SCD3, CH3SCD3) at the conical intersection

Abstract

Conical intersection seam comprised of crossing surfaces of two lowest excited states of dimethyl sulfide (DMS) has been directly accessed by the one-photon excitation from the ground equilibrium state. Since the S–C bond rupture takes place promptly, the molecular structure on the excited state effectively belongs to C_S symmetry. Namely, excited states of 1¹B₁ and 1¹A₂ in C_2V become 1¹A′′ and 2¹A′′ states in C_S, respectively, and the optical transition from the ground equilibrium state to the dissociating molecule at the conical intersection seam is symmetry-allowed to facilitate the nonadiabatic transition on the 2¹A′′ state, leading eventually to the CH₃S + CH₃ products. The dynamic study of DMS, in this sense, gives the great opportunity to unravel the vibronic structure of the conical intersection seam by the conventional one-photon excitation method. In this work, utilizing the photofragment excitation (PHOFEX) spectroscopic method, the vibronic structures of DMS and its isotope analogs (CD₃SCD₃, CH₃SCD₃) at the conical intersection seam have been revealed, providing accurate lifetimes and detailed dynamics associated with individual vibronic transitions. The lifetime of the excited DMS is estimated to be ∼100 fs, indicating that the dissociation is complete within one single oscillation in the conical intersection region. It is also found that the symmetric CSC stretching mode is strongly coupled to the reaction coordinate, as manifested by our experimental finding that the fragmentation yield of the S–CD₃ bond is enhanced compared to that of the S–CH₃ bond in the CH₃SCD₃ dissociation reaction only when the CSC symmetric stretching vibrational mode is excited at the conical intersection region. This work demonstrates that the better understanding of the excited state could make the bond-selective chemistry into reality.