Reaction Mechanisms and Kinetics of CN and CCH with H2CS: Implications for Interstellar Sulfur Chemistry

Abstract

We report an ab initio and master-equation investigation of the gas-phase reactions of thioformaldehyde (H2CS) with CN and CCH radicals, motivated by the recent detection of the S-containing species HCSCN and HCSCCH in cold interstellar environments. Structures and frequencies were obtained at the DSD-PBEP86/aug-cc-pVTZ level, with energetics refined by CCSD(T)-F12a calculations. Entrance capture was treated using a full multipolar long-range interaction within μJ-VTST, while postcapture dynamics and product branching were described using an energy-grained master equation. The CN + H2CS reaction proceeds through orientation-dependent entrance channels. Two barrierless addition pathways lead to a connected multiwell network that preferentially forms cyano thioformaldehyde, HCSCN + H, whereas abstraction-type channels leading to HNC + HCS or HCN + HCS contribute only marginally. The calculated kinetics indicate capture-controlled low-temperature reactivity and a strong preference for HCSCN formation. For CCH + H2CS, barrierless capture gives access to two connected entrance adducts. Although the cyclic product is the most exothermic channel, its formation is kinetically hindered by a high-lying late transition state. The flux is shared between propynethial formation, HCSCCH + H, and the HCCH + HCS channel, with the latter being favored. These results show that subtle differences in radical structure, bonding preferences, and entrance-channel topology strongly affect product branching in S-containing radical–molecule reactions. The computed mechanisms and rate coefficients provide useful input for astrochemical models of sulfur chemistry in cold molecular clouds and for interpreting recent molecular detections in sources such as TMC-1.