Quasi-Classical Trajectory Dynamics Study of the Reaction OH + H2S→H2O + SH and Its Isotopic Variants: Comparison with Experiment

Abstract

The hydrogen abstraction reaction OH + H2S→H2O + SH plays an important role in acid rain formation, air pollution and climate change. In this work, the product energy disposals of the reaction and its isotopic variants OD + H2S and OD + D2S are calculated on a new ab-initio-based ground electronic state potential energy surface (PES) using the quasi-classical trajectory method. The PES is developed by fitting a total of 72,113 points calculated at the level of UCCSD(T)-F12a/aug-cc-pVTZ and using the fundamental invariant-neural network method, resulting in a total RMSE of 4.14 meV. The product H2O formed in the OH + H2S reaction at 298 K is found to be largely populated in the first overtone states of its symmetric and asymmetric stretching modes, while the vibrational distributions of the products HOD and D2O in the isotopically substituted reactions are visibly different. The computed product vibrational state distributions agree reasonably well with experimental results and are rationalized by the sudden vector projection model.