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A new potential energy surface, PES-2024, accurately models the OH + CH3SH reaction, including methyl and thiol hydrogen abstraction. Quasi-classical trajectory calculations show energy primarily deposited into water vibrational modes, matching experimental data.

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Area of Science:

  • Chemical Kinetics
  • Theoretical Chemistry
  • Computational Chemistry

Background:

  • The OH + CH3SH reaction is complex, featuring 18 degrees of freedom and two distinct reaction channels: methyl-H and thiol-H abstraction.
  • Intermediate complexes in both entrance and exit channels add to the reaction's complexity.
  • Accurate modeling requires a detailed potential energy surface (PES) that captures these intricate features.

Purpose of the Study:

  • To develop the first analytical full-dimensional potential energy surface (PES-2024) for the polyatomic OH + CH3SH gas-phase reaction.
  • To accurately describe both methyl- and thiol-H abstraction reaction channels.
  • To provide a reliable theoretical tool for investigating the reaction dynamics and product state distributions.

Main Methods:

  • Development of the PES-2024 within the valence bond-molecular mechanics (VB-MM) framework.
  • Utilized a reduced set of high-level ab initio calculations as input data for PES construction.
  • Performed quasi-classical trajectory (QCT) calculations at room temperature using the developed PES.

Main Results:

  • PES-2024 successfully describes both methyl- and thiol-H abstraction pathways, forming water (H2O).
  • The surface accurately represents the reaction topology, including high exothermicity, low energy barriers, and intermediate complexes.
  • QCT calculations revealed that available energy is predominantly channeled into vibrational excitations of the H2O product (44% and 47% for stretching and bending modes).

Conclusions:

  • The newly developed PES-2024 provides a robust description of the OH + CH3SH reaction dynamics.
  • The theoretical vibrational state distributions of H2O products align well with recent experimental findings.
  • PES-2024 serves as a reliable surface for future theoretical studies of this important gas-phase reaction.