New Potential Energy Surface for the H + Cl2 Reaction and Quantum Dynamics Studies.

The reaction of H + Cl-2 -> HCl + Cl plays a crucial role in various fields. However, no previous study has investigated this reaction using accurate quantum mechanical methods. In this paper, we construct a global potential energy surface (PES) using the neural network method with more than 20,000 ab initio energies obtained by the MRCI-F12+Q method with the aug-cc-pV5Z basis and extrapolated to the complete basis set limit. The spin-orbit coupling of the Cl atom has been considered in the PES. With this new PES, product state-resolved quantum dynamics calculations for the H + Cl-2 (v(0) = 0, j(0) = 0-2) -> HCl + Cl reaction was carried out. Numerical results show that the initial rotational excitation of the Cl-2 has negligible effects on the reactivity. Product state-resolved integral cross sections (ICS) and rate constants reveal that the HCl is most favorably produced in its v ' = 2 vibrational state. The calculated product vibrational state-resolved and total reaction rate constants suggest that the new global PES is accurate enough, as compared with the available experimental measurements.