A Theoretical Study on the Dynamics of O(P-3) + H2S((1)A(1)) Reaction on an Interpolated Potential Energy Surface

作者：Masoumpour Marziyeh Sadat; Mousavipour Seyed Hosein^*

来源：Bulletin of the Chemical Society of Japan, 2017, 90(10): 1141-1151.

DOI：10.1246/bcsj.20170107

Quasi-classical trajectory calculations at the DFT level and CVT calculations at the CCSD(T) level are performed to study the dynamics of O(P-3) + H2S((1)A(1)) reaction on the lowest triplet potential energy surface. In the dynamics part the potential energy surface has been constructed by interpolation technique following the method introduced by Collins and his coworkers. Total and individual classical reactive cross sections are calculated at collision energies from 13.1 to 126.0 kJ mol(-1). The rate constants from QCT calculation are compared with those calculated from canonical variational transition state theory at the G3(MP2)B3 and CCSD(T)/Aug-cc-pVTZ levels. The energy partitioning in reactive collisions for the formation of main products (OH + SH and H + HSO) and in non-reactive collisions for the reactants is investigated. At 52.5 kJ mol(-1) initial collision energy about 42% and 49% of the total available energy goes into the translational energy and internal motions of H + HSO products, respectively, while for SH + OH products these quantities were found to be about 25% and 40% of the total available energy. The rest of the available energy is allocated in the rotational degrees.

• 出版日期2017-10