Direct dynamics simulation of the thermal O(3P) + dimethylamine reaction in the triplet surface. I. Rate constant and product branching

Abstract

AbstractIn order to provide atomistic details for the mechanism of the collisional dynamics of O(3P) and dimethylamine (DMA) in the triplet electronic surface, direct dynamics simulations are reported herein. The simulations are performed at the U‐HSE06/aug‐cc‐pVDZ level of theory. The results are reported for the relative collision energy of 7.8 kcal/mol. For the vibrational and rotational excitations, following temperature regimes have been considered: 200 and 10 K, respectively. Simulations reveal that the reaction can lead to two product channels in the considered energy regime: (1) 2OH + 2CH3NHCH2 and (2) 2OH + 2CH3NCH3. The computed reaction cross section for pathways 1 and 2 are as follows: 17.89 0.20 Å2 and 3.28 0.03 Å2, whereas the computed microcanonical reaction rate constants for pathways 1 and 2 are as follows: (4.21 0.05)*10−10 and (7.72 0.07)*10−11 cm3/(molecule sec). Both pathways follow direct and indirect H abstraction processes. Among the direct pathways, stripping and rebound mechanisms have been observed, whereas the indirect pathway involves formation of a post‐reaction complex having lifetime ~0.4–0.5 ps. The velocity scattering angle distribution for the reaction is dominated by scattering in the sideways (60–120 ) and backward (120–180 ) directions with some contribution from the scattering in the forward direction (0–60 ).