Theoretical study on reaction mechanism and kinetics of HNCS with CN

Abstract

We presented a theoretical study on the detailed reaction mechanism and kinetics of the CN radical with the HNCS molecule. The barrierless minimum energy path and the most favorable entrance channel have been determined by constructing a two-dimensional potential energy surface of the C atom of CN attacking the HNCS molecule. The reaction of the C atom attacking the S atom was finally identified as the dominant entrance channel based on the rate constants' results calculated with the canonical variational transition state theory. The master equation method was employed to calculate the products' branching ratios, the overall rate constant, and the pressure dependence of the title reaction. The B3LYP∕6-311+G(2d,p) method was employed for all the geometrical optimizations and a multi-level extrapolation method based on the CCSD(T) and MP2(FC) energies was employed for further energy refinements.

Pressure and temperature dependent kinetics and the reaction mechanism of Criegee intermediates with vinyl alcohol: a theoretical study

“…The corresponding structure of the minima of TST rate constants was taken as the variational transition state and used to the subsequent master equation calculation to evaluate the product distribution. This is similar to the variational approach applied to the barrierless reactions by Lin et al 74,75 The location of minimum energy path and the variation of TST rate constants for the dissociation process are given in Fig. S2 (ESI †).…”

“…This is similar to the variational approach applied to the barrierless reactions by Lin et al . 74,75 The location of minimum energy path and the variation of TST rate constants for the dissociation process are given in Fig. S2 (ESI†).…”

Density functional theoretical study on the reaction mechanism of HNCS with SiHF radical

“…At the same time HNCS and its derived free radical NCS are also important intermediates of sulfur-containing fuel combustion process, they can participate in the process of removal the toxic NO 4 compounds from rapid combustion exhaust gas too [1,6]. Theoretical study of the reaction mechanism for small molecules with HNCS is a hot topic in recent years [9][10][11][12][13][14][15][16][17][18][19][20]. Apparently, as important intermediates of many silicon fluoride reactions, it is important theoretical and practical significance to research SiHF radical.…”