jp9b03500_si_001.pdf (1.32 MB)
Kinetic Study and Rate Coefficient Calculations of the Reaction of 1‑Hydroxyethyl Radical with Nitric Oxide
journal contribution
posted on 2019-08-22, 19:15 authored by Xiaowen Wang, Jinou Song, Zhongwei MengThe
kinetic study of the reaction of 1-hydroxyethyl radicals (CH3CHOH) with nitric oxide (NO) was performed over the temperature
range of 200–1100 K and the pressure range of 1.0 × 10–5 to 10.0 bar. The geometries of all of the stationary
points were optimized at the B3LYP/6–311++G(df,pd) level of
theory, and the energetics were refined at the CCSD(T)/cc-pVTZ level
of theory. Eight reaction pathways were explored, and they all consisted
of a common first step involving the formation of a deep potential
well. Three favorable pathways were confirmed, and they were the channels
producing the adducts CH3CO(NHOH) and CH3NOHCHO
and the products H2O and CH3CNO. The Rice–Ramsperger–Kassel
−Marcus-canonical variational transition state theory method
with Eckart tunneling correction was used to calculate the rate coefficients
of the system. The predicted total rate coefficients agree well with
the available literature data and show negative temperature dependence
and positive pressure dependence. The reaction producing the adduct
CH3CHOHNO in the entrance channel is dominant at 1.0 bar,
and its branching ratio is almost 100% at a temperature less than
670 K. At 3.0 Torr, it is only dominant at a temperature less than
600 K.