Quantum chemical and kinetic study of the reaction between CCl2 and NO2 radicals
Year: 2024
Type: article
Abstract: The dependence of the rate constant of the recombination reaction of CCl2 and NO2 radicals on temperature and pressure was studied. Quantum-chemical calculations were employed to characterize relevant aspects of the potential energy surface for this process. The limiting rate constants between 300 and 2000 K were analyzed using the unimolecular reactions theory. The resulting low pressure rate constant can be represented as k0 = [He] (1.4 ± 0.2) x 10-26 (T/300 K)(-8.72±0.04)exp(-(1520 ± 10) K/T) cm3 molecule-1 s-1. The corresponding expressions for the high pressure limit rate constants, derived from a simplified version of the statistical adiabatic channel (SSACM) and from a SACM combined with classical trajectory calculations (SACM/CT), are (2.3 ± 1.9) x 10-11 (T/300 K)(-1.01±0.39)exp(-(810 ± 80) K/T) and (8.8 ± 5.3) x 10-13 (T/300 K)(0.82±0.13) cm3 molecule-1 s-1. The falloff curves were represented in terms of these limiting rate constants. Reported experimental results are well described with the present model. Our calculations indicate that the CCl2 + NO2 reaction proceeds via the stabilization of the energized CCl2NO2 adduct, and that the CCl2 + NO2 → CCl2O + NO channel becomes relevant at high temperatures.
Source: Conicet
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7014917656
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