Investigation of Product Formation in the O(1D, 3P) + N2O Reactions: Comparison of Experimental and Theoretical Kinetics

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 126; no. 7; pp. 1103 - 1113
• Main Authors: Pham, Tien V, Lin, M. C
• Format: Journal Article
• Language: English
• Published: American Chemical Society 24.02.2022
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.1c09477

The spin-forbidden and spin-allowed reactions of the excited and ground electronic state O­(1D, 3P) + N2O­(X 1Σ+) systems have been studied theoretically. Quantum calculations at the UCCSD­(T)/CBS­(T, Q, 5)//CCSD/aug-cc-pVTZ level have located two crossing points, MSX1 and MSX2, with energies of 11.2 and 22.7 kcal mol–1 above O­(3P) + N2O, respectively. The second-order P-independent rate constants for the adiabatic and non-adiabatic thermal reactions predicted by adiabatic TST/VTST and non-adiabatic TST, respectively, agree closely with the available literature results. The second-order rate constant, k 2a = 9.55 × 10–11 exp­(−26.09 kcal mol–1/RT) cm3 molecule–1 s–1, for the O­(3P) + N2O → 2NO reaction, contributed by both the dominant MSX2 and the minor TS1-a channels, is in reasonable accord with prior experiments and recommendations, covering the temperature range of 1200–4100 K. The calculated rate constant, k 2b = 4.47 × 10–12 exp­(−12.9 kcal mol–1/RT) cm3 molecule–1 s–1, for the O­(3P) + N2O → N2 + O2(a1Δg) reaction, occurring exclusively via MSX1, is also in good agreement with the combined experimental data measured in a shock tube study at T = 1940–3340 K (ref 16) and the result measured by Fourier transform infrared spectroscopy in the temperature range of 988–1083 K (ref 17). Moreover, the spin-allowed rate constants predicted for the singlet-state reactions, k 1a = (7.06–7.46) × 10–11 cm3 molecule–1 s–1 for O­(1D) + N2O → 2NO and k 1b = (4.36–4.66) × 10–11 cm3 molecule–1 s–1 for O­(1D) + N2O → N2 + O2(a1Δg) in the temperature range of 200–350 K, agree quantitatively with the experimentally measured data, while the total rate constant k 1 = k 1a + k 1b was also found to be in excellent accordance with many reported values.