Semiclassical Transition State Theory (SCTST) Rate Coefficients for the Unimolecular Decomposition of the Ethoxy (CH3CH2O) Radical

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-11, Vol.128 (46), p.9998-10008
• Main Authors: Nguyen, Thanh Lam, Jones, Gregory H., Changala, Bryan, Giri, Binod Raj, Barker, John R., Stanton, John F.
• Format: Article
• Language: English
• Subjects: A: Combustion and Plasma Chemistry
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c05775

The thermal unimolecular decay of ethoxy is important in high-temperature combustion environments where the ethoxy radical is a key reactive intermediate. Two dissociation pathways of ethoxy, including the β-C–C scission to yield CH3 + CH2O and the H-elimination to make H + CH3CHO, were characterized using a high-level coupled-cluster-based composite quantum chemical method (mHEAT-345­(QΛ)). The former route is found to be dominant while the latter is insignificant, in agreement with previous experimental and theoretical studies. Thermal rate coefficients are calculated for P = 0.001–658 atm (of air) and T = 300–2500 K using semiclassical transition state theory (SCTST) in combination with a pragmatic two-dimensional E,J-resolved master equation (2DME). The effects of tunneling and anharmonicity on the calculated rate constants are also examined. The tunneling factor is found to be inversely dependent on pressure, contrary to previous observations of pressure-dependent tunneling in entrance channels.