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• W2028876131 abstract "The effect of pressure, temperature, H∕D isotopes, and C isotopes on the kinetics of the OH+CO reaction are investigated using Rice-Ramsperger-Kassel-Marcus theory. Pressure effects are treated with a step-ladder plus steady-state model and tunneling effects are included. New features include a treatment of the C isotope effect and a proposed nonstatistical effect in the reaction. The latter was prompted by existing kinetic results and molecular-beam data of Simons and co-workers [J. Phys. Chem. A 102, 9559 (1998); J. Chem. Phys. 112, 4557 (2000); 113, 3173 (2000)] on incomplete intramolecular energy transfer to the highest vibrational frequency mode in HOCO*. In treating the many kinetic properties two small customary vertical adjustments of the barriers of the two transition states were made. The resulting calculations show reasonable agreement with the experimental data on (1) the pressure and temperature dependence of the H∕D effect, (2) the pressure-dependent C12∕C13 isotope effect, (3) the strong non-Arrhenius behavior observed at low temperatures, (4) the high-temperature data, and (5) the pressure dependence of rate constants in various bath gases. The kinetic carbon isotopic effect is usually less than 10 per mil. A striking consequence of the nonstatistical assumption is the removal of a major discrepancy in a plot of the kOH+CO∕kOD+CO ratio versus pressure. A prediction is made for the temperature dependence of the OD+CO reaction in the low-pressure limit at low temperatures." @default.
• W2028876131 created "2016-06-24" @default.
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• W2028876131 date "2005-09-01" @default.
• W2028876131 modified "2023-10-17" @default.
• W2028876131 title "On the theory of the CO+OH reaction, including H and C kinetic isotope effects" @default.
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• W2028876131 doi "https://doi.org/10.1063/1.2031208" @default.
• W2028876131 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/16164345" @default.
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