The kinetics and dynamics of the multichannel multiwell reaction of CO(1Σ+) with OH(2Π): theoretical investigation

Abstract

The kinetics and mechanism of the gas-phase reaction between carbon monoxide and hydroxyl radical have been theoretically investigated on the lowest potential energy surface. The dynamics of the reaction of CO(1 Σ +) with OH(2 Π) is studied by stochastic one-dimensional chemical master equation (CEM) simulation method. The role of the energized intermediates on the kinetics of the reaction was investigated by determination the fraction of different intermediates and products at the early stages of the reaction. The temperature dependence of the rate constants of the each individual channels of the reaction over a wide range of temperature (200-2000 K) was studied. The calculated rate constants from the CEM simulation were compared with those obtained from the RRKM-SSA [Rice-Ramsperger-Kassel-Marcus (RRKM) theory and Steady State Approximation (SSA)] method based on strong collision assumption. At lower temperatures, the calculated RRKM-SSA rate constant was found to be twice of the calculated by CEM, although the results are in good agreement with experimental values.

Substituent Dependence on the Reactions of Criegee Intermediates with Carbon Dioxide and Carbon Monoxide

“…If one looks at the CO reaction from an atmospheric perspective, comparing these CI+CO rate coefficients with atmospheric reactions involving CO is essential. The primary decay pathway for CO in the atmosphere is the reaction with OH radical [47–49] . Fulle et al.…”

“…The primary decay pathway for CO in the atmosphere is the reaction with OH radical. [47][48][49] Fulle et al have performed lab measurements and obtained high pressure room temperature rate coefficients of 8.4×10 À 13 cm 3 s À 1 for this reaction. [47] This value is six orders of magnitude faster than the values we have obtained for CI + CO.…”

Probing the Thermochemistry Properties and Rate Kinetics of Trimethyl Phosphate (TMP): An H-Atom Abstraction (HAA) Reactions Perspective

“…The thermochemistry of the TMP and its three radical products were studied using the MultiWell program suite . These species’ thermodynamic and kinetic properties of interest can be used for other extensive TMP studies (kinetic modeling and experiments).…”

“…37,49 The thermochemistry of the TMP and its three radical products were studied using the MultiWell 50 program suite. 51 These species' thermodynamic and kinetic properties of interest can be used for other extensive TMP studies (kinetic modeling and experiments). The MultiWell program suite performs kinetic calculations, employing statistical thermodynamics and rate theories for thermochemistry 52 data and rate constants.…”

Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

“…One noteworthy point is that lower levels of theory often fail to predict the linear PRCs and transition states found using the high level of theory in the present work. These failures result in erroneously predicting first‐order transition states when the high level of theory finds a second‐order saddle point, as discussed in Paper I (for a recent example, see Masoumpour and Daryanavard 66 ).…”