Detailed kinetics of tetrafluoroethene ozonolysis.

The C2F4 + O3 reaction plays an important role in the oxidation process of perfluoroalkenes in the atmosphere. The detailed reaction mechanism was explored using the accurate electronic structure method, CCSD(T)/CBS//B3LYP/aug-cc-pVTZ. The 1,3-cycloaddition of O3 with C2F4 to form the primary ozonide was found to be the rate-determining step of the oxidation process with a small barrier (i.e., 7.3 kcal mol-1 at 0 K). The temperature- and pressure-dependent behaviors of the title reaction were characterized in the range of 200-1000 K & 0.1-760 Torr using the integrated deterministic and stochastic master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) rate model with the inclusion of the corrections for anharmonicity and tunneling treatments. It is found that the anharmonic effect plays a role in the kinetic behaviors (e.g., lower the rate by a factor of ∼ two at 298 K) while the tunneling correction is insignificant. The total rate constants were found to be pressure-independent under the considered conditions, shown as ktot(T) = 4.80 × 10-23 × T2.69 × exp(-2983.4 K/T) (cm3 per molecule per s), which confirms the latest experimental data by Acerboni et al. (G. Acerboni, N. R. Jensen, B. Rindone and J. Hjorth, Chem. Phys. Lett., 1999, 309, 364-368); thus this study helps to resolve a long-term controversy among the previous measurements. The sensitivity analyses on the derived rate coefficients and time-resolved species mole fraction with respect to the ab initio input parameters were also performed to further understand as well as quantify the kinetic behaviors for the title reaction.

On-the-fly kinetics of hydrogen abstraction from polycyclic aromatic hydrocarbons by methyl/ethyl radicals.

This work provides a rigorous procedure, within the framework of the Reaction Class Transition State Theory (RC-TST) and the Structure-Activity Relationship (SAR), for predicting reliable thermal rate constants on-the-fly for hydrogen abstraction reactions by methyl/ethyl radicals from Polycyclic Aromatic Hydrocarbons (PAHs) in a temperature range of 300-3000 K. All necessary RC-TST parameters were derived from ab initio calculations for a representative set of 36 reactions on which different error analyses and comparisons with available literature data were carried out. In addition to the good agreement between the RC-TST rate constants and the literature data, the detailed error analyses show that RC-TST/SAR, utilizing either the Linear Energy Relationship (LER) where only the reaction energy is needed or Barrier Height Grouping (BHG) where no additional data is needed, can predict the thermal rate constants for any reaction in the title reaction class with an average systematic error of less than 50% when compared to the explicit rate calculations. Therefore, the constructed RC-TST procedure can be confidently used to obtain reliable rate constants on the fly in an attempt to effectively construct detailed kinetic mechanisms for PAH-related fuels.

Ab initio kinetics of the HOSO2 + 3O2 → SO3 + HO2 reaction.

The detailed kinetic mechanism of the HOSO2 + 3O2 reaction, which plays a pivotal role in the atmospheric oxidation of SO2, was investigated using accurate electronic structure calculations and novel statistical thermodynamic/kinetic models. Explored using the accurate composite method W1U, the detailed potential energy surface (PES) revealed that the addition of O2 to a HOSO2 radical to form the adduct (HOSO4) proceeds via a transition state with a slightly positive barrier (i.e., 0.7 kcal mol-1 at 0 K). Such a finding compromises a long-term hypothesis about this channel of being a barrierless process. Moreover, the overall reaction was found to be slightly exothermic by 1.7 kcal mol-1 at 0 K, which is in good agreement with recent studies. On the newly-constructed PES, the temperature- and pressure-dependent behaviors of the title reaction were characterized in a wide range of conditions (T = 200-1000 K & P = 10-760 Torr) using the integrated deterministic and stochastic master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) rate model in which corrections for hindered internal rotation (HIR) and tunneling treatments were included. The calculated numbers were found to be in excellent agreement with literature data. The sensitivity analyses on the derived rate coefficients with respect to the ab initio input parameters (i.e., barrier height and energy transfer) were also performed to further understand the kinetic behaviors of the title reaction. The detailed kinetic mechanism, consisting of thermodynamic and kinetic data (in NASA polynomial and modified Arrhenius formats, respectively), was also provided at different T & P for further use in the modeling/simulation of any related systems.

Global minimum profile error (GMPE) - a least-squares-based approach for extracting macroscopic rate coefficients for complex gas-phase chemical reactions.

Master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) has shown to be a powerful framework for modeling kinetic and dynamic behaviors of a complex gas-phase chemical system on a complicated multiple-species and multiple-channel potential energy surface (PES) for a wide range of temperatures and pressures. Derived from the ME time-resolved species profiles, the macroscopic or phenomenological rate coefficients are essential for many reaction engineering applications including those in combustion and atmospheric chemistry. Therefore, in this study, a least-squares-based approach named Global Minimum Profile Error (GMPE) was proposed and implemented in the MultiSpecies-MultiChannel (MSMC) code (Int. J. Chem. Kinet., 2015, 47, 564) to extract macroscopic rate coefficients for such a complicated system. The capability and limitations of the new approach were discussed in several well-defined test cases.

Kinetics of Thermal Unimolecular Decomposition of Acetic Anhydride: An Integrated Deterministic and Stochastic Model.

An integrated deterministic and stochastic model within the master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) framework was first used to characterize temperature- and pressure-dependent behaviors of thermal decomposition of acetic anhydride in a wide range of conditions (i.e., 300-1500 K and 0.001-100 atm). Particularly, using potential energy surface and molecular properties obtained from high-level electronic structure calculations at CCSD(T)/CBS, macroscopic thermodynamic properties and rate coefficients of the title reaction were derived with corrections for hindered internal rotation and tunneling treatments. Being in excellent agreement with the scattered experimental data, the results from deterministic and stochastic frameworks confirmed and complemented each other to reveal that the main decomposition pathway proceeds via a 6-membered-ring transition state with the 0 K barrier of 35.2 kcal·mol-1. This observation was further understood and confirmed by the sensitivity analysis on the time-resolved species profiles and the derived rate coefficients with respect to the ab initio barriers. Such an agreement suggests the integrated model can be confidently used for a wide range of conditions as a powerful postfacto and predictive tool in detailed chemical kinetic modeling and simulation for the title reaction and thus can be extended to complex chemical reactions.