An ab Initio/Transition State Theory Study of the Reactions of Ċ5H9 Species of Relevance to 1,3-Pentadiene, Part II: Pressure Dependent Rate Constants and Implications for Combustion Modeling.

Abstract

The temperature- and pressure-dependence of rate constants for several radicals and unsaturated hydrocarbons reactions (1,3-C5H8/1,4-C5H8/cyC5H8 + Ḣ, C2H4 + Ċ3H5-a, C3H6 + Ċ2H3) are analyzed in this paper. The abstraction reactions of these systems are also calculated and compared with available literature data. Ċ5H9 radicals can be produced via Ḣ atom addition reactions to the pentadiene isomers and cyclopentene, and also by H-atom abstraction reactions from 1- and 2-pentene and cyclopentane. Comprehensive Ċ5H9 potential energy surface (PES) analyses and high-pressure limiting rate constants for related reactions have been explored in part I of this work ( J. Phys. Chem. A 2019, 123 (22), 9019-9052). In this work, a chemical kinetic model is constructed based on the computed thermochemistry and high-pressure limiting rate constants from part I, to further understand the chemistry of different C5H8 molecules. The most important channels for these addition reactions are discussed in the present work based on reaction pathway analyses. The dominant reaction pathways for these five systems are combined together to generate a simplified Ċ5H9 PES including nine reactants, 25 transition states (TSs), and nine products. Spin-restricted single point energies are calculated for radicals and TSs on the simplified PES at the ROCCSD(T)/aug-cc-pVTZ level of theory with basis set corrections from MP2/aug-cc-pVXZ (where X = T and Q). Temperature- and pressure-dependent rate constants are calculated using RRKM theory with a Master Equation analysis, with restricted energies used for minima on the simplified Ċ5H9 PES and unrestricted energies for other species, over a temperature range of 300-2000 K and in the pressure range 0.01-100 atm. The rate constants calculated are in good agreement with those in the literature. The chemical kinetic model is updated with pressure-dependent rate constants and is used to simulate the species concentration profiles for Ḣ atom addition to cyclopentane and cyclopentene. Through detailed analyses and comparisons, this model can reproduce the experimental measurements of species qualitatively and quantitatively with reasonably good agreement.