High-Accuracy Heats of Formation for Alkane Oxidation: From Small to Large via the Automated CBH-ANL Method.

It is generally challenging to obtain high-accuracy predictions for the heat of formation for species with more than a handful of heavy atoms, such as those of importance in standard combustion mechanisms. To this end, we construct the CBH-ANL approach and illustrate that, for a set of 194 alkane oxidation species, it can be used to produce Δ(0 K) values with 2σ uncertainties of 0.2-0.

Hierarchical Study of the Reactions of Hydrogen Atoms with Alkenes: A Theoretical Study of the Reactions of Hydrogen Atoms with C-C Alkenes.

The present study complements our previous studies of the reactions of hydrogen atoms with C alkene species including 1- and 2-pentene and the branched isomers (2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene), by studying the reactions of hydrogen atoms with C-C alkenes (ethylene, propene, 1- and 2-butene, and isobutene). The aim of the current work is to develop a hierarchical set of rate constants for Ḣ atom addition reactions to C-C alkenes, both linear and branched, which can be used in the development of chemical kinetic models. High-pressure limiting and pressure-dependent rate constants are calculated using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory and a one-dimensional master equation (ME).

Theoretical Study of the Reaction of Hydrogen Atoms with Three Pentene Isomers: 2-Methyl-1-butene, 2-Methyl-2-butene, and 3-Methyl-1-butene.

This paper presents a comprehensive potential energy surface (PES) for hydrogen atom addition to and abstraction from 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene and the subsequent ß-scission and H atom transfer reactions. Thermochemical parameters for species on the ĊH potential energy surface (PES) were calculated as a function of temperature (298-2000 K), using a series of isodesmic reactions to determine the formation enthalpies. High-pressure limiting and pressure-dependent rate constants were calculated using Rice-Ramsperger-Kassel-Marcus theory with a one-dimensional master equation.

Hindered rotor benchmarks for the transition states of free radical additions to unsaturated hydrocarbons.

The hindered internal rotors of 32 transition states (TSs) formed through four free radicals, namely methyl, vinyl, ethyl, methoxy (ĊH3, Ċ2H3, Ċ2H5, CH3) additions to acetylene, ethylene, allene, propyne, and propene (C2H2/C2H4/C3H4-a/C3H4-p/C3H6) are studied. To validate the uncertainties of rate constants that stem from the use of different electronic structure methods to treat hindered rotors, the rotations of the newly formed C-C and/or C-O rotors in the transition states are calculated using commonly used DFT methods (B3LYP, M06-2X, ωB97X-D and B2PLYP-D3 with two Pople basis sets (6-31+G(d,p), 6-311++G(d,p)) and cc-pVTZ). The hindrance potential energies V(χ) calculated using the M06-2X/6-311++G(d,p) method are benchmarked at the CCSD(T), CCSD(T)-F12, DLPNO-CCSD(T) levels of theory with cc-pVTZ-F12 and cc-pVXZ (X = T, Q) basis sets and are extrapolated to the complete basis set (CBS) limit.

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

The temperature- and pressure-dependence of rate constants for several radicals and unsaturated hydrocarbons reactions (1,3-CH/1,4-CH/cyCH + Ḣ, CH + ĊH-a, CH + ĊH) are analyzed in this paper. The abstraction reactions of these systems are also calculated and compared with available literature data. ĊH 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.

Ab Initio/Transition-State Theory Study of the Reactions of ĊH Species of Relevance to 1,3-Pentadiene, Part I: Potential Energy Surfaces, Thermochemistry, and High-Pressure Limiting Rate Constants.

In this study, the reactions of ĊH radicals are theoretically investigated, with a particular emphasis on hydrogen atom addition reactions to 1,3-pentadiene (CH) to form ĊH radicals, although the subsequent isomerization and decomposition reactions of the ĊH radicals are also of direct relevance to the radicals formed from the pyrolysis and oxidation of species including pentene and cyclopentane. Moreover, H-atom abstraction reactions by hydrogen atoms from 1,3-pentadiene are also investigated. The geometries and frequencies of 63 potential energy surface (PES) minima and 88 transition states are optimized at the ωB97XD/aug-cc-pVTZ level of theory.

Theoretical, Experimental, and Modeling Study of the Reaction of Hydrogen Atoms with 1- and 2-Pentene.

Alkyl radicals are prominent in combustion chemistry as they are formed by hydrocarbon decomposition or from a radical attack on hydrocarbons. Accurate determinations of the thermochemistry and kinetics of their unimolecular isomerization and decomposition reactions and related addition reactions of alkenes are therefore important in simulating the combustion chemistry of virtually all hydrocarbon fuels. In this work, a comprehensive potential energy surface (PES) for Ḣ-atom addition to and abstraction from 1- and 2-pentene, and the subsequent C-C and C-H β-scission reactions, and H-atom transfer reactions has been considered.

Modeling Nitrogen Species as Pollutants: Thermochemical Influences.

To simulate emissions of nitrogen-containing compounds in practical combustion environments, it is necessary to have accurate values for their thermochemical parameters, as well as accurate kinetic values to describe the rates of their formation and decomposition. Significant disparity is observed in the literature for the former, and we therefore present herein high-accuracy ab initio gas-phase thermochemistry for 60 nitrogenous compounds, many of which are important in the formation and consumption chemistry of NOx species. Several quantum-chemical composite methods (CBS-APNO, G3, and G4) were utilized to derive enthalpies of formation via the atomization method.

Benchmarking Compound Methods (CBS-QB3, CBS-APNO, G3, G4, W1BD) against the Active Thermochemical Tables: Formation Enthalpies of Radicals.

The 298.15 K formation enthalpies of 38 radicals with molecular formula CxHyOz have been computed via the atomization procedure using the five title methods. The computed formation enthalpies are then benchmarked against the values recommended in the Active Thermochemical Tables (ATcT).

Revisiting the Kinetics and Thermodynamics of the Low-Temperature Oxidation Pathways of Alkanes: A Case Study of the Three Pentane Isomers.

This paper describes our developing understanding of low-temperature oxidation kinetics. We have investigated the ignition of the three pentane isomers in a rapid compression machine over a wide range of temperatures and pressures, including conditions of negative temperature coefficient behavior. The pentane isomers are small alkanes, yet have structures that are complex enough to allow for the application of their kinetic and thermochemical rules to larger molecules.

Benchmarking Compound Methods (CBS-QB3, CBS-APNO, G3, G4, W1BD) against the Active Thermochemical Tables: A Litmus Test for Cost-Effective Molecular Formation Enthalpies.

The theoretical atomization energies of some 45 CxHyOz molecules present in the Active Thermochemical Tables compilation and of particular interest to the combustion chemistry community have been computed using five composite model chemistries as titled. The species contain between 1-8 "heavy" atoms, and a few are conformationally diverse with up to nine conformers. The enthalpies of formation at 0 and 298.

The pyrolysis of 2-methylfuran: a quantum chemical, statistical rate theory and kinetic modelling study.

Due to the rapidly growing interest in the use of biomass derived furanic compounds as potential platform chemicals and fossil fuel replacements, there is a simultaneous need to understand the pyrolysis and combustion properties of such molecules. To this end, the potential energy surfaces for the pyrolysis relevant reactions of the biofuel candidate 2-methylfuran have been characterized using quantum chemical methods (CBS-QB3, CBS-APNO and G3). Canonical transition state theory is employed to determine the high-pressure limiting kinetics, k(T), of elementary reactions.

A high temperature and atmospheric pressure experimental and detailed chemical kinetic modelling study of 2-methyl furan oxidation.

An experimental ignition delay time study for the promising biofuel 2-methyl furan (2MF) was performed at equivalence ratios of 0.5, 1.0 and 2.