Thermochemistry of radicals formed by hydrogen abstraction from 1-butanol, 2-methyl-1-propanol, and butanal.

Ewa Papajak, Prasenjit Seal, Xuefei Xu, Donald G Truhlar

Index: J. Chem. Phys. 137(10) , 104314, (2012)

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Abstract

We calculate the standard state entropy, heat capacity, enthalpy, and Gibbs free energy for 13 radicals important for the combustion chemistry of biofuels. These thermochemical quantities are calculated from recently proposed methods for calculating partition functions of complex molecules by taking into account their multiple conformational structures and torsional anharmonicity. The radicals considered in this study are those obtained by hydrogen abstraction from 1-butanol, 2-methyl-1-propanol, and butanal. Electronic structure calculations for all conformers of the radicals were carried out using both density functional theory and explicitly correlated coupled cluster theory with quasipertubative inclusion of connected triple excitations. The heat capacity and entropy results are compared with sparsely available group additivity data, and trends in enthalpy and free energy as a function of radical center are discussed for the isomeric radicals.