Theoretical Study on Abstraction and Addition Reaction Kinetics for a Medium-Size Unsaturated Methyl Ester: Methyl-3-hexenoate + H/OH Radicals.

Abstract

Combustion chemistry of methyl esters with long alkyl chains and different degrees of unsaturation has been of particular interest for biodiesel combustion. Methyl-3-hexenoate (mhx3d) with a medium-size unsaturated aliphatic chain is regarded as a valuable surrogate of biodiesel components. Here, the abstraction and addition reaction kinetics of mhx3d + H/OH radicals are comprehensively investigated. An accurate and efficient exchange-correlation density functional M06-2X/ma-TZVP is validated by the DLPNO-CCSD(T)/CBS(T-Q) benchmark calculations and is used for the multistructural search, geometry optimization, potential energy profiles, and direct dynamic calculations. The multistructural torsional (MS-T) anharmonicity, variational effects, and tunneling effects including one-dimensional Winger tunneling, multidimensional zero-curvature tunneling (ZCT), and small-curvature tunneling (SCT) are also evaluated in rate coefficient calculations. The existence of reactant complexes of the abstraction and addition reactions is neglected for mhx3d + H due to weak van der Waals interaction but is considered for mhx3d + OH. Therefore, a pre-equilibrium model is employed to obtain the rate coefficients for mhx3d + OH. The calculation results show that the MS-T factor ranges from 0.29 to 11.41, the tunneling transmission coefficient calculated by SCT is in the range of 1.0-4.0, and the recrossing transmission coefficient is between 0.65 and 1.0. Moreover, the two OH-addition reactions exhibit negative temperature coefficient behavior. The branching ratios show that the H/OH-addition reactions are dominant at lower temperature, especially for mhx3d + H. Rate coefficients of the title reactions are fitted in terms of a modified three-parameter Arrhenius expression.