The role of low-lying conformers and pressure effect in kinetic modeling of hydrogen abstraction of tertiary amyl methyl ether by OH radicals

摘要

In this short communication, the kinetic discrepancy between calculation and experiment for the hydrogen abstraction reaction of t-amyl methyl ether by OH radicals is resolved by combining (i) an accurate potential energy surface, including the newly found lowest-lying structures of the reactant and transition states, explored at the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ level and (ii) a rigorous master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) rate model, which includes the corrections of the hindered internal rotation and tunneling effects, to account for pressure and temperature effects.