Ab Initio Kinetics for the Decomposition of α-Hydroxybutyl Radicals of n-Butanol

摘要

The decomposition kinetics of α-hydroxybutyl radicals of n-butanol was theoretically studied by using ab initio transition state theory based master equation analysis. Stationary points on the C_4H_9O potential energy surface were calculated at either the RQCISD(T)/CBS//B3LYP/6-311++G(d,p) level or the RQCISD(T)/CBS//CASPT2/aug-cc-pVDZ level. Rate coefficients were calculated over broad ranges of temperature (300-2500K) and pressure (1.3×10~(-3)-10~2atm) with the transition state theory-based multiwell master equation approach. The "well merging" phenomenon was observed and analyzed for its influence on the pressure-dependent rate coefficients. Comparison between the theoretical results with available experimental data shows excellent agreement.