Ambient reaction kinetics of atmospheric oxygenated organics with the OH radical: a computational methodology study

Abstract

The gas phase hydrogen abstraction reaction kinetics of short chained oxygenated hydrocarbons of atmospheric relevance has been studied using density functional theory, basis set extrapolation procedures, Møller–Plesset second order perturbation theory and Coupled-Cluster Singles Doubles. The rate constants for the reaction of the OH radical with nine different oxygenated compounds: CH₃OH, CH₃CH₂OH, H₂CO, CH₃CHO, CH₃COCH₃, CH₃OCH₃, HCOOH, CH₃COOH, HCOOCH₃ with a total of 18 individual hydrogen abstraction reactions have been computationally determined and compared to experimental data. The performance of DFT in predicting the imaginary vibrational frequency of the nuclear motion at the transition state has been evaluated to assess tunnelling effects using Wigner, Bell and Eckart tunnelling corrections. Several different hybrid methodologies utilizing DFT/MP2 structures, vibrational frequencies and explicitly correlated Coupled Cluster single point energy corrections have been investigated to identify an approach for obtaining reliable reaction kinetics. Our investigation shows that CCSD(T)-F12a/VTZ-F12//BH&HLYP/aug-cc-pVTZ using a Bell or Eckart tunnelling correction yields rate constants within a factor of ∼3 of experimental data and branching ratios within experimental uncertainty for the test set of short chained oxygenated compounds of atmospheric relevance.