Thermal rate constants and kinetic isotope effects of the H + H2O2 reactions: barrier height and reaction energy from single- and multireference methods

Abstract

Context: One of the more significant sub-mechanisms of H₂/O₂ combustion involves the reaction of hydrogen peroxide with hydrogen atoms (H + H₂O₂), resulting in the production of OH + H₂O (R1) and H₂ + HO₂ (R2) paths. Previous experimental and ab initio calculations reveal some variations in the barrier height for (R1). To improve the energetics of both (R1) and (R2), single reference and multireference ab initio methods are employed, and the rate constants and H/D kinetic isotope effects (KIEs) are calculated as a function of temperature. For (R1), the best results for the barrier height and reaction energies computed with the CASPT2(15,11)/aug-cc-pV6Z are 5.2 and - 70.3 kcal.mol^-1, respectively. CCSD(T)/aug-cc-pV5Z + CV (core-valence) calculations for (R2) give 9.7 and - 15.6 kcal.mol^-1 to those parameters. The CVT/SCT rate constants of both paths agree well with the fitted rate constants from uncertainty-weighted statistical analysis of the 14-mechanism of H₂/O₂. The kinetic isotopic effect (k^H/k^D) for the reaction D + H₂O₂ → DH + HO₂ was found to be 0.47, which is in excellent agreement with the experimental value of 0.43.

Methods: The structures of reactants, transition state, and products of (R1) and (R2) are calculated with the aug-cc-pVTZ basis set and M062X DFT, CCSD(T), and CASSCF methods. The barrier heights and reaction energies of (R1) and (R2) are computed using the M06-2X, CCSD(T), MRCI, and CASPT2 methods and various basis sets. The rate constants are calculated with the variational transition state theory including multidimensional tunneling corrections (VTST-MT), with potential energy surfaces built by the M06-2X/aug-cc-pVTZ approach.

Keywords: CASPT2; CCSD(T); H + H2O2; M06-2X surface; MRCI; Rate constants.