Theoretical study on mechanisms of the high-temperature reactions C2H3 + H2O and C2H4 + OHElectronic supplementary information (ESI) available: Figures of optimized geometries of the fragments of C2H5O radicals, C2H5O isomers and C2H5O transition states and table of harmonic vibration frequencies of C2H3, H2O, TSR/P1, C2H4 and OH. See http://www.rsc.org/suppdata/cp/b1/b109758j/

Abstract

The potential energy surface of the radical-molecule reaction C2H3 + H2O in the gas phase is explored at the 6-31G(d,p) and 6-311G(d,p) B3LYP and single-point QCISD(T)/6-311G(2df,p) levels. The most favorable channel is the direct H-abstraction from H2O to C2H3 leading to product P1 C2H4 + OH, whereas the other channels leading to the products P2 CH3 + CH2O, P3 CH3CHO + H, P4cis-CH2CHOH + H and P4′ trans-CH2CHOH + H are kinetically much less competitive. For the direct H-abstraction channel, high-level energetic calculations at the QCISD(T)/6-311G(2df,p), QCISD(T)/6-311+G(2df,2p) and G2 levels using the B3LYP/6-31G(d,p) and QCISD/6-31G(d,p) optimized geometries are further performed to estimate the thermal rate constants over a wide temperature range 200–5000 K for comparison with future laboratory measurements. The calculated barrier heights at the QCISD(T)/6-311+G(2df,2p) and G2 levels based on the QCISD/6-31G(d,p) geometries with zero-point vibrational energy (ZPVE) correction are 12.6 and 13.0 kcal mol−1, respectively. The results indicate that the C2H3 + H2O reaction might play an important role at high temperatures (T > 1800 K) in the presence of gaseous water and should be incorporated in the C2H3-modeling of hydrocarbon-fuel combustion processes. Discussions are also made in comparison with the analogous reactions C2H3 + H2 and C2H + H2O. While the addition-elimination mechanism of another important radical-molecule reaction C2H4 + OH has been the subject of extensive theoretical and experimental studies, its H-abstraction process leading to C2H3 + H2O has received little attention. For the C2H4 + OH → C2H3 + H2O channel, our calculations predict ZPVE-corrected barriers, 5.6 and 5.4 kcal mol−1, respectively, at the QCISD(T)/6-311+G(2df,2p)//QCISD/6-31G(d,p) and G2//QCISD/6-31G(d,p) levels, and reveal its importance at high temperatures (T > 560 K). In the range 720–1173 K, the calculated high-level rate constants are quantitatively in good agreement with the measured values. However, our calculated activation energy, 9.5 and 9.3 kcal mol−1 at the QCISD(T)/6-311+G(2df,2p)//QCISD/6-31G(d,p) and G2//QCISD/6-31G(d,p) levels with ZPVE correction, respectively, suggests that the experimentally determined value 4–5 kcal mol−1 may be underestimated and future rate constant measurements over a wide temperature range including T > 1200 K may be desirable.