TY - JOUR
T1 - Theoretical kinetics for the decomposition of iso-butanol and related (CH3)2 CH + CH2OH reactions
AU - Zhou, Chong Wen
AU - Klippenstein, Stephen J.
AU - Simmie, John M.
AU - Curran, Henry J.
PY - 2013
Y1 - 2013
N2 - The potential energy surface for the thermal decomposition of iso-butanol has been investigated using high level ab initio electronic structure methods. Temperature and pressure dependent rate coefficients for the three channels with the lower energy barriers, forming (CH3)2 CH + CH 2OH (k1), CH3 CHCH2OH+ CH 3 (k2) and (CH3)2C=CH 2+H2O (k3) were computed with the master equation method employing ab initio transition state theory estimates for the microcanonical rate coefficients. The two radical forming channels were treated with variable-reaction-coordinate transition state theory employing directly sampled CASPT2(2e,2o)/cc-pVDZ orientation dependent interaction energies coupled with one-dimensional basis set and relaxation corrections. The other channel was treated with conventional TST including Eckart tunneling and one-dimensional hindered rotor corrections. For temperatures higher than 1000 K and pressures of 1 Torr or greater, the direct C-C bond fission forming (CH3) 2 CH + CH2OH is dominant, while the formations of CH 3 CHCH2OH + CH3 and (CH3) 2C=CH2+H2O together contribute less than 20%. The bi-molecular recombination of (CH3)2 CH + CH 2OH has also been investigated, with the formation of iso-butanol found to be dominant at high pressure and the production of CH3 CHCH2OH + CH3 favored at low pressure.
AB - The potential energy surface for the thermal decomposition of iso-butanol has been investigated using high level ab initio electronic structure methods. Temperature and pressure dependent rate coefficients for the three channels with the lower energy barriers, forming (CH3)2 CH + CH 2OH (k1), CH3 CHCH2OH+ CH 3 (k2) and (CH3)2C=CH 2+H2O (k3) were computed with the master equation method employing ab initio transition state theory estimates for the microcanonical rate coefficients. The two radical forming channels were treated with variable-reaction-coordinate transition state theory employing directly sampled CASPT2(2e,2o)/cc-pVDZ orientation dependent interaction energies coupled with one-dimensional basis set and relaxation corrections. The other channel was treated with conventional TST including Eckart tunneling and one-dimensional hindered rotor corrections. For temperatures higher than 1000 K and pressures of 1 Torr or greater, the direct C-C bond fission forming (CH3) 2 CH + CH2OH is dominant, while the formations of CH 3 CHCH2OH + CH3 and (CH3) 2C=CH2+H2O together contribute less than 20%. The bi-molecular recombination of (CH3)2 CH + CH 2OH has also been investigated, with the formation of iso-butanol found to be dominant at high pressure and the production of CH3 CHCH2OH + CH3 favored at low pressure.
KW - Ab initio
KW - Iso-butanol
KW - Thermal decomposition
KW - Variable-reaction-coordinate transition state theory
UR - https://www.scopus.com/pages/publications/84873336051
U2 - 10.1016/j.proci.2012.06.034
DO - 10.1016/j.proci.2012.06.034
M3 - Article
SN - 1540-7489
VL - 34
SP - 501
EP - 509
JO - Proceedings of the Combustion Institute
JF - Proceedings of the Combustion Institute
IS - 1
ER -