Logo of Science Foundation Ireland  Logo of the Higher Education Authority, Ireland7 CapacitiesGPGPU Research Projects
Ireland's High-Performance Computing Centre | ICHEC
Home | News | Infrastructure | Outreach | Services | Research | Support | Education & Training | Consultancy | About Us | Login

Publication

Title:Theoretical kinetics for the decomposition of iso-butanol and related (CH3)2CH + CH2OH reactions
Authors:Chong-Wen Zhou, Stephen J. Klippenstein, John M. Simmie, Henry J. Curran, 2013
Abstract: 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)2C.H+C.H2OH(k1), CH3C.HCH2OH+C.H3(k2) and (CH3)2C=CH2 + 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)2C.H+C.H2OH is dominant, while the formations of CH3C.HCH2OH+C.H3 and (CH3)2C=CH2 + H2O together contribute less than 20%. The bi-molecular recombination of (CH3)2C.H+C.H2OH has also been investigated, with the formation of iso-butanol found to be dominant at high pressure and the production of CH3C.HCH2OH+C.H3 favored at low pressure.
ICHEC Project:Computational Quantum Chemistry and Kinetics of the Interaction of OH and HO2 Radicals with Biofuels
Publication:Proceedings of the Combustion Institute (2013) 34 501-509
URL: http://www.sciencedirect.com/science/article/pii/S1540748912001423
Keywords: Iso-butanol; Thermal decomposition; Ab initio; Variable-reaction-coordinate transition state theory
Status: Published

return to publications list