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


Title:Hydrogen Abstraction from n-Butanol by the Hydroxyl Radical: High Level Ab Initio Study of the Relative Significance of Various Abstraction Channels and the Role of Weakly Bound Intermediates
Authors:Jerzy Moc and John M. Simmie, 2010
Abstract: We have investigated the mechanism of the reaction of H abstraction from n-butanol by the hydroxyl radical (HO•) using high level ab initio methods in conjunction with the correlation consistent basis sets up to quadruple-ζ quality (cc-pVQZ). This reaction is of significance in the atmosphere and combustion. The focus of the study has been on the relative importance of the abstractions from the specific n-butanol sites and on the role of reaction intermediates involved. Our results show that abstractions from the Cα and Cγ positions are kinetically most favored and nearly barrierless, with barrier height estimates of 0.10 and 0.47 kcal/mol, respectively, at the CCSD(T)/cc-pVQZ level. We have determined that the indicated barrier height order, Cα < Cγ < Cβ < Cδ < OH, parallels that for the n-butanol bond dissociation energies established recently. The kinetically and thermodynamically most favored Cα abstraction occurs via a mechanism including the formation of the n-butanol···HO• prereaction complex. The weakly bound postreaction complexes between the product radicals and H2O have been identified for all the specific site abstraction reactions, with their calculated CCSD(T) binding energies of up to about 3 kcal/mol after correcting for the basis set superposition error. G3 method has been found to yield consistent results with those obtained from the CCSD(T) calculations for the predicted orders of both the H abstraction barrier heights and their exothermicities.
ICHEC Project:BurnQuest: Towards a World Class Combustion Chemistry Centre
Publication:Journal of Physical Chemistry A (2010) 114(17): 5558–5564
URL: http://dx.doi.org/10.1021/jp1009065
Status: Published

return to publications list