Multi-path variational transition state theory for chiral molecules: the site-dependent kinetics for abstraction of hydrogen from 2-butanol by hydroperoxyl radical, analysis of hydrogen bonding in the transition state, and dramatic temperature dependence of the activation energy.

ABSTRACT: The goal of the present work is modeling the kinetics of a key reaction involved in the combustion of the biofuel 2-butanol. To accomplish this we extended multi-path variational transition state theory (MP-VTST) with the small curvature tunneling (SCT) approximation to include multistructural anharmonicity factors for molecules with chiral carbons. We use the resulting theory to predict the site-dependent rate constants of the hydrogen abstraction from 2-butanol by hydroperoxyl radical. The generalized transmission coefficients were averaged over the four lowest-energy reaction paths. The computed forward reaction rate constants indicate that hydrogen abstraction from the C-2 site has the largest contribution to the overall reaction from 200 K to 2400 K, with a contribution ranging from 9

SUBMITTER: Bao JL 

PROVIDER: S-EPMC5950756 | biostudies-literature | 2015 Oct

REPOSITORIES: biostudies-literature