Alkyl hydrogen atom abstraction reactions of the CN radical with ethanol

Abstract

We present a study of the abstraction of alkyl hydrogen atoms from the β and α positions of ethanol by the CN radical in solution using the Empirical Valence Bond (EVB) method. We have built separate 2 × 2 EVB models for the H and H reactions, where the atom transfer is parameterized using ab initio calculations. The intra- and intermolecular potentials of the reactant and product molecules were modelled with the General AMBER Force Field, with some modifications. We have carried out the dynamics in water and chloroform, which are solvents of contrasting polarity. We have computed the potential of mean force for both abstractions in each of the solvents. They are found to have a small and early barrier along the reaction coordinate with a large energy release. Analyzing the solvent structure around the reaction system, we have found two solvents to have little effect on either reaction. Simulating the dynamics from the transition state, we also study the fate of the energies in the HCN vibrational modes. The HCN molecule is born vibrationally hot in the CH stretch in both reactions and additionally in the HCN bends for the H abstraction reaction. In the early stage of the dynamics, we find that the CN stretch mode gains energy at the expense of the energy in CH stretch mode.

Proton Tunneling in a Two-Dimensional Potential Energy Surface with a Non-linear System-Bath Interaction: Thermal Suppression of Reaction Rate

“…We notice that our model also includes a linear coupling of the RPV mode which has been found to be quite significant in molecular dynamics simulation of hydrogen atom transfer. 60 In order to calculate the reaction rate, we employ the eigenstates representation for both ĤS and V (q, R). (See Appendix A.…”