Reaction Ergodography for Unimolecular Decomposition of Ethanol

Article abstract of DOI:10.1021/ja00320a006

Some unimolecular decomposition paths of ethanol were analyzed by ab initio MO calculations in relation to the mode selective chemical reactions.The geometries and energies of the reactants, transition states, reaction intermediates, and products have been determined for five elementary reaction processes on the singlet potential energy surface of the ground state.The most energetically preferable path is the one for the formation of ethylene.Reaction ergodography along the intrinsic reaction coordinate (IRC) for the decomposition path leading to ethylene clarified two distinct roles of the vibrational modes of ethanol: (1) the vibrational mode excited by the CO2 laser corresponds to the direction of the reaction path to ethylene and (2) the vibrational mode excited by the HF laser plays a role of energy transfer to the decomposing path to ethylene.