Direct ab initio MD study on the hydrogen abstraction reaction of triplet state acetone from methanol molecule

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Solvent re-orientation process of triplet acetone-methanol complex and intermolecular hydrogen atom abstraction reaction on the triplet state energy surface, (CH3)2C=O (T1) + CH3OH → (CH3)2C-OH + CH2OH in gas phase, have been investigated by means of density functional theory (DFT) and direct ab-initio molecular dynamics (MD) methods. The static DFT calculation of hydrogen abstraction reaction at the T1 state showed that the transition state is 16.4 and 30.9 kcal/mol lower than the energy levels of S1 and S2 states, respectively, and 9.2 kcal/mol higher than the bottom of T1 state. The product state, (CH3)2C-OH--CH2OH, is 8.4 kcal/mol lower in energy than the level of T1 state. The direct ab-initio MD calculation showed that the product is rapidly formed within 150 fs and the separated products (CH3)2C-OH + CH2OH were formed. The mechanism of reaction dynamics of the triplet acetone-methanol complex was discussed on the basis of theoretical results.