ハイブリッド量子力学/分子力場計算を用いた超臨界水中でのグリセルアルデヒドの変換反応

概要

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Ab initio density functional theory and quantum mechanics / molecular mechanics (QM/MM) simulation were performed to elucidate catalytic role of water on glyceraldehyde conversion in supercritical water (SCW). The reactant and solvent in a first solvation shell were treated as B3LYP / AUG-cc-pVDZ, and for the solvent molecules we used the flexible SPC-3P water model. A direct participation of water molecule on transition structure reduced activation energy barrier for the reaction. Threshold energy of retro-aldol reaction is the lowest among three pathways. We calculated solvation free energies by means of free energy perturbation method based on solvent-solvent and solute-solvent interactions to explain the effect of solution structure around solute. At high water density condition dehydration pathway is preferred reaction mechanism. However, the retro-aldol reaction mechanism was the preferred reaction pathway at low water densities in SCW. Solvation structure can be catalyzed dehydration reaction, but it can not be catalyzed retro-aldol reaction.
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