複雑な系における微視的溶媒和に関する理論的研究: 遷移金属錯体の反応とイオン液体中の化学現象

京都大学0048新制・課程博士博士(工学)甲第17525号工博第3684号新制||工||1560(附属図書館)30291京都大学大学院工学研究科分子工学専攻(主査)教授 佐藤 啓文, 教授 今堀 博, 教授 山本 量一学位規則第4条第1項該当Doctor of Philosophy (Engineering)Kyoto UniversityDFA

A theoretical study of the liquid structure of nitromethane with RISM method

An integral equation theory for molecular liquids, reference interaction site model (RISM), was applied to understand the liquid structure of nitromethane, which is extensively used as a solvent. In the theory, liquid structure is described by a set of pair correlation functions. With the aid of ab initio molecular orbital calculations, representative peaks were able to be related to specific configurations of molecules

Ab Initio Study on an Excited-State Intramolecular Proton-Transfer Reaction in Ionic Liquid

An excited-state intramolecular proton transfer (ESIPT) reaction of 4′-<i>N</i>,<i>N</i>-dimethylamino-3-hydroxyflavone in room temperature ionic liquid is theoretically investigated using RISM-SCF-SEDD, which is a hybrid method of molecular liquid theory and ab initio molecular orbital theory. The photo-excitation and proton-transfer processes are computed by considering the solvent fluctuation. The calculated absorption and emission energy are in good agreement with the experiments. The changes in the dipole moment indicate that the drastic solvation relaxation is accompanied by the excitation and an ESIPT process, which is consistent with the remarkable dynamic Stokes shift observed in the experiments. We calculated the nonequilibrium free-energy contour as a function of the proton coordinate and the solvation coordinate. We conclude that although immediately after the excitation the barrier height of the ESIPT process is relatively small, the barrier becomes larger as the solvation relaxation to the excited normal state proceeds. The solvation relaxation process is also investigated on the basis of microscopic solvation structure obtained by RISM calculations