non-equllibrium dynamics of hydrogen-bonded molecular assembly

2022 Fiscal Year Final Research Report

• Project/Area Number: 20K05476
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Nagasaki University
• Principal Investigator: Shigemitsu Yasuhiro 長崎大学, 工学研究科, 教授 (50432969)
• Co-Investigator(Kenkyū-buntansha): 北條 博彦 東京大学, 生産技術研究所, 教授 (20357940)
• Project Period (FY): 2020-04-01 – 2023-03-31
• Keywords: 反応速度解析 / 動的溶媒効果 / 遷移状態理論

Outline of Final Research Achievements

The non-equilibrium dynamics of the molecular assembled systems shares the fundamental principles with the so-called dynamic solvent effects which arise in the chemical reactions in highly viscous solvents under high pressure, where the chemical equilibrium between solute and solvent system is violated. In the present theory-experiment joint studies on several soft materials, the non-equilibrium solvation theory developed by our group was applied to the hydrogen-bonded molecular assemblies. First, we were engaged in the preliminary analysis and simulation build-up. Then, the large-scale MD simulations (MS-TIS pathsampling calculations) were done to directly estimate the reaction rate constant which is compared and analyzed with the theoretical models and the experiments. Highly accurate QM calculations were done to analyze the polymorph-dependent luminescence of the inter/intra hydrogen-bonded HPIP molecules.

Free Research Field

反応有機化学

Academic Significance and Societal Importance of the Research Achievements

遷移状態理論（TST）で解釈できない特異的な反応・立体選択性を示す非平衡反応は、有機合成化学において極めて重要であるだけでなく、プロトンリレーや光合成電子移動など基礎生化学的過程においても本質的な役割を果たしている。非平衡反応機構研究の展望として、現象論的マクロモデルを脱皮して、分子間相互作用に遡って動的溶媒効果の微視的起源を解明し、さらには非平衡反応の制御という応用展開へと向かうと思われる。本研究の成果をさらに発展させ、分子レベル知見から非平衡反応速度定数を予測することができれば、動的溶媒効果の本質的解明・非平衡反応の制御・さらには工業化学展開への道が拓けると期待される。