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Effect of water density on the absorption maximum of hydrated electrons in sub- and supercritical water up to 400 $$^{circ}$$C

亜臨界及び400$$^{circ}$$Cまで超臨界水中における水和電子の吸収ピークに対する密度効果

Jay-Gerin, J.-P.*; Lin, M.; 勝村 庸介; He, H.*; 室屋 裕佐*; Meesungnoen, J.*

Jay-Gerin, J.-P.*; Lin, M.; Katsumura, Yosuke; He, H.*; Muroya, Yusa*; Meesungnoen, J.*

本研究では重水中25MPa下での、380, 390, 400$$^{circ}$$Cにおける水和電子の密度依存性の吸収スペクトル測定を行うとともに、その結果と報告値を比較検討した。その結果、25MPa一定圧力下では吸収ピークエネルギーは温度の上昇とともに、超臨界水状態も含め単調に減少するのに対し、一定密度(0.2, 0.65g/cm$$^{3}$$)では臨界点近傍で最小値を示すことを見いだした。この挙動は超臨界水中の局所密度や局所の構造の揺らぎの観点から説明できる。

In this work, we measure the density dependent absorption spectra of hydrated electron in D$$_{2}$$O at 380, 390, and 400$$^{circ}$$C, and then compare with the literature data for subcritical water. The results show that at a fixed pressure (25 MPa), ${it E$_{A-max}$}$ decreases monotonically with increasing temperature in passing through the liquid-supercritical water (SCW) phase transition at t$$_{c}$$. By contrast, at a fixed density (0.2 and 0.65g/cm$$^{3}$$), ${it E$_{A-max}$}$ exhibits a minimum near ${it t$_{c}$}$. These behaviors are explained in terms of local density and configurational fluctuations of water structure in SCW.

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パーセンタイル:61.14

分野:Chemistry, Physical

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