Temperature effect on the absorption spectrum of the hydrated electron paired with a lithium cation in deuterated water

重水中における水和電子・リチウムイオンペアの吸収スペクトルに対する温度効果

Lin, M.; 熊谷 友多   ; Lampre, I.*; Coudert, F.*; 室屋 裕佐*; Boutin, A.*; Mostafavi, M.*; 勝村 庸介

Lin, M.; Kumagai, Yuta; Lampre, I.*; Coudert, F.*; Muroya, Yusa*; Boutin, A.*; Mostafavi, M.*; Katsumura, Yosuke

The absorption spectra of the hydrated electron in 1.0 to 4.0 M LiCl or LiClO DO solutions were measured by pulse radiolysis techniques from room temperature to 300C at a pressure of 25 MPa. The results show that when the temperature is increased and the density is decreased, the spectrum of the electron in presence of a lithium cation is shifted to lower energies. Quantum classical molecular dynamics (QCMD) simulations of an excess electron in bulk water and in the presence of a Li have been performed to compare with the experimental results. According to the QCMD simulations, the change in the shape of the spectrum is due to one of the three p-like excited states of the solvated electron destabilized by core repulsion. The study of s to p transition energies for the three p excited states reveals that for temperatures higher than room temperature, there is a broadening of each individual s to p absorption band due to a less structured water solvation shell.