title: Temperature effect on the absorption spectrum of the hydrated electron paired with a lithium cation in deuterated water.
abstract: The absorption spectra of the hydrated electron in 1.0 to 4.0 M LiCl or LiClO4 deuterated water solutions were measured by pulse radiolysis techniques from room temperature to 300 degrees C at a constant pressure of 25 MPa. The results show that when the temperature is increased and the density is decreased, the absorption spectrum of the electron in the 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 lithium cation 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 --> 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 --> p absorption band due to a less structured water solvation shell.
authors: Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113-8656, Japan.
authors: Mingzhang
authors: M
authors: Lin
authors: Yuta
authors: Y
authors: Kumagai
authors: Isabelle
authors: I
authors: Lampre
authors: François-Xavier
authors: FX
authors: Coudert
authors: Yusa
authors: Y
authors: Muroya
authors: Anne
authors: A
authors: Boutin
authors: Mehran
authors: M
authors: Mostafavi
authors: Yosuke
authors: Y
authors: Katsumura