Temperature effect on the absorption spectrum of the hydrated electron paired with a lithium cation in deuterated water.
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.
Lin
Mingzhang
M
Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113-8656, Japan.
Kumagai
Yuta
Y
Lampre
Isabelle
I
Coudert
François-Xavier
FX
Muroya
Yusa
Y
Boutin
Anne
A
Mostafavi
Mehran
M
Katsumura
Yosuke
Y