The absorption spectra of the hydrated electron in 1.0 to 4.0 M LiCl or LiClO
4 deuterated water solutionswere measured by pulse radiolysis techniques from room temperature to 300
C at a constant pressure of 25MPa. The results show that when the temperature is increased and the density is decreased, the absorptionspectrum of the electron in the presence of a lithium cation is shifted to lower energies. Quantum classicalmolecular dynamics (QCMD) simulations of an excess electron in bulk water and in the presence of a lithiumcation 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 electrondestabilized by core repulsion. The study of s
p transition energies for the three p-excited states revealsthat for temperatures higher than room temperature, there is a broadening of each individual s
p absorptionband due to a less structured water solvation shell.