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

Kumagai, Yuta   ; Lin, M.; Lampre, I.*; Mostafavi, M.*; Muroya, Yusa*; Katsumura, Yosuke

The absorption spectra of the hydrated electron in concentrated LiCl, LiClO, LiSO, MgCl and Mg(ClO) deuterated water solutions were measured by pulse radiolysis techniques from room temperature to 300 C at a constant pressure of 25 MPa. As salt effects, shifts to shorter wavelengths and broadening of the absorption band of the solvated electron were observed at room temperature. At elevated temperatures, similar spectral shifts were observed. The broadening of the spectrum, on the other hand, becomes smaller with increasing temperature. These result indicate that high concentration of salts not only form an ion atmosphere to cause the spectral shifts, but also affect the solvation structure of an electron. The smaller broadening at elevated temperatures suggest that a decrease in the density expand the distance between solvated electron and surrounding ions, and that therefore the effect on the solvation structure becomes smaller.