Temperature effect on vertical detachment energy of bulk hydrated electron by dielectric continuum theory

Abstract

In this work, vertical detachment energy (VDE), continuum slope (CS) and solvent reorganization energy (SRE) of solvated electrons in bulk liquids were calculated by the formulas derived from electron cavity model within the framework of dielectric continuum (DC) theory. The predicted VDE was in good agreement with the reported experimental data, which indicated that DC theory was a good approach to describe the energy level of solvated electrons in vertical detachment. Moreover, the effects of temperature on VDE, CS and SRE of bulk hydrated electron were discussed from 25 to $$500\,^{\circ }\hbox {C}$$ at an extreme pressure of 25 MPa. As temperature increases, VDE and CS were found to shift to lower energies (spectral red-shift), while SRE exhibited a maximum under supercritical condition and decreased significantly to about 0.53 eV at $$500\, ^{\circ }\hbox {C}$$ . Those significant energy changes near $$375\, ^{\circ }\hbox {C}$$ may be caused by extraordinary water properties at the critical point.