Journal of Physical Chemistry, Vol.98, No.38, 9649-9656, 1994
Temperature-Dependence of the Stability of a Hydrated Electron - An Integral-Equation Study
The excess electron in liquid water has been studied by using integral equation theories, the reference interaction site model (RISM)-polaron theory, and the extended RISM theory. A renormalized integral equation based on the closure proposed by Laria et al. (J. Chem. Phys. 1991, 95, 4444)is presented. Special attention has been paid to the temperature dependence of the stability of the excess electron. : The temperature dependence of the average potential energy and the cavity formation energy of the excess electron has exhibited extrema similar to those observed in various thermodynamic properties of pure water. The correlation between the behavior of the solvation thermodynamic quantities and the structure of liquid water is discussed. The observed red shift of the peak of the optical absorption spectrum with increasing temperature has been successfully reproduced.
Keywords:EXTENDED RISM EQUATION;EXCESS ELECTRONS;SIMPLE FLUIDS;ABSORPTION SPECTRUM;POLARON THEORY;SIMULATION;SOLVATION;SOLVENTS;MODELS