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Hydrated electron: computer simulation of a quantum particle in a classical fluid

Thesis/Dissertation ·
OSTI ID:7056534

The equilibrium properties of the hydrated electron are investigated using the Feynman Path Integral formulation of Quantum Statistical Mechanics combined with Molecular Dynamics computer simulations. In the framework of the model of liquid water used in these computations (SPC model), it is found that the electron gets localized in a cavity of 2.2 A surrounded by a diffuse shell of water molecules oriented in the average with the OH bonds toward the center of the cavity. Most of the features of the optical spectrum become clear through the study of the effect of the fluctuations of the liquid environment on the shape of the potential well trapping the electron. In particular, it is shown that the width of the spectrum is caused by inhomogeneous broadening. Moreover, the analysis of the characteristic decay times of the potential autocorrelation functions provides a possible explanation for the mechanism of diffusion of they hydrated electron. Finally, the computation of the magnetic susceptibility of the localized electron gives another way to estimate the radius of the electronic distribution inside of the trap.

Research Organization:
Wisconsin Univ., Madison (USA)
OSTI ID:
7056534
Country of Publication:
United States
Language:
English