Abstract
A theoretical treatment is performed of the mechanism (suggested in N. F. Bunkin andA. V. Lobeev, Z. Phys. Chem. 214, 269 (2000)) of ionic effect on the Rayleigh line wing under conditions of light scattering by liquid electrolytic solutions. The mechanism consists essentially in that the fluctuation electric field caused by Brownian motion of ions dissolved in a liquid leads, because of the Kerr polarization effect, to fluctuations of optical anisotropy of the scattering medium. The spectral characteristics of the Rayleigh line wing are obtained using the fluctuation-dissipative theorem as applied to equilibrium thermal electromagnetic field. Expressions are derived for the integral intensity and spectral width (Δν) of the Rayleigh line wing in terms of parameters of liquid solution such as the temperature T, the viscosity η, the concentration of dissolved ions ni, and the coefficient of their diffusion Di. It is demonstrated that Δν ∝ exp(−W/2T), where W is the activation energy of ion mobility bi = Di/T. The possible region of validity of developed theoretical concepts as applied to the experimental data for the Rayleigh line wing in electrolytic solutions is discussed.
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