Statistical mechanical description of liquid systems in electric field

Abstract

We formulate the statistical mechanical description of liquid systems for both polarizable and polar systems in an electric field in the $\mathbf{E}$-ensemble, which is the pendant to the thermodynamic description in terms of the free energy at constant potential. The contribution of the electric field to the configurational integral $\tilde{Q}_{N}(\mathbf{E})$ in the $\mathbf{E}$-ensemble is given in an exact form as a factor in the integrand of $\tilde{Q}_{N}(\mathbf{E})$. We calculate the contribution of the electric field to the Ornstein-Zernike formula for the scattering function in the $\mathbf{E}$-ensemble. As an application we determine the field induced shift of the critical temperature for polarizable and polar liquids, and show that the shift is upward for polarizable liquids and downward for polar liquids.