Physics – Condensed Matter – Statistical Mechanics
Scientific paper
2008-10-10
Physics
Condensed Matter
Statistical Mechanics
6 pages
Scientific paper
10.1103/PhysRevE.79.041104
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.
Stepanow Semjon
Thurn-Albrecht Thomas
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