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Statistical mechanical description of liquid systems in an electric field

by: Semjon Stepanow, Thomas T. Albrecht
Physical Review E, Vol. 79, No. 4. (Apr 2009), 041104, doi:10.1103/physreve.79.041104  Key: citeulike:4312708

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Abstract

We formulate the statistical mechanical description of liquid systems for both polarizable and polar systems in an electric field in the 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 Q̃N(E) in the E ensemble is given in an exact form as a factor in the integrand of Q̃N(E). We calculate the contribution of the electric field to the Ornstein-Zernike formula for the scattering function in the 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.


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