The dielectric virial expansion and the models of dipolar hard-sphere fluid

摘要

The virial expansion technique to determine the dielectric constant epsilon of dipolar hard-sphere fluid is developed. It is shown that the formalism allows to bring into agreement the results of Debye's, Onsager's, and Langevin's to the problem. The third virial coefficient of epsilon is considered as a series over dipolar parameter lambda=m(2)/d(3)kT. The terms up to O(lambda(11)) are calculated analytically providing a correct description of the third virial coefficient for small and intermediate values of lambda (0 <=lambda <= 4). The results of the dielectric virial series are compared with the Monte Carlo data for epsilon found by Matyushov and Ladanyi [J. Chem. Phys. 110, 994 (1999)]. The theory is in agreement with simulations only at small values of lambda <= 2. At higher polarities, the virial series diverges. Realization of the renormalization procedure permits to enlarge the range of applicability of the virial series. In this way, the new expression for the dielectric constant as a function of two dipolar parameters, lambda and y=4 pi nm(2)/9kT, has been found explicitly. The expression gives a perfect upper bound of the dielectric constant and is more reliable for determination of epsilon than the previously known ones. (C) 2007 American Institute of Physics.