Morozov Konstantin I
Institute of Continuous Media Mechanics, UB of Russian Academy of Sciences, 614013 Perm, Russia.
J Chem Phys. 2007 May 21;126(19):194506. doi: 10.1063/1.2736370.
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<or=lambda<or=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<or=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.
开发了用于确定偶极硬球流体介电常数ε的维里展开技术。结果表明，该形式体系能够使德拜、昂萨格和朗之万对该问题的结果达成一致。将ε的第三维里系数视为偶极参数λ = m²d³/kT的级数。解析计算了直至O(λ¹¹)的项，对于λ的小值和中间值(0≤λ≤4)，能正确描述第三维里系数。将介电维里级数的结果与马秋绍夫和拉达尼[《化学物理杂志》110, 994 (1999)]得到的ε的蒙特卡罗数据进行了比较。该理论仅在λ≤2的小值时与模拟结果一致。在更高极性下，维里级数发散。实施重整化程序可以扩大维里级数的适用范围。通过这种方式，明确得到了作为两个偶极参数λ和y = 4πnm²/9kT的函数的介电常数新表达式。该表达式给出了介电常数的完美上限，并且在确定ε时比先前已知的表达式更可靠。
