Facultad de Ciencias, Universidad Nacional Autónoma de México, Circuito Exterior de Ciudad Universitaria, D.F. 04510, Mexico.
J Chem Phys. 2010 Feb 28;132(8):084502. doi: 10.1063/1.3314728.
Mesoscopic nonequilibrium thermodynamics is used to formulate a model describing nonhomogeneous and non-Debye dielectric relaxation. The model is presented in terms of a Fokker-Planck equation for the probability distribution of noninteracting polar molecules in contact with a heat bath and in the presence of an external time-dependent electric field. Memory effects are introduced in the Fokker-Planck description through integral relations containing memory kernels, which in turn are used to establish a connection with fractional Fokker-Planck descriptions. The model is developed in terms of the evolution equations for the first two moments of the distribution function. These equations are solved by following a perturbative method from which the expressions for the complex susceptibilities are obtained as a function of the frequency and the wave number. Different memory kernels are considered and used to compare with experiments of dielectric relaxation in glassy systems. For the case of Cole-Cole relaxation, we infer the distribution of relaxation times and its relation with an effective distribution of dipolar moments that can be attributed to different segmental motions of the polymer chains in a melt.
介观非平衡热力学用于构建一个描述非均匀和非德拜介电弛豫的模型。该模型以福克-普朗克方程的形式呈现,用于描述与热浴接触的非相互作用极性分子在外部时变电场中的概率分布。通过包含记忆核的积分关系,在福克-普朗克描述中引入了记忆效应,这些关系反过来又与分数福克-普朗克描述建立了联系。该模型是根据分布函数的前两个矩的演化方程发展起来的。通过遵循微扰方法求解这些方程,得到了复介电常数作为频率和波数函数的表达式。考虑了不同的记忆核,并将其用于与玻璃态系统中介电弛豫的实验进行比较。对于科尔-科尔弛豫的情况,我们推断了弛豫时间的分布及其与有效偶极矩分布的关系,这可以归因于聚合物链在熔体中的不同段运动。