A molecular theory of collective orientational relaxation in pure and binary dipolar liquids

Chandra, Amalendu ; Bagchi, Biman (1989) A molecular theory of collective orientational relaxation in pure and binary dipolar liquids Journal of Chemical Physics, 91 (3). pp. 1829-1842. ISSN 0021-9606

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Official URL: http://jcp.aip.org/resource/1/jcpsa6/v91/i3/p1829_...

Related URL: http://dx.doi.org/10.1063/1.457088


A molecular theory of collective orientational relaxation of dipolar molecules in a dense liquid is presented. Our work is based on a generalized, nonlinear, Smoluchowski equation (GSE) that includes the effects of intermolecular interactions through a mean-field force term. The effects of translational motion of the liquid molecules on the orientational relaxation is also included self-consistently in the GSE. Analytic expressions for the wave-vector-dependent orientational correlation functions are obtained for one component, pure liquid and also for binary mixtures. We find that for a dipolar liquid of spherical molecules, the correlation function φ(k,t) for l=1, where l is the rank of the spherical harmonics, is biexponential. At zero wave-vector, one time constant becomes identical with the dielectric relaxation time of the polar liquid. The second time constant is the longitudinal relaxation time, but the contribution of this second component is small. We find that polar forces do not affect the higher order correlation functions (l>1) of spherical dipolar molecules in a linearized theory. The expression of φ(k,t) for a binary liquid is a sum of four exponential terms. We also find that the wave-vector-dependent relaxation times depend strongly on the microscopic structure of the dense liquid. At intermediate wave vectors, the translational diffusion greatly accelerates the rate of orientational relaxation. The present study indicates that one must pay proper attention to the microscopic structure of the liquid while treating the translational effects. An analysis of the nonlinear terms of the GSE is also presented. An interesting coupling between the number density fluctuation and the orientational fluctuation is uncovered.

Item Type:Article
Source:Copyright of this article belongs to American Institute of Physics.
Keywords:Smoluchowski Equation; Orientation; Relaxation; Binary Mixtures Liquids; Correlation Functions; Relaxation Time; Liquid Structure; Dielectric Properties
ID Code:4497
Deposited On:18 Oct 2010 07:41
Last Modified:28 Jan 2011 04:02

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