Bridging the gap between phenomenology and microscopic theory: asymptotes in nematic colloids.
The Ornstein-Zernike equation is applied to nematic colloids with up-down symmetry to determine how the electrostatic analogy and other phenomenological results appear in molecular theory. In contrast to phenomenological approaches, the molecular theory does not assume particular boundary conditions (anchoring) at colloidal surfaces. For our molecular parameters the resulting anchoring appears to be realistic, neither rigid nor infinitely weak. For this case, the effective force between a colloidal pair at large separation remains essentially constant over the entire region of nematic stability. We show that a simple van der Waals approximation gives a potential of mean force that in some important aspects is similar to the phenomenological results obtained in the limit of weak anchoring; at large separations the potential varies as Sigma8, where Sigma is the colloidal diameter. In contrast, the more sophisticated mean spherical approximation yields a Sigma6 dependence consistent with phenomenological calculations employing rigid boundary conditions. We show that taking proper account of the correlation (or magnetic coherence) length xi inherent in the nematic sample is essential in an analysis of the Sigma dependence. At infinite xi the leading Sigma dependence is Sigma6, but this shifts to Sigma8 when xi is finite. The correlation length also influences the orientational behavior of the effective interaction. The so-called quadrupole interaction that determines the long-range behavior at infinite xi transforms into a superposition of screened "multipoles" when xi is finite. The basic approach employed in this paper can be readily applied to a broad range of physically interesting systems. These include patterned and nonspherical colloids, colloids trapped at interfaces, and nematic fluids in confined geometries such as droplets.
Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada.
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Sokolovska
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Sokolovskii
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Patey