title: Molecular diffusion in liquid crystals and chiral discrimination. I. Theory.
abstract: The possibility of using cholesteric phases for discriminating enantiomers of a chiral solute on the basis of their different transport properties, motivates the investigation of the translational diffusion by taking fully into account the roto-translational coupling. In this article a detailed theoretical analysis is presented for the transport properties evaluated according to the asymptotic limit of the mean-squared displacement. A general relation is derived for the transport coefficients, having as main ingredients the mean-field potential due to the mesophase, and the diffusion tensor with its purely translational and rotational components, and with the blocks describing the roto-translational coupling. The application of the theory to nematic phases shows that the roto-translational coupling generates a dynamical contribution reducing the transport coefficients evaluated by taking into account only the translational diffusion components in the center of diffusion. The theory is also specialized to a cholesteric phase with a given helical pitch for the director arrangement, in a form which is suitable for calculations of model systems of chiral solutes to be presented in a forthcoming paper.
authors.affiliation: Dipartimento di Scienze Chimiche and Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), Università di Padova, via Marzolo 1, I-35131 Padova, Italy.
authors.forename: Diego
authors.initials: D
authors.lastname: Frezzato
authors.forename: Giorgio J
authors.initials: GJ
authors.lastname: Moro
authors.forename: Claudio
authors.initials: C
authors.lastname: Zannoni