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In the present paper, the fundamental problem of calculating the electric field gradient (EFG) experienced by a highly idealized solute, represented by a general point quadrupole immersed in an anisotropic uniaxial medium, has been tackled. Following a generalized reaction field approach (based upon the original ideas and the “mean-field philosophy” due to Kirkwood and Onsager) in the linear response approximation, a closed analytical expression of the EFG has been derived (to the best of our knowledge, for the first time). The obtained expression is particularly simple and elegant, also thanks to the oversimplifying approximation that the virtual cavity containing the solute is assumed to be perfectly spherical. This compact and manageable formula, obtained by a rigorous mathematical derivation (unlike other mean-field phenomenological models previously suggested in literature) can be useful to investigate and better understand a likely orientational mechanism, partly responsible for the ordering of small solutes dissolved in nematic mesophases, based on the interaction between the electric quadrupole of the solute and the electric field gradient of the anisotropic uniaxial medium (in the next paper of this issue, the formulation obtained in this work is widely tested on a variety of uniaxial and biaxial solutes dissolved in different nematic solvents). [ABSTRACT FROM AUTHOR]

In the previous paper of this issue, [Celebre, G.; Ionescu, A.J. Phys. Chem. Bdoi: 10.1021/jp907310g], following a generalized reaction field approach in the linear response approximation, we were successful in obtaining an analytical compact expression for the mean-field anisotropic orientational potential UQ−EFGtheoretically experienced by a highly idealized nonionic and apolar solute, considered as a point quadrupole immersed in a uniaxial polarizable continuum medium (model of a nematic solvent comprised of dipolar mesogenic molecules). The term UQ−EFGdescribes the electrostatic interaction between the electric quadrupole of the solute and the electric field gradient induced at the solute by the surrounding medium polarized by the distribution of electric charges representing the quadrupolar solute itself. In the present paper, the obtained potential has been considered as an additional orientational interaction contributing to the solute ordering, besides the well-recognized and very effective “short-range” (size-and-shape-dictated) mechanisms. Since in our theory the solvent is characterized by its dielectric tensor, the model has been widely tested by taking as references the experimental order parameters of several uniaxial and biaxial different small rigid probe molecules (H2, N2, acetylene, allene, propyne, benzene, hexafluorobenzene, 1,4-difluorobenzene, and norbornadiene) dissolved in the nematic solvents ZLI1132 (Δε ≫ 0) and EBBA (Δε < 0); moreover, the order parameters of the same solutes in the so-called nematic “magic mixture” (45 wt % EBBA + 55 wt % ZLI1132), where the short-range orientational effects are commonly believed to be very dominant, have been conventionally assumed as reference of the absence of electrostatic orientational effects. The experimental order parameters of the treated solutes, obtained in the past by liquid crystal NMR and available from literature, have been then compared with those theoretically predicted by our theoretical approach in order to obtain useful hints about two basic points, (a) the real physical nature of the interactions (other than the “size-and-shape”) involved in the orientational mechanisms and (b) the conceptual effectiveness of the suggested mean-field approach in describing this kind of phenomena. Successes and failures of the approach in the predictions are discussed at length, along with their possible reasons and implications. [ABSTRACT FROM AUTHOR]