Identification of electronic intermolecular electrostatic interactions that can significantly enhance poling-induced order is important to the advancement of the field of organic electro-optics. Here, we demonstrate an example of such improvement achieved through exploitation of the interaction of coumarin pendant groups in chromophore-containing macromolecules. Acentric order enhancement is explained in terms of lattice-symmetry effects, where constraint of orientational degrees of freedom alters the relationship between centrosymmetric and acentric order. We demonstrate both experimentally and theoretically that lattice dimensionality can be defined using the relationship between centrosymmetric order and acentric order. Experimentally: Acentric order is determined by attenuated total reflection measurement of electro-optic activity coupled with hyper-Rayleigh scattering measurement of molecular first hyperpolarizability, and centrosymmetric order is determined by the variable angle polarization referenced absorption spectroscopy method. Theoretically: Order is determined from statistical mechanical models that predict the properties of soft condensed matter.

Coarse-grained models of molecular interactions are of interest because they convey the essence of molecular interactions in simple and easy to understand form. However, coarse-grained models fail to adequately predict some material properties, such as the failure of the Stockmayer model to reproduce the dielectric behavior of highly polar liquids. We examine the behavior of the Stockmayer fluid over a range of dipole densities that covers known organic solvents, as well as that of an ellipsoidal Stockmayer-like fluid, using NVT rigid-body Monte Carlo simulations. Both fluids are examined under different electrostatic boundary conditions and ensemble sizes. While the Stockmayer model predicts that liquids of similar dipole density to acetonitrile would be ferroelectric and have a dielectric constant far higher than shown by experiment, the ellipsoidal model provides a better accounting of dielectric behavior. This result bodes well for the use of coarse-grained solvent models for large-scale simulations.

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The Stockmayer fluid, composed of dipolar spheres, has a well-known isotropic-ferroelectric phase transition at high dipole densities. However, there has been little investigation of the ferroelectric transition in nearly spherical fluids at dipole densities corresponding to those found in many polar solvents and in guest-host organic electro-optic materials. In this work, we examine the transition to ordered phases of low-aspect-ratio spheroids under both unperturbed and poled conditions, characterizing both the static dielectric response and thermodynamic properties of spheroidal systems. Spontaneous ferroelectric ordering was confined to a small region of aspect ratios about unity, indicating that subtle changes in sterics can have substantial influence on the behavior of coarse-grained liquid models. Our results demonstrate the importance of molecular shape in obtaining even qualitatively correct dielectric responses and provide an explanation for the success of the Onsager model as a phenomenological representation for the dielectric behavior of polar organic liquids.

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