Orientational dynamics in supercooled glycerol computed from MD simulations: self and cross contributions.

The orientational dynamics of supercooled glycerol is probed using molecular dynamics simulations for temperatures ranging from 323 K to 253 K, through correlation functions of first and second ranks of Legendre polynomials, pertaining respectively to dielectric spectroscopy (DS) and depolarized dynamic light scattering (DDLS). The self, cross, and total correlation functions are compared with relevant experimental data. The computations reveal the low sensitivity of DDLS to cross-correlations, in agreement with what is found in experimental work, and strengthen the idea of directly comparing DS and DDLS data to evaluate the effect of cross-correlations in polar liquids. The analysis of the net static cross-correlations and their spatial decomposition shows that, although cross-correlations extend over nanometric distances, their net magnitude originates, in the case of glycerol, from the first shell of neighbouring molecules. Accessing the angular dependence of the static correlation allows us to get a microscopic understanding of why the rank-1 correlation function is more sensitive to cross-correlation than its rank-2 counterpart.

Kinetic Yvon-Born-Green theory of the linear dielectric constant and complex permittivity of isotropic polar fluids.

The theory of the linear static dielectric constant and linear complex permittivity of isotropic polar fluids is formulated starting from the coupled Langevin equations describing the rototranslational dynamics of long-range interacting molecules with thermal agitation and subjected to external forces and torques. To this aim, adequate reduced densities are introduced and equations governing their dynamics derived. In the equilibrium zero frequency limit, integral expressions for the Kirkwood correlation factor g_{K} are given, transparently showing that the popular method consisting in comparing g_{K} with 1 in order to deduce pair dipolar ordering has no serious theoretical grounding. In the dynamical situation, the complex permittivity spectrum of a simple liquid is shown to exhibit an infinite discrete set of relaxation times, some of which may have thermally activated behavior. The theory is also shown to contain all previous results derived in the area provided molecular inertial effects are ignored, so restricting the range of validity of the theory to frequencies much below the far-infrared region. Finally, the theory can be adapted without much effort to relaxation of interacting magnetic nanoparticles for which macroscopic magnetic anisotropy arising from the assembly of nanoparticles is neglected.

Temperature dependence of the Kirkwood correlation factor and linear dielectric constant of simple isotropic polar fluids.

The theory developed in an accompanying paper [Déjardin, Phys. Rev. E 105, 024109 (2022)10.1103/PhysRevE.105.024109] is used to compute the Kirkwood correlation factor of simple polar fluids of different nature. From this calculation, the theoretical static permittivity is readily obtained, which is compared with experimental values. This is accomplished by fitting only one parameter accounting for induction or dispersion forces and torques, which is necessarily connected with the individual molecular polarizability but not explicitly related to the physical properties due to the nonadditivity of such energies. Excellent agreement between theoretical and experimental static permittivities is obtained over a very broad temperature range for a number of associated and nonassociated liquids. Finally, limitations of the present theory are given.

Dynamic Kerr effect in a strong uniform AC electric field for interacting polar and polarizable molecules in the mean field approximation.

Analytical formulas for the electric birefringence response of interacting polar and anisotropically polarizable molecules due to a uniform alternating electric field are derived using Berne's forced rotational diffusion model [B. J. Berne, J. Chem. Phys. 62, 1154 (1975)] in the nonlinear version described by Warchol and Vaughan [J. Chem. Phys. 71, 502 (1979)]. It is found for noninteracting molecules that the signal consists of a frequency-dependent DC component superimposed on an oscillatory part with a frequency twice that of the AC driving field. However, unlike noninteracting molecules, the AC part strongly deviates from its dilute counterpart. This suggests a possible way of motivating new experimental studies of intermolecular interactions involving electro-optical methods and complementary nonlinear dielectric relaxation experiments.

External dc bias-field effects in the nonlinear ac stationary response of dipolar particles in a mean-field potential.

External dc bias-field effects on the nonlinear dielectric relaxation and dynamic Kerr effect of a system of permanent dipoles in a uniaxial mean-field potential are studied via the rotational Brownian motion model postulated in terms of the infinite hierarchy of differential-recurrence equations for the statistical moments f_{n}(t)=〈P_{n}〉(t) (the expectation value of the Legendre polynomials P_{n}). By solving these equations, the nonlinear dielectric and Kerr-effect ac stationary responses are evaluated for arbitrary dc field strength via perturbation theory in the ac field. Simple analytic equations based on the large separation of the time scales of the fast intrawell and slow overbarrier (interwell) relaxation processes are also derived.

Stochastic dynamics of collective modes for Brownian dipoles.

The individual motion of a colloidal particle is described by an overdamped Langevin equation. When rotational degrees of freedom are relevant, these are described by a corresponding Langevin process. Our purpose is to show that the microscopic local density of colloids, in terms of a space and rotation state, also evolves according to a Langevin equation. The latter can then be used as the starting point of a variety of approaches, ranging from dynamical density functional theory to mode-coupling approximations.