We report the combined results of molecular dynamics simulations and theoretical calculations concerning various dynamical arrest transitions in a model system representing a dipolar fluid, namely, N (soft core) rigid spheres interacting through a truncated dipole-dipole potential. By exploring different regimes of concentration and temperature, we find three distinct scenarios for the slowing down of the dynamics of the translational and orientational degrees of freedom: At low (η = 0.2) and intermediate (η = 0.4) volume fractions, both dynamics are strongly coupled and become simultaneously arrested upon cooling. At high concentrations (η ≥ 0.6), the translational dynamics shows the features of an ordinary glass transition, either by compressing or cooling down the system, but with the orientations remaining ergodic, thus indicating the existence of partially arrested states. In this density regime, but at lower temperatures, the relaxation of the orientational dynamics also freezes. The physical scenario provided by the simulations is discussed and compared against results obtained with the self-consistent generalized Langevin equation theory, and both provide a consistent description of the dynamical arrest transitions in the system. Our results are summarized in an arrested states diagram which qualitatively organizes the simulation data and provides a generic picture of the glass transitions of a dipolar fluid. PACS numbers: xxxxxxxx yyyyyyyy

We investigate the static correlations of a dipolar fluid in terms of the irreducible coefficients of the spherical harmonic expansion of the static structure factor. To this end, we develop a theoretical framework based on a soft-core version of Wertheim’s solution of the mean spherical approximation (MSA), which renders the analytical determination of such coefficients possible. The accuracy of this approximation is tested by a comparison against the results obtained with the assistance of extensive molecular dynamics simulations at different regimes of concentration and temperature. Crucial aspects for the comparison of the results provided by the two methods are carefully discussed, concerning the different reference frames used in theory and simulations to describe rotations and orientations, and leading to important differences in the behavior of correlation functions with the same combination of spherical harmonic indices. We find a remarkable agreement between the two approaches in the fluid regime, thus providing a first stringent comparison of the irreducible coefficients of the spherical harmonic expansion of the dipolar fluid’s static structure factor, provided by the MSA theory and molecular dynamics simulations.

The non-equilibrium self-consistent generalized Langevin equation theory of irreversible processes in liquids is extended to describe the positional and orientational thermal fluctuations of the instantaneous local concentration profile n(r, Ω, t) of a suddenly-quenched colloidal liquid of particles interacting through non spherically-symmetric pairwise interactions, whose mean value n(r, Ω, t) is constrained to remain uniform and isotropic, n(r, Ω, t) = n(t). Such self-consistent theory is cast in terms of the time-evolution equation of the covariance σ(t) = δn lm (k; t)δn † lm (k; t) of the fluctuations δn lm (k; t) = n lm (k; t)−n lm (k; t) of the spherical harmonics projections n lm (k; t) of the Fourier transform of n(r, Ω, t). The resulting theory describes the non-equilibrium evolution after a sudden temperature quench of both, the static structure factor projections S lm (k, t) and the two-time correlation function F lm (k, τ ; t) ≡ δn lm (k, t)δn lm (k, t + τ ), where τ is the correlation delay time and t is the evolution or waiting time after the quench. As a concrete and illustrative application we use the resulting self-consistent equations to describe the irreversible processes of equilibration or aging of the orientational degrees of freedom of a system of strongly interacting classical dipoles with quenched positional disorder.

The recently developed non-equilibrium self-consistent generalized Langevin equation theory of the dynamics of liquids of non-spherically interacting particles [J. Phys. Chem. B 120, 7975 (2016)] is applied to the description of the irreversible relaxation of a thermally and mechanically quenched dipolar fluid. Specifically, we consider a dipolar hard-sphere liquid quenched (at tw = 0) from full equilibrium conditions towards different ergodic–non-ergodic transitions. Qualitatively different scenarios are predicted by the theory for the time evolution of the system after the quench (tw > 0), that depend on both the kind of transition approached and the specific features of the protocol of preparation. Each of these scenarios is characterized by the kinetics displayed by a set of structural correlations, and also by the development of two characteristic times describing the relaxation of the translational and rotational dynamics, allowing us to highlight the crossover from equilibration to aging in the system and leading to the prediction of different underlying mechanisms and relaxation laws for the dynamics at each of the glass transitions explored.