arXiv subjects

S. -H. Chong

Publications and source records attributed to S. -H. Chong.

8 recordsLinked to original sources

arXiv2005

Evidence for the weak steric hindrance scenario in the supercooled-state reorientational dynamics

We use molecular-dynamics computer simulations to study the translational and reorientational dynamics of a glass-forming liquid of dumbbells. For sufficiently elongated molecules the standard strong steric hindrance scenario for the rotational dynamics is found. However, for small elongations we find a different scenario -- the weak steric hindrance scenario -- caused by a new type of glass transition in which the orientational dynamics of the molecule's axis undergoes a dynamical transition with a continuous increase of the non-ergodicity parameter. These results are in agreement with the theoretical predictions by the mode-coupling theory for the glass transition.

cond-mat.soft↗

arXiv2004

Structural relaxation in supercooled orthoterphenyl

We report molecular-dynamics simulation results performed for a model of molecular liquid orthoterphenyl in supercooled states, which we then compare with both experimental data and mode-coupling-theory (MCT) predictions, aiming at a better understanding of structural relaxation in orthoterphenyl. We pay special attention to the wavenumber dependence of the collective dynamics. It is shown that the simulation results for the model share many features with experimental data for real system, and that MCT captures the simulation results at the semiquantitative level except for intermediate wavenumbers connected to the overall size of the molecule. Theoretical results at the intermediate wavenumber region are found to be improved by taking into account the spatial correlation of the molecule's geometrical center. This supports the idea that unusual dynamical properties at the intermediate wavenumbers, reported previously in simulation studies for the model and discernible in coherent neutron-scattering experimental data, are basically due to the coupling of the rotational motion to the geometrical-center dynamics. However, there still remain qualitative as well as quantitative discrepancies between theoretical prediction and corresponding simulation results at the intermediate wavenumbers, which call for further theoretical investigation.

cond-mat.soft↗

arXiv2003

Structural relaxation in a supercooled molecular liquid

We perform molecular-dynamics simulations of a molecular system in supercooled states for different values of inertia parameters to provide evidence that the long-time dynamics depends only on the equilibrium structure. This observation is consistent with the prediction of the mode-coupling theory for the glass transition and with the hypothesis that the potential energy-landscape controls the slow dynamics. We also find that dynamical properties at intermediate wavenumber depend on the spatial correlation of the molecule's geometrical center.

cond-mat.soft↗

arXiv2002

Mode-coupling theory for structural and conformational dynamics of polymer melts

A mode-coupling theory for dense polymeric systems is developed which unifyingly incorporates the segmental cage effect relevant for structural slowing down and polymer chain conformational degrees of freedom. An ideal glass transition of polymer melts is predicted which becomes molecular-weight independent for large molecules. The theory provides a microscopic justification for the use of the Rouse theory in polymer melts, and the results for Rouse-mode correlators and mean-squared displacements are in good agreement with computer simulation results.

cond-mat.soft↗

arXiv2002

Structural relaxation in a system of dumbbell molecules

The interaction-site-density-fluctuation correlators, the dipole-relaxation functions, and the mean-squared displacements of a system of symmetric dumbbells of fused hard spheres are calculated for two representative elongations of the molecules within the mode-coupling theory for the evolution of glassy dynamics. For large elongations, universal relaxation laws for states near the glass transition are valid for parameters and time intervals similar to the ones found for the hard-sphere system. Rotation-translation coupling leads to an enlarged crossover interval for the mean-squared displacement of the constituent atoms between the end of the von Schweidler regime and the beginning of the diffusion process. For small elongations, the superposition principle for the reorientational $α$-process is violated for parameters and time intervals of interest for data analysis, and there is a strong breaking of the coupling of the $α$-relaxation scale for the diffusion process with that for representative density fluctuations and for dipole reorientations.

cond-mat.soft↗

arXiv2001

Idealized glass transitions for a system of dumbbell molecules

The mode-coupling theory for ideal glass transitions in simple systems is generalized to a theory for the glassy dynamics of molecular liquids using the density fluctuations of the sites of the molecule's constituent atoms as the basic structure variables. The theory is applied to calculate the liquid-glass phase diagram and the form factors for the arrested structure of a system of symmetric dumbbells of fused hard spheres. The static structure factors, which enter the equations of motion as input, are calculated as function of the packing fraction $ϕ$ and the molecule's elongation $ζ$ within the reference-interaction-site-model and Percus-Yevick theories. The critical packing fraction $ϕ_{c}$ for the glass transition is obtained as non-monotone function of $ζ$ with a maximum near $ζ= 0.43$. A transition line is calculated separating a small-$ζ$-glass phase with ergodic dipole motion from a large-$ζ$-glass phase where also the reorientational motion is arrested. The Debye-Waller factors at the transition are found to be somewhat larger for sufficiently elongated systems than those for the simple hard-sphere system, but the wave-number dependence of the glass-form factors is quite similar. The dipole reorientations for $ζ\ge 0.6$ are arrested as strongly as density fluctuations with wave vectors at the position of the first sharp diffraction peak.

cond-mat.soft↗

arXiv2001

The mean-squared displacement of a molecule moving in a glassy system

The mean-squared displacement (MSD) of a hard sphere and of a dumbbell molecule consisting of two fused hard spheres immersed in a dense hard-sphere system is calculated within the mode-coupling theory for ideal liquid-glass transitions. It is proven that the velocity correlator, which is the second time derivative of the MSD, is the negative of a completely monotone function for times within the structural-relaxation regime. The MSD is found to exhibit a large time interval for structural relaxation prior to the onset of the $α$-process which cannot be described by the asymptotic formulas for the mode-coupling-theory-bifurcation dynamics. The $α$-process for molecules with a large elongation is shown to exhibit an anomalously wide cross-over interval between the end of the von-Schweidler decay and the beginning of normal diffusion. The diffusivity of the molecule is predicted to vary non-monotonically as function of its elongation.

cond-mat.soft↗

arXiv2000

A mode-coupling theory for the glassy dynamics of a diatomic probe molecule immersed in a simple liquid

Generalizing the mode-coupling theory for ideal liquid-glass transitions, equations of motion are derived for the correlation functions describing the glassy dynamics of a diatomic probe molecule immersed in a simple glass-forming system. The molecule is described in the interaction-site representation and the equations are solved for a dumbbell molecule consisting of two fused hard spheres in a hard-sphere system. The results for the molecule's arrested position in the glass state and the reorientational correlators for angular-momentum index $\ell = 1$ and $\ell = 2$ near the glass transition are compared with those obtained previously within a theory based on a tensor-density description of the molecule in order to demonstrate that the two approaches yield equivalent results. For strongly hindered reorientational motion, the dipole-relaxation spectra for the $α$-process can be mapped on the dielectric-loss spectra of glycerol if a rescaling is performed according to a suggestion by Dixon et al. [Phys. Rev. Lett. {\bf 65}, 1108 (1990)]. It is demonstrated that the glassy dynamics is independent of the molecule's inertia parameters.

cond-mat.soft↗