Structural relaxation in supercooled orthoterphenyl

TL;DR

This study uses molecular dynamics simulations and mode-coupling theory to analyze structural relaxation in supercooled orthoterphenyl, revealing the importance of geometrical-center correlations and highlighting areas for theoretical improvement.

Contribution

It provides a detailed comparison of simulation, experimental data, and MCT predictions for orthoterphenyl, emphasizing the role of geometrical-center dynamics in intermediate wavenumber behavior.

Findings

Simulation results align with experimental data in many aspects.

MCT captures the dynamics at a semi-quantitative level, except at intermediate wavenumbers.

Accounting for spatial correlations of the molecule's geometrical center improves theoretical predictions.

Abstract

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.