Role of anisotropy in understanding the molecular grounds for density scaling in dynamics of glass-forming liquids

Abstract

Molecular Dynamics (MD) simulations of glass-forming liquids play a pivotal role in uncovering the molecular nature of the liquid vitrification process. In particular, much focus was given to elucidating the interplay between the character of intermolecular potential and molecular dynamics behaviour. This has been tried to achieve by simulating the spherical particles interacting via isotropic potential. However, when simulation and experimental data are analysed in the same way by using the density scaling approaches, serious inconsistency is revealed between them. Similar scaling exponent values are determined by analysing the relaxation times and pVT data obtained from computer simulations. In contrast, these values differ significantly when the same analysis is carried out in the case of experimental data. As discussed thoroughly herein, the coherence between results of simulation and experiment can be achieved if anisotropy of intermolecular interactions is introduced to MD simulations. In practice, it has been realized in two different ways: (1) by using the anisotropic potential of the Gay–Berne type or (2) by replacing the spherical particles with quasi-real polyatomic anisotropic molecules interacting through isotropic Lenard–Jones potential. In particular, the last strategy has the potential to be used to explore the relationship between molecular architecture and molecular dynamics behaviour. Finally, we hope that the results presented in this review will also encourage others to explore how ‘anisotropy’ affects remaining aspects related to liquid–glass transition, like heterogeneity, glass transition temperature, glass forming ability, etc.