How attractive and repulsive interactions affect structure ordering and dynamics of glass-forming liquids.

Abstract

The theory developed in our previous papers [Phys. Rev. E 99, 030101(R) (2019)10.1103/PhysRevE.99.030101; Phys. Rev. E 103, 032611 (2021)10.1103/PhysRevE.103.032611] is applied in this paper to investigate the dependence of slowing down of dynamics of glass-forming liquids on the attractive and repulsive parts of intermolecular interactions. Through an extensive comparison of the behavior of a Lennard-Jones glass-forming liquid and that of its WCA reduction to a model with truncated pair potential without attractive tail, we demonstrate why the two systems exhibit very different dynamics despite having nearly identical pair correlation functions. In particular, we show that local structures characterized by the number of mobile and immobile particles around a central particle markedly differ in the two systems at densities and temperatures where their dynamics show large difference and nearly identical where dynamics nearly overlap. We also show how the parameter ψ(T) that measures the role of fluctuations embedded in the system on size of the cooperatively reorganizing cluster (CRC) and the crossover temperature T_{a} depend on the intermolecular interactions. These parameters stemming from the intermolecular interactions characterize the temperature and density dependence of structural relaxation time τ_{α}. The quantitative and qualitative agreements found with simulation results for the two systems suggest that our theory brings out the underlying features that determine the dynamics of glass-forming liquids.