A comparative study of the correlation between the structure and the dynamics for systems interacting via attractive and repulsive potentials (2306.16149v2)

Abstract: We present the study of the structure-dynamics correlation for systems interacting via attractive Lennard- Jones and its repulsive counterpart, the WCA potentials. The structural order parameter (SOP) is related to the microscopic mean-field caging potential. At a particle level, the SOP shows a distribution. Although the two systems have similar pair structures, their average SOP differs. However, this difference alone is insufficient to explain the well known slowing down of the dynamics in LJ system at low temperatures. The slowing down can be explained in terms of a stronger coupling between the SOP and the dynamics. To understand the origin of this system specific coupling, we study the difference in the microscopic structure between the hard and soft particles. We find that for the LJ system, the structural differences of the hard and soft particles are more significant and have a much stronger temperature dependence compared to the WCA system. Thus the study suggests that attractive interaction creates more structurally different communities. This broader difference in the structural communities is probably responsible for stronger coupling between the structure and dynamics. Thus the system specific structure-dynamics correlation, which also leads to a faster slowing down in the dynamics, appears to have a structural origin. A comparison of the predictive power of our SOP with the local energy and two body excess entropy shows that in the LJ system, the dynamics is driven by enthalpy, whereas in the WCA system, it is driven by entropy, and our SOP can capture both these contributions.