Toward a better understanding of activation volume and dynamic decoupling of glass-forming liquids under compression

TL;DR

This paper uses a theoretical framework to analyze how pressure affects molecular dynamics in glass-forming liquids, revealing relationships between activation volume, decoupling, and pressure-dependent relaxation behaviors.

Contribution

It introduces a theoretical analysis of activation volume and dynamic decoupling under pressure, linking these phenomena with the differential activation free energy.

Findings

Decoupling exponent grows exponentially with pressure below 2 GPa.

Decoupling exponent and activation volume are interrelated.

Theoretical relationships explain previous experimental and simulation results.

Abstract

We theoretically investigate physical properties of the pressure-induced activation volume and dynamic decoupling of ternidazole, glycerol, and probucol by the Elastically Collective Nonlinear Langevin Equation theory. Based on the predicted temperature dependence of activated relaxation under various compression, the activation volume is determined to characterize effects of pressure on molecular dynamics of materials. We find that the decoupling of the structural relaxation time of compressed systems from their bulk uncompressed value is governed by the power-law rule. The decoupling exponent exponentially grows with pressure below 2 GPa. The decoupling exponent and activation volume are intercorrelated and have a connection with the differential activation free energy. We numerically and mathematically analyze relationships among these quantities to explain many results in previous experiments and simulations.