In search of invariants for viscous liquids in the density scaling regime: Investigations of dynamic and thermodynamic moduli

TL;DR

This study investigates dynamic and thermodynamic moduli in viscous liquids to identify invariants in the density scaling regime, revealing that certain ratios are not constant but can be transformed into invariant forms through a change of variables.

Contribution

The paper introduces a new invariant ratio of thermodynamic and dynamic moduli in the V-T representation for viscous liquids obeying density scaling laws.

Findings

The ratios $M_{p-T}$ and $B_T/M_{p-T}$ are not constant over wide temperature ranges.

Transforming $M_{p-T}$ to the V-T representation yields a new invariant $B_T/M_{V-T}$.

The invariant characterizes thermodynamics and molecular dynamics in supercooled liquids.

Abstract

In this paper, we report on nontrivial results of our investigations of dynamic and thermodynamic moduli in search of invariants for viscous liquids in the density scaling regime by using selected supercooled van der Waals liquids as representative materials. Previously, the dynamic modulus $M_{p-T}$ (defined in the pressure-temperature representation by the ratio of isobaric activation energy and activation volume) as well as the ratio $B_{T}/M_{p-T}$ (where $B_T$ is the thermodynamic modulus defined as the inverse isothermal compressibility) have been suggested as some kind of material constants. We have established that they are not valid in the explored wide range of temperatures $T$ over dozen decades of structural relaxation times $\tau $. The temperature dependences of $M_{p-T}$ and $B_T/M_{p-T}$ have been elucidated by comparison with the well-known measure of the relative contribution of temperature and density fluctuations to molecular dynamics near the glass transition, i.e., the ratio of the isochoric and isobaric activation energies, $E^{act}_{V}/E^{act}_{p}$. Then, we have implemented an idea to transform the definition of the dynamic modulus $M_{p-T}$ from the p-T representation to the V-T one. This idea relied on the disentanglement of combined temperature and density fluctuations involved in isobaric parameters has resulted in finding an invariant for viscous liquids in the density scaling regime, which is the ratio of the thermodynamic and dynamic moduli, $B_{T}/M_{V-T}$. In this way, we have constituted a characteristic of thermodynamics and molecular dynamics, which remains unchanged in the supercooled liquid state for a given material, the molecular dynamics of which obeys the power density scaling law.