Effect of pressure on the number of dynamically correlated molecules when approaching the glass transition

TL;DR

This study experimentally investigates how pressure influences the number of dynamically correlated molecules near the glass transition, revealing an increase in correlations with pressure that challenges existing theories.

Contribution

It provides new dielectric spectroscopy data under high pressure and separates density and temperature contributions to dynamically correlated molecules, improving understanding of glass transition dynamics.

Findings

N_{corr} increases with pressure along the glass transition line

Pressure effects on N_{corr} contradict recent reports and theories

Extended data set enhances the estimate of dynamic heterogeneity

Abstract

We characterize the heterogeneous character of the dynamics of liquids approaching the glass transition through an experimental determination of the number of dynamically correlated molecules N_{corr} as obtained from dynamical susceptibilities. To do so, we have obtained a new set of dielectric spectroscopy data for liquid dibutyl-phtalate on a fine and extended temperature and pressure grid, and we have used it in conjunction with high-pressure data from the literature. We have been able to evaluate the contributions to N_{corr} that are due to fluctuations associated with density and with temperature separately, thereby improving the estimate of N_{corr}. We find that N_{corr} increases along the glass transition line, and more generally along any isochronic line, as pressure increases (up to 1 GPa), a result which is at odds with recent reports and theoretical predictions.