Numerical determination of the exponents controlling the relationship between time, length and temperature in glass-forming liquids

TL;DR

This study numerically determines the exponents linking time, length, and temperature in glass-forming liquids, revealing values that reproduce the Vogel-Fulcher-Tammann law despite differing from theoretical predictions.

Contribution

It provides the first numerical measurement of the exponents governing relaxation dynamics in glass-formers, challenging existing theoretical assumptions.

Findings

Measured exponents: ψ=1, θ=2

Exponents reproduce the VFT law

Results differ from previous theories

Abstract

There is a certain consensus that the very fast growth of the relaxation time $\tau$ occurring in glass-forming liquids on lowering the temperature must be due to the thermally activated rearrangement of correlated regions of growing size. Even though measuring the size of these regions has defied scientists for a while, there is indeed recent evidence of a growing correlation length $\xi$ in glass-formers. If we use Arrhenius law and make the mild assumption that the free-energy barrier to rearrangement scales as some power $\psi$ of the size of the correlated regions, we obtain a relationship between time and length, $T\log\tau \sim \xi^\psi$. According to both the Adam-Gibbs and the Random First Order theory the correlation length grows as $\xi \sim (T-T_k)^{-1/(d-\theta)}$, even though the two theories disagree on the value of $\theta$. Therefore, the super-Arrhenius growth of the relaxation time with the temperature is regulated by the two exponents $\psi$ and $\theta$ through the relationship $T\log\tau \sim (T-T_k)^{-\psi/(d-\theta)}$. Despite a few theoretical speculations, up to now there has been no experimental determination of these two exponents. Here we measure them numerically in a model glass-former, finding $\psi=1$ and $\theta=2$. Surprisingly, even though the values we found disagree with most previous theoretical suggestions, they give back the well-known VFT law for the relaxation time, $T\log\tau \sim (T-T_k)^{-1}$.