Dynamical instability causes the demise of a supercooled tetrahedral liquid

TL;DR

This study uses Monte Carlo simulations to analyze how a supercooled tetrahedral liquid relaxes and ultimately destabilizes, revealing a two-stage relaxation process driven by a dynamical crossover and culminating in rapid crystallization.

Contribution

It identifies a two-time-scale relaxation mechanism and links the dynamical crossover to the instability leading to crystallization in supercooled tetrahedral liquids.

Findings

Relaxation involves slow and fast fluctuation time-scales.

A dynamical crossover triggers the change in relaxation behavior.

Crystallization occurs after the crossover due to instability at a specific potential energy.

Abstract

We investigate the relaxation mechanism of a supercooled tetrahedral liquid at its limit of stability using isothermal isobaric ($NPT$) Monte Carlo (MC) simulations. In similarity with systems which are far from equilibrium but near the onset of jamming [O'Hern et.al., Phys. Rev. Lett. {\bf 93}, 165702 (2004)], we find that the relaxation is characterized by two time-scales: the decay of long-wavelength (slow) fluctuations of potential energy is controlled by the the slope $[\partial (G/N)/\partial \phi]$ of the Gibbs free energy ($G$) at a unique value of per particle potential energy $\phi = \phi_{mid}$. The short-wavelength (fast) fluctuations are controlled by the bath temperature $T$. The relaxation of the supercooled liquid is initiated with a dynamical crossover after which the potential energy fluctuations are biased towards values progressively lesser than $\phi_{mid}$. The dynamical crossover leads to the change of time-scale, i.e., the decay of long-wavelength potential energy fluctuations (intermediate relaxation). Because of the condition [$\partial^2 (G/N)/\partial \phi^2 = 0$] at $\phi = \phi_{mid}$, the slope $[\partial (G/N)/\partial \phi]$ has a unique value and governs the intermediate stage of relaxation, which ends just after the crossover. In the subsequent stage, there is a relatively rapid crystallization due to lack of long-wavelength fluctuations and the instability at $\phi_{mid}$, i.e., the condition that $G$ decreases as configurations with potential energies lower than $\phi_{mid}$ are accessed. The dynamical crossover point and the associated change in the time-scale of fluctuations is found to be consistent with the previous studies.