Manifestation of Random First Order Transition theory in Wigner glasses

TL;DR

This study uses simulations of charged colloidal particles to demonstrate that the Random First Order Transition (RFOT) theory accurately describes the static and dynamic behaviors observed during the liquid to glass transition in Wigner glasses.

Contribution

It provides the first comprehensive validation of RFOT theory in Wigner glasses through detailed simulation evidence of ergodicity breaking and dynamic slowdown.

Findings

Ergodicity breaks at volume fraction =0.1, with diffusion constants vanishing as ( - )^g.

Relaxation times follow the VFT law with the glass transition at =0.47.

Density correlations decay as a stretched exponential with exponent 0.45.

Abstract

We use Brownian dynamics simulations of a binary mixture of highly charged spherical colloidal particles to illustrate many of the implications of the Random First Order Transition (RFOT) theory (PRA 40 1045 (1989)), which is the only theory that provides a unified description of both the statics and dynamics of the liquid to glass transition. In accord with the RFOT, we find that as the volume fraction of the colloidal particles \f, the natural variable that controls glass formation in colloidal systems, approaches \f_A there is an effective ergodic to non-ergodic dynamical transition, which is signalled by a dramatic slowing down of diffusion. In addition, using the energy metric we show that the system becomes non-ergodic as \f_A is approached. The time t^*, at which the four-point dynamical susceptibility achieves a maximum, also diverges near \f_A. Remarkably, three independent measures(translational diffusion coefficients, ergodic diffusion coefficients,as well t^*) all signal that at \f_A=0.1 ergodicity is effectively broken. The translation diffusion constant, the ergodic diffusion constant, and (t^*)^-1 all vanish as (\f_A-\f)^g with both \f_A and g being the roughly the same for all three quantities. Below \f_A transport involves crossing suitable free energy barriers. In this regime, the density-density correlation function decays as a stretched exponential exp(-t/tau_a)^b with b=0.45. The \f-dependence of the relaxation time \tau_a is well fit using the VFT law with the ideal glass transition occurring at \f_K=0.47. By using an approximate measure of the local entropy (s_3) we show that below \f_A the law of large numbers, which states that the distribution of s_3 for a large subsample should be identical to the whole sample, is not obeyed. The comprehensive analyses provided here for Wigner glass forming charged colloidal suspensions fully validate the concepts of the RFOT.