Generalized mode-coupling theory of the glass transition. I. Numerical results for Percus-Yevick hard spheres

TL;DR

This paper advances the microscopic understanding of the glass transition by numerically analyzing a hierarchical generalized mode-coupling theory (GMCT) for hard spheres, showing improved accuracy over standard MCT and preserving key scaling laws.

Contribution

It provides the first comprehensive numerical analysis of high-order GMCT for hard spheres, demonstrating systematic improvements over standard MCT in predicting glassy dynamics.

Findings

Higher-order GMCT remedies standard MCT's underestimation of critical density.

Scaling laws of MCT are preserved at all GMCT levels.

Predicted critical exponents improve with increased hierarchy levels.

Abstract

Mode-coupling theory (MCT) constitutes one of the few first-principles-based approaches to describe the physics of the glass transition, but the theory's inherent approximations compromise its accuracy in the activated glassy regime. Here we show that microscopic generalized mode-coupling theory (GMCT), a recently proposed hierarchical framework to systematically improve upon standard MCT, provides a promising pathway toward a more accurate first-principles description of glassy dynamics. We present a comprehensive numerical analysis for Percus-Yevick hard spheres by performing explicitly wavenumber- and time-dependent GMCT calculations up to sixth order. Specifically, we calculate the location of the critical point, the associated non-ergodicity parameters, the time-dependent dynamics of the density correlators at both absolute and reduced packing fractions, and we test several universal scaling relations in the $\alpha$- and $\beta$-relaxation regimes. It is found that higher-order GMCT can successfully remedy some of standard MCT's pathologies, including an underestimation of the critical glass transition density and an overestimation of the hard-sphere fragility. Furthermore, we numerically demonstrate that the celebrated scaling laws of standard MCT are preserved in GMCT at all closure levels, and that the predicted critical exponents manifestly improve as more levels are incorporated in the GMCT hierarchy. Although formally the GMCT equations should be solved up to infinite order to reach full convergence, our finite-order GMCT calculations unambiguously reveal a uniform convergence pattern for the dynamics. We thus argue that GMCT can provide a feasible and controlled means to bypass MCT's main uncontrolled approximation, offering hope for the future development of a quantitative first-principles theory of the glass transition.