Mechanical relaxation and the notion of time-dependent extent of ergodicity during the glass transition

Abstract

A postulate that ergodicity and entropy continuously decrease to zero on cooling a liquid to a glassy state was used to support the view that glass has no residual entropy, and the features of mechanical relaxation spectra were cited as proof for the decrease. We investigate whether such spectra and the relaxation isochrones can serve as the proof. We find that an increase in the real component of elastic moduli with an increase in spectral frequency does not indicate continuous loss of ergodicity and entropy, and the spectra do not confirm isothermal glass transition or loss of entropy. Variation in ergodicity and entropy with the spectral frequency has untenable consequences for both thermodynamics and molecular dynamics and implies that, despite a broad distribution of its relaxation times, an equilibrium liquid can be considered as always ergodic. Perturbation from equilibrium used to obtain a spectrum does not have the effect of dynamic freezing and unfreezing, and Maxwell-Voigt models for the mechanical response function have neither the characteristic irreversibility of liquid-glass transition nor are commutable to ergodicity or entropy.