Non-equilibrium entropy of glasses formed by continuous cooling

We propose a generalized definition of entropy accounting for the continuous breakdown of ergodicity at the laboratory glass transition. Our approach is applicable through all regimes of glass forming, from the equilibrium liquid state through the glass transition range and into the glassy state at low temperatures. The continuous loss of ergodicity during the laboratory glass transition is accompanied by a loss of entropy as the system gradually becomes trapped in a subset of the configurational phase space. Using a hierarchical master equation approach, We compute the configurational entropy of selenium, a simple but realistic glass-former, for cooling rates covering 25 orders of magnitude, viz., 10(-12) to 10(12) K/s. In all cases, the entropy of glass is zero in the limit of absolute zero temperature, since here the system is necessarily confined to a single microstate. (C) 2009 Elsevier B.V. All rights reserved.