Out-of-equilibrium thermodynamic relations in systems with aging and slow relaxation.

The experimental time scale dependence of thermodynamic relations in out-of-equilibrium systems with aging phenomena is investigated theoretically by using only aging properties of the two-time correlation functions and the generalized fluctuation-dissipation theorem. We show that there are two experimental time regimes characterized by different thermal properties. In the first regime where the waiting time is much longer than the measurement time, the principle of minimum work holds even though a system is out of equilibrium. In the second regime where both the measurement time and the waiting time are long, the thermal properties are completely different from properties in equilibrium. For the single-correlation-scale systems such as p-spin spherical spin glasses, contrary to a fundamental assumption of thermodynamics, the work done in an infinitely slow operation depends on the path of change of the external field even when the waiting time is infinite. On the other hand, for the multi-correlation-scale systems such as Sherrington-Kirkpatrick model, the work done in an infinitely slow operation is independent of the path. Our results imply that in order to describe thermodynamic properties of systems with aging it is essential to consider the experimental time scales and history of a system as a state variable is necessary.