The tight Second Law inequality for coherent quantum systems and finite-size heat baths

We propose a new form of the Second Law inequality that defines a tight bound for extractable work from the non-equilibrium quantum state. In classical thermodynamics, the optimal work is given by the difference of free energy, what according to the result of Skrzypczyk et al. can be generalized for individual quantum systems. The saturation of this bound, however, requires an infinite bath and an ideal energy storage that is able to extract work from coherences. The new inequality, defined in terms of the ergotropy (rather than free energy), incorporates both of those important microscopic effects. In particular, we derive a formula for the locked energy in coherences, i.e. a quantum contribution that cannot be extracted as a work, and we find out its thermodynamic limit. Furthermore, we establish a general relation between ergotropy and free energy of the arbitrary quantum system coupled to the heat bath, what reveals that the latter is indeed the ultimate thermodynamic bound regarding work extraction, and shows that ergotropy can be interpreted as the generalization of the free energy for the finite-size heat baths.