Correlating thermal machines and the second law at the nanoscale

Abstract

Thermodynamics at the nanoscale is known to differ significantly from its familiar macroscopic counterpart: the possibility of state transitions is not determined by free energy alone, but by an infinite family of free-energy-like quantities; strong fluctuations (possibly of quantum origin) allow to extract less work reliably than what is expected from computing the free energy difference. However, these known results rely crucially on the assumption that the thermal machine is not only exactly preserved in every cycle, but also kept uncorrelated from the quantum systems on which it acts. Here we lift this restriction: we allow the machine to become correlated with the microscopic systems on which it acts, while still exactly preserving its own state. Surprisingly, we show that this restores the second law in its original form: free energy alone determines the possible state transitions, and the corresponding amount of work can be invested or extracted from single systems exactly and without any fluctuations. At the same time, the work reservoir remains uncorrelated from all other systems and parts of the machine. Thus, microscopic machines can increase their efficiency via clever "correlation engineering" in a perfectly cyclic manner, which is achieved by a catalytic system that can sometimes be as small as a single qubit (though some setups require very large catalysts). Our results also solve some open mathematical problems on majorization which may lead to further applications in entanglement theory.