Under a general framework, shortcuts to adiabatic processes are shown to be possible in classical systems. We then study the distribution function of the work done on a small system initially prepared at thermal equilibrium. It is found that the work fluctuations can be significantly reduced via shortcuts to adiabatic processes. For example, in the classical case probabilities of having very large or almost zero work values are suppressed. In the quantum case negative work may be totally removed from the otherwise non-positive-definite work values. We also apply our findings to a micro Otto-cycle-based heat engine. It is shown that the use of shortcuts, which directly enhances the engine output power, can also increase the heat engine efficiency substantially, in both quantum and classical regimes.

A result of great theoretical and experimental interest, the Jarzynski equality predicts a free energy change ΔF of a system at inverse temperature β from an ensemble average of nonequilibrium exponential work, i.e., 〈e^{-βW}〉=e^{-βΔF}. The number of experimental work values needed to reach a given accuracy of ΔF is determined by the variance of e^{-βW}, denoted var(e^{-βW}). We discover in this work that var(e^{-βW}) in both harmonic and anharmonic Hamiltonian systems can systematically diverge in nonadiabatic work protocols, even when the adiabatic protocols do not suffer from such divergence. This divergence may be regarded as a type of dynamically induced phase transition in work fluctuations. For a quantum harmonic oscillator with time-dependent trapping frequency as a working example, any nonadiabatic work protocol is found to yield a diverging var(e^{-βW}) at sufficiently low temperatures, markedly different from the classical behavior. The divergence of var(e^{-βW}) indicates the too-far-from-equilibrium nature of a nonadiabatic work protocol and makes it compulsory to apply designed control fields to suppress the quantum work fluctuations in order to test the Jarzynski equality.

Work is one of the most basic notion in statistical mechanics, with work fluctuation theorems being one central topic in nanoscale thermodynamics. With Hamiltonian chaos commonly thought to provide a foundation for classical statistical mechanics, here we present general salient results regarding how (classical) Hamiltonian chaos generically impacts on nonequilibrium work fluctuations. For isolated chaotic systems prepared with a microcanonical distribution, work fluctuations are minimized and vanish altogether in adiabatic work protocols. For isolated chaotic systems prepared at an initial canonical distribution at inverse temperature β, work fluctuations depicted by the variance of e −βW are also minimized by adiabatic work protocols. This general result indicates that, if the variance of e −βW diverges for an adiabatic work protocol, it diverges for all nonadiabatic work protocols sharing the same initial and final Hamiltonians. Such divergence is hence not an isolated event and thus greatly impacts on the efficiency of using the Jarzynski's equality to simulate free energy differences. Theoretical results are illustrated in a Sinai model. Our general insights shall boost studies in nanoscale thermodynamics and are of fundamental importance in designing useful work protocols.

Abstract:The well-known Jarzynski equality, often written in the form e −β∆F = e −βW , provides a non-equilibrium means to measure the free energy difference ∆F of a system at the same inverse temperature β based on an ensemble average of non-equilibrium work W. The accuracy of Jarzynski's measurement scheme was known to be determined by the variance of exponential work, denoted as var e −βW . However, it was recently found that var e −βW can systematically diverge in both classical and quantum cases. Such divergence will necessarily pose a challenge in the applications of Jarzynski equality because it may dramatically reduce the efficiency in determining ∆F. In this work, we present a deformed Jarzynski equality for both classical and quantum non-equilibrium statistics, in efforts to reuse experimental data that already suffers from a diverging var e −βW . The main feature of our deformed Jarzynski equality is that it connects free energies at different temperatures and it may still work efficiently subject to a diverging var e −βW . The conditions for applying our deformed Jarzynski equality may be met in experimental and computational situations. If so, then there is no need to redesign experimental or simulation methods. Furthermore, using the deformed Jarzynski equality, we exemplify the distinct behaviors of classical and quantum work fluctuations for the case of a time-dependent driven harmonic oscillator dynamics and provide insights into the essential performance differences between classical and quantum Jarzynski equalities.