Fluctuation Theorems

TL;DR

Fluctuation theorems provide fundamental insights into irreversibility, statistical fluctuations, and free energy changes in nonequilibrium systems, extending thermodynamics to finite and small systems.

Contribution

This paper reviews the development, significance, and applications of fluctuation theorems in understanding nonequilibrium statistical mechanics.

Findings

Fluctuation theorems describe statistical fluctuations in nonequilibrium systems.

They enable quantitative predictions for small, short-term monitored systems.

Theorems are relevant for nanotechnology and biological processes.

Abstract

Fluctuation theorems, which have been developed over the past 15 years, have resulted in fundamental breakthroughs in our understanding of how irreversibility emerges from reversible dynamics, and have provided new statistical mechanical relationships for free energy changes. They describe the statistical fluctuations in time-averaged properties of many-particle systems such as fluids driven to nonequilibrium states, and provide some of the very few analytical expressions that describe nonequilibrium states. Quantitative predictions on fluctuations in small systems that are monitored over short periods can also be made, and therefore the fluctuation theorems allow thermodynamic concepts to be extended to apply to finite systems. For this reason, fluctuation theorems are anticipated to play an important role in the design of nanotechnological devices and in understanding biological processes. These theorems, their physical significance and results for experimental and model systems are discussed.