Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic Hysteresis

Nonequilibrium work relations have fundamentally advanced our understanding of molecular processes. In recent years, fluctuation theorems have been extensively applied to understand transitions between equilibrium steady-states, commonly described by simple control parameters such as molecular extension of a protein or polymer chain stretched by an external force in a quiescent fluid. Despite recent progress, far less is understood regarding the application of fluctuation theorems to processes involving nonequilibrium steady-states such as those described by polymer stretching dynamics in nonequilibrium fluid flows. In this work, we apply the Crooks fluctuation theorem to understand the nonequilibrium thermodynamics of dilute polymer solutions in flow. We directly determine the nonequilibrium free energy for single polymer molecules in flow using a combination of single molecule experiments and Brownian dynamics simulations. We further develop a time-dependent extensional flow protocol that allows for probing viscoelastic hysteresis over a wide range of flow strengths. Using this framework, we define quantities that uniquely characterize the coil-stretch transition for polymer chains in flow. Overall, generalized fluctuation theorems provide a powerful framework to understand polymer dynamics under far-from-equilibrium conditions.

Empirical evidence of a fluctuation theorem for the wind mechanical power input into the ocean

Ocean dynamics is predominantly driven by the shear stress between the atmospheric winds and ocean currents. The mechanical power input to the ocean is fluctuating in space and time and the atmospheric wind sometimes decelerates the ocean currents. Building on 24 years of global satellite observations, the input of mechanical power to the ocean is analysed. A fluctuation theorem (FT) holds when the logarithm of the ratio between the occurrence of positive and negative events, of a certain magnitude of the power input, is a linear function of this magnitude and the averaging period. The flux of mechanical power to the ocean shows evidence of a FT for regions within the recirculation area of the subtropical gyre but not over extensions of western boundary currents. A FT puts a strong constraint on the temporal distribution of fluctuations of power input, connects variables obtained with different lengths of temporal averaging, guides the temporal down- and up-scaling and constrains the episodes of improbable events.

A Theoretical Analysis of the Integral Fluctuation Theorem for Accelerated Colloidal Systems in the Long-Time Limit

A quantitative description of the second law of thermodynamics in relatively small classical systems and over short time scales comes from the fluctuation-dissipation theorem. It has been well established both theoretically and experimentally, the validity of the fluctuation theorem to small scale systems that are disturbed from their initial equilibrium states. Some experimental studies in the past have also explored the validity of the fluctuation theorem to nonequilibrium steady states at long time scales in the asymptotic limit. To this end, a theoretical and/or purely numerical model of the integral fluctuation theorem has been presented. An approximate general expression for the dissipation function has been derived for accelerated colloidal systems trapped/confined in power-law traps. Thereafter, a colloidal particle trapped in a harmonic potential (generated by an accelerating one-dimensional optical trap) and undergoing Brownian motion has been considered for the numerical study. A toy model of a quartic potential trap in addition to the harmonic trap has also been considered for the numerical study. The results presented herein show that the integral fluctuation theorem applies not only to equilibrium steady state distributions but also to nonequilibrium steady state distributions of ideal colloidal systems in accelerated frames of reference over long time scales.

On the analysis of the integral fluctuation theorem for accelerated colloidal systems in the long-time limit

A quantitative description of the violation of the second law of thermodynamics in relatively small classical systems and over short time scales comes from the fluctuation-dissipation theorem. It has been well established both theoretically and experimentally, the validity of the fluctuation theorem to small scale systems that are disturbed from their initial equilibrium states. Some experimental studies in the past have also explored the validity of the fluctuation theorem to nonequilibrium steady states at long time scales in the asymptotic limit. To this end, a theoretical and/or purely numerical model of the integral fluctuation theorem has been presented. An approximate general expression for the dissipation function has been derived for accelerated colloidal systems trapped/confined in power-law traps. Thereafter, a colloidal particle trapped in a harmonic potential (generated by an accelerating one-dimensional optical trap) and undergoing Brownian motion has been considered for the numerical study. A toy model of a quartic potential trap in addition to the harmonic trap has also been considered for the numerical study. The results presented herein show that the integral fluctuation theorem applies not only to equilibrium steady state distributions but also to nonequilibrium steady state distributions of colloidal systems in accelerated frames of reference over long time scales.