We experimentally demonstrate the fluctuation theorem, which predicts appreciable and measurable violations of the second law of thermodynamics for small systems over short time scales, by following the trajectory of a colloidal particle captured in an optical trap that is translated relative to surrounding water molecules. From each particle trajectory, we calculate the entropy production/consumption over the duration of the trajectory and determine the fraction of second law-defying trajectories. Our results show entropy consumption can occur over colloidal length and time scales.

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 arXiv:0709.3888v2 [cond-mat.stat-mech]

We present experimental evidence of the Rayleigh-Plateau instability of a single chain in poor solvent conditions using single molecule force microscopy. Poly(N-isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) are adsorbed onto silicon nitride surfaces in various solutions corresponding to poor and good solvent conditions. In good solvent conditions, the force-separation profile is identical to that described previously and attributed to the elastic stretching of single polymer chains. However, in poor solvent conditions, we see a dramatically different force profile, characterized by steps or plateaus of constant force. These plateaus represent the "pull-out" of chain segments from collapsed globules of polymer collected at each of the separating surfaces. A statistical analysis of the large number of force profiles collected indicates that these plateaus are quantized, suggesting pull-out of several chains of different length. Moreover, the frequency of the steps suggests that we can distinguish pulled loops from pulled tails.

The puzzle of how time-reversible microscopic equations of mechanics lead to the time-irreversible macroscopic equations of thermodynamics has been a paradox since the days of Boltzmann. Boltzmann simply sidestepped this enigma by stating "as soon as one looks at bodies of such small dimension that they contain only very few molecules, the validity of this theorem [the second law of thermodynamics and its description of irreversibility] must cease." Today we can state that the transient fluctuation theorem (TFT) of Evans and Searles is a generalized, second-law-like theorem that bridges the microscopic and macroscopic domains and links the time-reversible and irreversible descriptions. We apply this theorem to a colloidal particle in an optical trap. For the first time, we demonstrate the TFT in an experiment and show quantitative agreement with Langevin dynamics.

Atomic force microscopy has been used to investigate the detachment of single polymer chains from surfaces and to measure the picoNewton forces required to extend the chain orthogonal to the surface. Such recent experiments show that the force−extension profiles provide interesting signatures which might be related to the progressive detachment of the chain from a surface. Using equilibrium scaling analysis, activation kinetics, and exactly solvable partition functions we predict force versus extension profiles for various extension rates. We also show how variation in the extension rate can distinguish heterogeneous monomer−surface contacts. The qualitative features that we predict, such as sawtooth force profiles with detachment forces which decrease with extension, maximal yielding forces at high extension rates, and featureless force profiles at large extension, are also seen in experiment.