Abstract. -We study a class of cyclic Brownian heat engines in the framework of finite-time thermodynamics. For infinitely long cycle times, the engine works at the Carnot efficiency limit producing, however, zero power. For the efficiency at maximum power, we find a universal expression, different from the endoreversible Curzon-Ahlborn efficiency. Our results are illustrated with a simple one-dimensional engine working in and with a time-dependent harmonic potential.

For a small system like a colloidal particle or a single biomolecule embedded in a heat bath, the optimal protocol of an external control parameter minimizes the mean work required to drive the system from one given equilibrium state to another in a finite time. In general, this optimal protocol obeys an integro-differential equation. Explicite solutions both for a moving laser trap and a time-dependent strength of such a trap show finite jumps of the optimal protocol to be typical both at the beginning and the end of the process.

For chemical reaction networks in a dilute solution described by a master equation, we define energy and entropy on a stochastic trajectory and develop a consistent nonequilibrium thermodynamic description along a single stochastic trajectory of reaction events. A first-law like energy balance relates internal energy, applied (chemical) work and dissipated heat for every single reaction. Entropy production along a single trajectory involves a sum over changes in the entropy of the network itself and the entropy of the medium. The latter is given by the exchanged heat identified through the first law. Total entropy production is constrained by an integral fluctuation theorem for networks arbitrarily driven by time-dependent rates and a detailed fluctuation theorem for networks in the steady state. Further exact relations like a generalized Jarzynski relation and a generalized Clausius inequality are discussed. We illustrate these results for a three-species cyclic reaction network which exhibits nonequilibrium steady states as well as transitions between different steady states.

PACS 05.70.LN -Nonequilibrium and irreversible thermodynamics PACS 05.40.-a -Fluctuation phenomena, random processes, noise, and Brownian motion PACS 87.16.-b -Subcellular structure and processes Abstract. -Molecular motors transduce chemical energy obtained from hydrolizing AT P into mechanical work exerted against an external force. We calculate their efficiency at maximum power output for two simple generic models and show that the qualitative behaviour depends crucially on the position of the transition state or, equivalently, on the load distribution factor. Specifically, we find a transition state near the initial state (sometimes characterized as a "power stroke") to be most favorable with respect to both high power output and high efficiency at maximum power. In this regime, driving the motor further out of equilibrium by applying higher chemical potential differences can even, counter-intuitively, increase the efficiency.

For systems in an externally controllable time-dependent potential, the optimal protocol minimizes the mean work spent in a finite-time transition between two given equilibrium states. For overdamped dynamics which ignores inertia effects, the optimal protocol has been found to involve jumps of the control parameter at the beginning and end of the process. Including the inertia term, we show that this feature not only persists but that even delta-peak-like changes of the control parameter at both boundaries make the process optimal. These results are obtained by analyzing two simple paradigmatic cases: First, a Brownian particle dragged by a harmonic optical trap through a viscous fluid and, second, a Brownian particle subject to an optical trap with time-dependent stiffness. These insights could be used to improve free energy calculations via either thermodynamic integration or "fast growth" methods using Jarzynski's equality.

Entropy production along a single stochastic trajectory of a biomolecule is discussed for two different sources of non-equilibrium. For a molecule manipulated mechanically by an AFM or an optical tweezer, entropy production (or annihilation) occurs in the molecular conformation proper or in the surrounding medium. Within a Langevin dynamics, a unique identification of these two contributions is possible. The total entropy change obeys an integral fluctuation theorem and a class of further exact relations, which we prove for arbitrarily coupled slow degrees of freedom including hydrodynamic interactions. These theoretical results can therefore also be applied to driven colloidal systems. For transitions between different internal conformations of a biomolecule involving unbalanced chemical reactions, we provide a thermodynamically consistent formulation and identify again the two sources of entropy production, which obey similar exact relations. We clarify the particular role degenerate states have in such a description. PACS numbers: 05.40.-a Fluctuation phenomena, random processes, noise, and Brownian motion, 05.70.-a Thermodynamics, 82.39.-k Chemical kinetics in biological systems, 87.15.-v Biomolecules: structure and physical properties

For systems in an externally controllable time dependent potential, the optimal protocol minimizes the mean work spent in a finite time transition between given initial and final values of a control parameter. For an initially thermalized ensemble, we consider both Hamiltonian evolution for classical systems and Schrödinger evolution for quantum systems. In both cases, we show that for harmonic potentials, the optimal work is given by the adiabatic work even in the limit of short transition times. This result is counter-intuitive because the adiabatic work is substantially smaller than the work for an instantaneous jump. We also perform numerical calculations for the optimal protocol for Hamiltonian dynamics in an anharmonic quartic potential. For a two-level spin system, we give examples where the adiabatic work can be reached in either a finite or an arbitrarily short transition time depending on the allowed parameter space.

For a three-state Markov system in a stationary state, we discuss whether, on the basis of data obtained from effective two-state (or on-off ) trajectories, it is possible to discriminate between an equilibrium state and a non-equilibrium steady state. By calculating the full phase diagram we identify a large region where such data will be consistent only with non-equilibrium conditions. This regime is considerably larger than the region with oscillatory relaxation, which has previously been identified as a sufficient criterion for non-equilibrium.