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Catalytic engines can use hydrogen peroxide as a chemical fuel in order to drive motion at the microscale. The chemo-mechanical actuation is a complex mechanism based on the interrelation between catalytic reactions and electro-hydrodynamics phenomena. We studied catalytic micropumps using fluorescence confocal microscopy to image the concentration of protons in the liquid. In addition, we measured the motion of particles with different charges in order to map the spatial distributions of the electric field, the electrostatic potential and the fluid flow. The combination of these two techniques allows us to contrast the gradient of the concentration of protons against the spatial variation in the electric field. We present numerical simulations that reproduce the experimental results. Our work sheds light on the interrelation between the different processes at work in the chemo-mechanical actuation of catalytic pumps. Our experimental approach could be used to study other electrochemical systems with heterogeneous electrodes.

We present a particle separation mechanism which induces motion of particles of different sizes in opposite directions. The mechanism is based on the combined action of a driving force and an entropic rectification of the Brownian fluctuations caused by the asymmetric form of the channel along which particles proceed. The entropic splitting effect shown could be controlled upon variation of the geometrical parameters of the channel and could be implemented in narrow channels and microfluidic devices., Comment: 5 pages, 4 figures. Accepted for publication in Phys. Rev. Lett

We demonstrate the appearance of a purely entropic stochastic resonance (ESR) occurring in a geometrically confined system, where the irregular boundaries cause entropic barriers. The interplay between a periodic input signal, a constant bias and intrinsic thermal noise leads to a resonant ESR-phenomenon in which feeble signals become amplified. This new phenomenon is characterized by the presence of two peaks in the spectral amplification at corresponding optimal values of the noise strength. The main peak is associated with the manifest stochastic resonance synchronization mechanism involving the inter-well noise-activated dynamics while a second peak relates to a regime of optimal sensitivity for intra-well dynamics. The nature of ESR, occurring when the origin of the barrier is entropic rather than energetic, offers new perspectives for novel investigations and potential applications. ESR by itself presents yet another case where one constructively can harvest noise in driven nonequilibrium systems., Comment: 6 pages, 7 figures ; Europhys. Lett., in press (2009)

We demonstrate the existence of stochastic resonance (SR) in confined systems arising from entropy variations associated to the presence of irregular boundaries. When the motion of a Brownian particle is constrained to a region with uneven boundaries, the presence of a periodic input may give rise to a peak in the spectral amplification factor and therefore to the appearance of the SR phenomenon. We have proved that the amplification factor depends on the shape of the region through which the particle moves and that by adjusting its characteristic geometric parameters one may optimize the response of the system. The situation in which the appearance of such entropic stochastic resonance (ESR) occurs is common for small-scale systems in which confinement and noise play an prominent role. The novel mechanism found could thus constitute an important tool for the characterization of these systems and can put to use for controlling their basic properties., Comment: 8 pages, 8 figures

We present a novel scheme for the appearance of Stochastic Resonance when the dynamics of a Brownian particle takes place in a confined medium. The presence of uneven boundaries, giving rise to an entropic contribution to the potential, may upon application of a periodic driving force result in an increase of the spectral amplification at an optimum value of the ambient noise level. This Entropic Stochastic Resonance (ESR), characteristic of small-scale systems, may constitute a useful mechanism for the manipulation and control of single-molecules and nano-devices., Comment: 4 pages, 3 figures

The dynamics of Brownian motion has widespread applications extending from transport in designed micro-channels up to its prominent role for inducing transport in molecular motors and Brownian motors. Here, Brownian transport is studied in micro-sized, two dimensional periodic channels, exhibiting periodically varying cross sections. The particles in addition are subjected to an external force acting alongside the direction of the longitudinal channel axis. For a fixed channel geometry, the dynamics of the two dimensional problem is characterized by a single dimensionless parameter which is proportional to the ratio of the applied force and the temperature of the particle environment. In such structures entropic effects may play a dominant role. Under certain conditions the two dimensional dynamics can be approximated by an effective one dimensional motion of the particle in the longitudinal direction. The Langevin equation describing this reduced, one dimensional process is of the type of the Fick-Jacobs equation. It contains an entropic potential determined by the varying extension of the eliminated channel direction, and a correction to the diffusion constant that introduces a space dependent diffusion. Different forms of this correction term have been suggested before, which we here compare for a particular class of models. We analyze the regime of validity of the Fick-Jacobs equation, both by means of analytical estimates and the comparisons with numerical results for the full two dimensional stochastic dynamics. For the nonlinear mobility we find a temperature dependence which is opposite to that known for particle transport in periodic potentials. The influence of entropic effects is discussed for both, the nonlinear mobility and the effective diffusion constant., Comment: 16 pages, 5 figures

We study biased, diffusive transport of Brownian particles through narrow, spatially periodic structures in which the motion is constrained in lateral directions. The problem is analyzed under the perspective of the Fick-Jacobs equation which accounts for the effect of the lateral confinement by introducing an entropic barrier in a one dimensional diffusion. The validity of this approximation, being based on the assumption of an instantaneous equilibration of the particle distribution in the cross-section of the structure, is analyzed by comparing the different time scales that characterize the problem. A validity criterion is established in terms of the shape of the structure and of the applied force. It is analytically corroborated and verified by numerical simulations that the critical value of the force up to which this description holds true scales as the square of the periodicity of the structure. The criterion can be visualized by means of a diagram representing the regions where the Fick-Jacobs description becomes inaccurate in terms of the scaled force versus the periodicity of the structure., Comment: 20 pages, 7 figures

We show that transport in the presence of entropic barriers exhibits peculiar characteristics which makes it distinctly different from that occurring through energy barriers. The constrained dynamics yields a scaling regime for the particle current and the diffusion coefficient in terms of the ratio between the work done to the particles and available thermal energy. This interesting property, genuine to the entropic nature of the barriers, can be utilized to effectively control transport through quasi one-dimensional structures in which irregularities or tortuosity of the boundaries cause entropic effects. The accuracy of the kinetic description has been corroborated by simulations. Applications to different dynamic situations involving entropic barriers are outlined., Comment: 4 pages, 5 figures. Accepted for publication in Phys. Rev. Lett

Concepts of everyday use like energy, heat, and temperature have acquired a precise meaning after the development of thermodynamics. Thermodynamics provides the basis for understanding how heat and work are related and with the general rules that the macroscopic properties of systems at equilibrium follow. Outside equilibrium and away from macroscopic regimes most of those rules cannot be applied directly. Here we present recent developments that extend the applicability of thermodynamic concepts deep into mesoscopic and irreversible regimes. We show how the probabilistic interpretation of thermodynamics together with probability conservation laws can be used to obtain Fokker-Planck equations for the relevant degrees of freedom. This approach provides a systematic method to obtain the stochastic dynamics of a system directly from its equilibrium properties. A wide variety of situations can be studied in this way, including many that were thought to be out of reach of thermodynamic theories, such as non-linear transport in the presence of potential barriers, activated processes, slow relaxation phenomena, and basic processes in biomolecules, like translocation and stretching., Comment: Feature Article, 32 pages, 5 figures

We show the existence of intermittent dynamics in one of the simplest model of a glassy system: the two-state model, which has been used to explain the origin of the violation of the fluctuation-dissipation theorem. The dynamics is analyzed through a Langevin equation for the evolution of the state of the system through its energy landscape. The results obtained concerning the violation factor and the non-Gaussian nature of the fluctuations are in good qualitative agreement with experiments measuring the effective temperature and the voltage fluctuations in gels and in polymer glasses. The method proposed can be useful to study the dynamics of other slow relaxation systems in which non-Gaussian fluctuations have been observed., Comment: 4 pages, 4 figures

We investigate the influence of a shear flow on the process of nucleation. Mesoscopic nonequilibrium thermodynamics is used to derive the Fokker-Planck equation governing the evolution of the cluster size distribution in a metastable phase subjected to a stationary flow. The presence of the flow manifests itself in the expression for the effective diffusion coefficient of a cluster and introduces modifications in the nucleation rate. The implications of these results in condensation and polymer crystallization are discussed., Comment: 10 pages, accepted for publication in J. Chem. Phys

We introduce a general formalism to analyze nucleation phenomena in inhomogeneous media which considers the influence of the metastable phase, which is treated as a heat bath in which clusters are embedded, in the dynamics of the nucleation process. A kinetic equation for the evolution of the probability density of the clusters, taking into account possible inhomogeneities in the bath, is derived using mesoscopic nonequilibrium thermodynamics. From it, we obtain the nucleation rate and analyze the role played by the metastable phase in the process. We discuss in particular condensation and polymer crystallization in a temperature gradient., Comment: 18 pages, 3 figures, accepted for publication in J. Chem. Phys

We analyze the validity of the fluctuation-dissipation theorem for slow relaxation systems in the context of mesoscopic nonequilibrium thermodynamics. We demonstrate that the violation arises as a natural consequence of the elimination of fast variables in the description of a glassy system, and it is intrinsically related to the underlying activated nature of slow relaxation. In addition, we show that the concept of effective temperature, introduced to characterize the magnitude of the violation, is not robust since it is observable-dependent, can diverge, or even be negative., Comment: 4 pages, 1 figure

We elucidate how the presence of noise may significantly interact with the synchronization mechanism of systems exhibiting frequency-locking. The response of these systems exhibits a rich variety of behaviors, such as resonances and anti-resonances which can be controlled by the intensity of noise. The transition between different locked regimes provokes the development of a multiple enhancement of the effective diffusion. This diffusion behavior is accompanied by a crest-like peak-splitting cascade when the distribution of the lockings is self-similar, as it occurs in periodic systems that are able to exhibit a Devil's staircase sequence of frequency-lockings., Comment: 7 pages, 6 figures, epl.cls. Accepted for publication in Europhysics Letters

We use the mesoscopic nonequilibrium thermodynamics theory to derive the general kinetic equation of a system in the presence of potential barriers. The result is applied to the description of the evolution of systems whose dynamics is influenced by entropic barriers. We analyze in detail the case of diffusion in a domain of irregular geometry in which the presence of the boundaries induces an entropy barrier when approaching the exact dynamics by a coarsening of the description. The corresponding kinetic equation, named Fick-Jacobs equation, is obtained, and its validity is generalized through the formulation of a scaling law for the diffusion coefficient which depends on the shape of the boundaries. The method we propose can be useful to analyze the dynamics of systems at the nanoscale where the presence of entropy barriers is a common feature., Comment: 16 pages, 5 figures. Accepted for publication in Phys. Rev. E

The role that translational-rotational degrees of freedom play in nucleation theories is reconsidered by the introduction of a new formalism that properly accounts for the effects of motion of clusters in nucleation rate. The analysis of the non-equilibrium kinetics of the process, performed by retaining the dynamics of the clusters, enables one to clarify some of the paradoxical aspects that the inclusion of these degrees of freedom has presented., Comment: 8 pages, 1 figure. Accepted for publication in J. Chem. Phys

We propose a method to analyze the dynamics of systems exhibiting slow relaxation which is based on mesoscopic non-equilibrium thermodynamics. The method allows us to obtain kinetic equations of the Fokker-Planck type for the probability functional and their corresponding Langevin equations. Our results are compared with the ones obtained by other authors., Comment: Contribution to the Proceedings of the ESFSPHINX meeting 'Glassy behaviour of Kinetically constrained models'. (Barcelona, March 22-25, 2001) To appear in a special issue of J. Phys. Cond. Matt

We analyze the diffusion of a Brownian particle in a fluid under stationary flow. By using the scheme of non-equilibrium thermodynamics in phase space, we obtain the Fokker-Planck equation which is compared with others derived from kinetic theory and projector operator techniques. That equation exhibits violation of the fluctuation dissipation-theorem. By implementing the hydrodynamic regime described by the first moments of the non-equilibrium distribution, we find relaxation equations for the diffusion current and pressure tensor, allowing us to arrive at a complete description of the system in the inertial and diffusion regimes. The simplicity and generality of the method we propose, makes it applicable to more complex situations, often encountered in problems of soft condensed matter, in which not only one but more degrees of freedom are coupled to a non-equilibrium bath., Comment: 10 pages, accepted in Phys. Rev. E

We report a new phenomenon occurring in field-responsive suspensions: shear-induced anomalous stresses. Competition between a rotating field and a shear flow originates a multiplicity of anomalous stress behaviors in suspensions of bounded dimers constituted by induced dipoles. The great variety of stress regimes includes non-monotonous behaviors, multi-resonances, negative viscosity effect and blockades. The reversibility of the transitions between the different regimes and the self-similarity of the stresses make this phenomenon controllable and therefore applicable to modify macroscopic properties of soft condensed matter phases, Comment: 5 pages, 6 figures, submitted to PRE

We introduce a new scheme to analyze the kinetics of homogeneous nucleation in terms of a global order parameter. Our approach is based on the application of the internal degrees of freedom formalism to derive a kinetic equation of the Kramers type formulated for a global reaction coordinate. We provide explicit expressions for the quantities and coefficients involved in the process, suitable for simulation. In addition, our picture recovers in the quasi-stationary case the transition rate obtained from the method of reactive flux. The equation we present may provide a link between theoretical approaches to homogeneous nucleation (generally formulated in terms of a kinetic equation of the Fokker-Planck type) and simulations (which mostly employ linear response theory). In this context, our scheme provides a theoretical framework to interpret and extend the results obtained in recent simulations., Comment: 10 pages, Revtex (no Figures). To appear in J. Chem. Phys