Destructive effect of fluctuations on the performance of a Brownian gyrator.

The Brownian gyrator (BG) is often called a minimal model of a nano-engine performing a rotational motion, judging solely upon the fact that in non-equilibrium conditions its torque, specific angular momentum  and specific angular velocity  have non-zero mean values. For a time-discretised (with time-step δt) model we calculate here the previously unknown probability density functions (PDFs) of  and . We show that for finite δt, the PDF of  has exponential tails and all moments are therefore well-defined. At the same time, this PDF appears to be effectively broad - the noise-to-signal ratio is generically bigger than unity meaning that  is strongly not self-averaging. Concurrently, the PDF of  exhibits heavy power-law tails and its mean is the only existing moment. The BG is therefore not an engine in the common sense: it does not exhibit regular rotations on each run and its fluctuations are not only a minor nuisance - on contrary, their effect is completely destructive for the performance. Our theoretical predictions are confirmed by numerical simulations and experimental data. We discuss some plausible improvements of the model which may result in a more systematic rotational motion.

Superionic liquids in conducting nanoslits: A variety of phase transitions and ensuing charging behavior.

We develop a theory of charge storage in ultranarrow slitlike pores of nanostructured electrodes. Our analysis is based on the Blume-Capel model in an external field, which we solve analytically on a Bethe lattice. The obtained solutions allow us to explore the complete phase diagram of confined ionic liquids in terms of the key parameters characterizing the system, such as pore ionophilicity, interionic interaction energy, and voltage. The phase diagram includes the lines of first- and second-order, direct and re-entrant phase transitions, which are manifested by singularities in the corresponding capacitance-voltage plots. Testing our predictions experimentally requires monodisperse, conducting ultranarrow slit pores, to permit only one layer of ions, and thick pore walls, to prevent interionic interactions across the pore walls. However, some qualitative features, which distinguish the behavior of ionophilic and ionophobic pores and their underlying physics, may emerge in future experimental studies of more complex electrode structures.

Nonequilibrium Fluctuations and Enhanced Diffusion of a Driven Particle in a Dense Environment.

We study the diffusion of a tracer particle driven out of equilibrium by an external force and traveling in a dense environment of arbitrary density. The system evolves on a discrete lattice and its stochastic dynamics is described by a master equation. Relying on a decoupling approximation that goes beyond the naive mean-field treatment of the problem, we calculate the fluctuations of the position of the tracer around its mean value on a lattice of arbitrary dimension, and with different boundary conditions. We reveal intrinsically nonequilibrium effects, such as enhanced diffusivity of the tracer induced by both the crowding interactions and the external driving. We finally consider the high-density and low-density limits of the model and show that our approximation scheme becomes exact in these limits.

Towards a full quantitative description of single-molecule reaction kinetics in biological cells.

The first-passage time (FPT), i.e., the moment when a stochastic process reaches a given threshold value for the first time, is a fundamental mathematical concept with immediate applications. In particular, it quantifies the statistics of instances when biomolecules in a biological cell reach their specific binding sites and trigger cellular regulation. Typically, the first-passage properties are given in terms of mean first-passage times. However, modern experiments now monitor single-molecular binding-processes in living cells and thus provide access to the full statistics of the underlying first-passage events, in particular, inherent cell-to-cell fluctuations. We here present a robust explicit approach for obtaining the distribution of FPTs to a small partially reactive target in cylindrical-annulus domains, which represent typical bacterial and neuronal cell shapes. We investigate various asymptotic behaviours of this FPT distribution and show that it is typically very broad in many biological situations, thus, the mean FPT can differ from the most probable FPT by orders of magnitude. The most probable FPT is shown to strongly depend only on the starting position within the geometry and to be almost independent of the target size and reactivity. These findings demonstrate the dramatic relevance of knowing the full distribution of FPTs and thus open new perspectives for a more reliable description of many intracellular processes initiated by the arrival of one or few biomolecules to a small, spatially localised region inside the cell.

Universal Long Ranged Correlations in Driven Binary Mixtures.

When two populations of "particles" move in opposite directions, like oppositely charged colloids under an electric field or intersecting flows of pedestrians, they can move collectively, forming lanes along their direction of motion. The nature of this "laning transition" is still being debated and, in particular, the pair correlation functions, which are the key observables to quantify this phenomenon, have not been characterized yet. Here, we determine the correlations using an analytical approach based on a linearization of the stochastic equations for the density fields, which is valid for dense systems of soft particles. We find that the correlations decay algebraically along the direction of motion, and have a self-similar exponential profile in the transverse direction. Brownian dynamics simulations confirm our theoretical predictions and show that they also hold beyond the validity range of our analytical approach, pointing to a universal behavior.

Cooperative behavior of biased probes in crowded interacting systems.

We study, via extensive numerical simulations, dynamics of a crowded mixture of mutually interacting (with a short-range repulsive potential) colloidal particles immersed in a suspending solvent, acting as a heat bath. The mixture consists of a majority component - neutrally buoyant colloids subject to internal stimuli only, and a minority component - biased probes (BPs) also subject to a constant force. In such a system each of the BPs alters the distribution of the colloidal particles in its vicinity, driving their spatial distribution out of equilibrium. This induces effective long-range interactions and multi-tag correlations between the BPs, mediated by an out-of-equilibrium majority component, and prompts the BPs to move collectively assembling in clusters. We analyse the size-distribution of the self-assembling clusters in the steady-state, their specific force-velocity relations and also properties of the effective interactions emerging between the BPs.

Diffusive escape through a narrow opening: new insights into a classic problem.

We study the mean first exit time (Tε) of a particle diffusing in a circular or a spherical micro-domain with an impenetrable confining boundary containing a small escape window (EW) of an angular size ε. Focusing on the effects of an energy/entropy barrier at the EW, and of the long-range interactions (LRIs) with the boundary on the diffusive search for the EW, we develop a self-consistent approximation to derive for Tε a general expression, akin to the celebrated Collins-Kimball relation in chemical kinetics and accounting for both rate-controlling factors in an explicit way. Our analysis reveals that the barrier-induced contribution to Tε is the dominant one in the limit ε → 0, implying that the narrow escape problem is not "diffusion-limited" but rather "barrier-limited". We present the small-ε expansion for Tε, in which the coefficients in front of the leading terms are expressed via some integrals and derivatives of the LRI potential. Considering a triangular-well potential as an example, we show that Tε is non-monotonic with respect to the extent of the attractive LRI, being minimal for the ones having an intermediate extent, neither too concentrated on the boundary nor penetrating too deeply into the bulk. Our analytical predictions are in good agreement with the numerical simulations.

Temporal Correlations of the Running Maximum of a Brownian Trajectory.

We study the correlations between the maxima m and M of a Brownian motion (BM) on the time intervals [0,t_{1}] and [0,t_{2}], with t_{2}>t_{1}. We determine the exact forms of the distribution functions P(m,M) and P(G=M-m), and calculate the moments E{(M-m)^{k}} and the cross-moments E{m^{l}M^{k}} with arbitrary integers l and k. We show that correlations between m and M decay as sqrt[t_{1}/t_{2}] when t_{2}/t_{1}→∞, revealing strong memory effects in the statistics of the BM maxima. We also compute the Pearson correlation coefficient ρ(m,M) and the power spectrum of M_{t}, and we discuss a possibility of extracting the ensemble-averaged diffusion coefficient in single-trajectory experiments using a single realization of the maximum process.

Velocity anomaly of a driven tracer in a confined crowded environment.

We consider a discrete model in which a tracer performs a random walk biased by an external force, in a dense bath of particles performing symmetric random walks constrained by hard-core interactions. We reveal the emergence of a striking velocity anomaly in confined geometries: in quasi-1D systems such as stripes or capillaries, the velocity of the tracer displays a long-lived plateau before ultimately dropping to a lower value. We develop an analytical solution that quantitatively accounts for this intriguing behavior. Our analysis suggests that such a velocity anomaly could be a generic feature of driven dynamics in quasi-1D crowded systems.

Charging dynamics of supercapacitors with narrow cylindrical nanopores.

We present a coarse-grained, continuum kinetic theory for charging supercapacitors with narrow cylindrical nanopores. The theory reveals that the occupancy of a nonpolarized pore and the energy barrier for ion-ion interdiffusion are the key issues controlling the different regimes of dynamic response. For 'ionophobic' pores, where the pore is empty at no applied voltage, charge density advances into the pore via diffusion-like dynamics. The mechanism of charging an 'ionophilic' pore is starkly different: for moderate ionophilicities, co-ions are expelled from the pore in a front-like manner, with significant 'congestion' at the pore entrance predicted for strong ionophilicity. We thus show that pore ionophilicity is detrimental to the speed of charging/discharging cycles, whereas making pores more ionophobic can substantially accelerate charging and cyclic recharging.

Anomalous fluctuations of currents in Sinai-type random chains with strongly correlated disorder.

We study properties of a random walk in a generalized Sinai model, in which a quenched random potential is a trajectory of a fractional Brownian motion with arbitrary Hurst parameter H, 0

Geometry-induced superdiffusion in driven crowded systems.

Recent molecular dynamics simulations of glass-forming liquids revealed superdiffusive fluctuations associated with the position of a tracer particle (TP) driven by an external force. Such an anomalous response, whose mechanism remains elusive, has been observed up to now only in systems close to their glass transition, suggesting that this could be one of its hallmarks. Here, we show that the presence of superdiffusion is in actual fact much more general, provided that the system is crowded and geometrically confined. We present and solve analytically a minimal model consisting of a driven TP in a dense, crowded medium in which the motion of particles is mediated by the diffusion of packing defects, called vacancies. For such nonglass-forming systems, our analysis predicts a long-lived superdiffusion which ultimately crosses over to giant diffusive behavior. We find that this trait is present in confined geometries, for example long capillaries and stripes, and emerges as a universal response of crowded environments to an external force. These findings are confirmed by numerical simulations of systems as varied as lattice gases, dense liquids, and granular fluids.

Geometrical optics of large deviations of fractional Brownian motion.

It has been shown recently that the optimal fluctuation method-essentially geometrical optics-provides a valuable insight into large deviations of Brownian motion. Here we extend the geometrical optics formalism to two-sided, -∞

Path integrals for fractional Brownian motion and fractional Gaussian noise.

Wiener's path integral plays a central role in the study of Brownian motion. Here we derive exact path-integral representations for the more general fractional Brownian motion (FBM) and for its time derivative process, fractional Gaussian noise (FGN). These paradigmatic non-Markovian stochastic processes, introduced by Kolmogorov, Mandelbrot, and van Ness, found numerous applications across the disciplines, ranging from anomalous diffusion in cellular environments to mathematical finance. Their exact path-integral representations were previously unknown. Our formalism exploits the Gaussianity of the FBM and FGN, relies on the theory of singular integral equations, and overcomes some technical difficulties by representing the action functional for the FBM in terms of the FGN for the subdiffusive FBM and in terms of the derivative of the FGN for the super-diffusive FBM. We also extend the formalism to include external forcing. The exact and explicit path-integral representations make inroads in the study of the FBM and FGN.

Ionic liquids in conducting nanoslits: how important is the range of the screened electrostatic interactions?

Analytical models for capacitive energy storage in nanopores attract growing interest as they can provide in-depth analytical insights into charging mechanisms. So far, such approaches have been limited to models with nearest-neighbor interactions. This assumption is seemingly justified due to a strong screening of inter-ionic interactions in narrow conducting pores. However, how important is the extent of these interactions? Does it affect the energy storage and phase behavior of confined ionic liquids? Herein, we address these questions using a two-dimensional lattice model with next-nearest and further neighbor interactions developed to describe ionic liquids in conducting slit confinements. With simulations and analytical calculations, we find that next-nearest interactions enhance capacitance and stored energy densities and may considerably affect the phase behavior. In particular, in some range of voltages, we reveal the emergence of large-scale mesophases that have not been reported before but may play an important role in energy storage.

Spectral fingerprints of nonequilibrium dynamics: The case of a Brownian gyrator.

The same system can exhibit a completely different dynamical behavior when it evolves in equilibrium conditions or when it is driven out-of-equilibrium by, e.g., connecting some of its components to heat baths kept at different temperatures. Here we concentrate on an analytically solvable and experimentally relevant model of such a system-the so-called Brownian gyrator-a two-dimensional nanomachine that performs a systematic, on average, rotation around the origin under nonequilibrium conditions, while no net rotation takes place under equilibrium ones. On this example, we discuss a question whether it is possible to distinguish between two types of a behavior judging not upon the statistical properties of the trajectories of components but rather upon their respective spectral densities. The latter are widely used to characterize diverse dynamical systems and are routinely calculated from the data using standard built-in packages. From such a perspective, we inquire whether the power spectral densities possess some "fingerprint" properties specific to the behavior in nonequilibrium. We show that indeed one can conclusively distinguish between equilibrium and nonequilibrium dynamics by analyzing the cross-correlations between the spectral densities of both components in the short frequency limit, or from the spectral densities of both components evaluated at zero frequency. Our analytical predictions, corroborated by experimental and numerical results, open a new direction for the analysis of a nonequilibrium dynamics.

Recognition capabilities of a Hopfield model with auxiliary hidden neurons.

We study the recognition capabilities of the Hopfield model with auxiliary hidden layers, which emerge naturally upon a Hubbard-Stratonovich transformation. We show that the recognition capabilities of such a model at zero temperature outperform those of the original Hopfield model, due to a substantial increase of the storage capacity and the lack of a naturally defined basin of attraction. The modified model does not fall abruptly into the regime of complete confusion when memory load exceeds a sharp threshold. This latter circumstance, together with an increase of the storage capacity, renders such a modified Hopfield model a promising candidate for further research, with possible diverse applications.

Superionic Liquids in Conducting Nanoslits: Insights from Theory and Simulations.

Mapping the theory of charging supercapacitors with nanostructured electrodes on known lattice models of statistical physics is an interesting task, aimed at revealing generic features of capacitive energy storage in such systems. The main advantage of this approach is the possibility to obtain analytical solutions that allow new physical insights to be more easily developed. But how general the predictions of such theories could be? How sensitive are they to the choice of the lattice? Herein, we address these questions in relation to our previous description of such systems using the Bethe-lattice approach and Monte Carlo simulations. Remarkably, we find a surprisingly good agreement between the analytical theory and simulations. In addition, we reveal a striking correlation between the ability to store energy and ion ordering inside a pore, suggesting that such ordering can be beneficial for energy storage.

Equilibrium properties of two-species reactive lattice gases on random catalytic chains.

We focus here on the thermodynamic properties of adsorbates formed by two-species A+B→⊘ reactions on a one-dimensional infinite lattice with heterogeneous "catalytic" properties. In our model hard-core A and B particles undergo continuous exchanges with their reservoirs and react when dissimilar species appear at neighboring lattice sites in presence of a "catalyst." The latter is modeled by supposing either that randomly chosen bonds in the lattice promote reactions (Model I) or that reactions are activated by randomly chosen lattice sites (Model II). In the case of annealed disorder in spatial distribution of a catalyst we calculate the pressure of the adsorbate by solving three-site (Model I) or four-site (Model II) recursions obeyed by the corresponding averaged grand-canonical partition functions. In the case of quenched disorder, we use two complementary approaches to find exact expressions for the pressure. The first approach is based on direct combinatorial arguments. In the second approach, we frame the model in terms of random matrices; the pressure is then represented as an averaged logarithm of the trace of a product of random 3×3 matrices-either uncorrelated (Model I) or sequentially correlated (Model II).