Linear sweep and cyclic voltammetry techniques are important tools for electrochemists and have a variety of applications in engineering. Voltammetry has classically been treated with the Randles-Sevcik equation, which assumes an electroneutral supported electrolyte. In this paper, we provide a comprehensive mathematical theory of voltammetry in electrochemical cells with unsupported electrolytes and for other situations where diffuse charge effects play a role, and present analytical and simulated solutions of the time-dependent Poisson-Nernst-Planck equations with generalized Frumkin-Butler-Volmer boundary conditions for a 1:1 electrolyte and a simple reaction. Using these solutions, we construct theoretical and simulated current-voltage curves for liquid and solid thin films, membranes with fixed background charge, and cells with blocking electrodes. The full range of dimensionless parameters is considered, including the dimensionless Debye screening length (scaled to the electrode separation), Damkohler number (ratio of characteristic diffusion and reaction times), and dimensionless sweep rate (scaled to the thermal voltage per diffusion time). The analysis focuses on the coupling of Faradaic reactions and diffuse charge dynamics, although capacitive charging of the electrical double layers is also studied, for early time transients at reactive electrodes and for nonreactive blocking electrodes. Our work highlights cases where diffuse charge effects are important in the context of voltammetry, and illustrates which regimes can be approximated using simple analytical expressions and which require more careful consideration.

Anomalous diffusion in crowded fluids, e.g., in cytoplasm of living cells, is a frequent phenomenon. A common tool by which the anomalous diffusion of a single particle can be classified is the time-averaged mean square displacement (TAMSD). A classical mechanism leading to the anomalous diffusion is the fractional Brownian motion (FBM). A validation of such process for single-particle tracking data is of great interest for experimentalists. In this paper we propose a rigorous statistical test for FBM based on TAMSD. To this end we analyze the distribution of the TAMSD statistic, which is given by the generalized chi-squared distribution. Next, we study the power of the test by means of Monte Carlo simulations. We show that the test is very sensitive for changes of the Hurst parameter. Moreover, it can easily distinguish between two models of subdiffusion: FBM and continuous-time random walk.

We characterize the carrier density profile of the ground state of graphene in the presence of particle-particle interaction and random charged impurity in zero gate voltage. We provide detailed analysis on the resulting spatially inhomogeneous electron gas, taking into account the particle-particle interaction and the remote Coulomb disorder on an equal footing within the Thomas-Fermi-Dirac theory. We present some general features of the carrier density probability measure of the graphene sheet. We also show that, when viewed as a random surface, the electron-hole puddles at zero chemical potential show peculiar self-similar statistical properties. Although the disorder potential is chosen to be Gaussian, we show that the charge field is non-Gaussian with unusual Kondev relations, which can be regarded as a new class of two-dimensional random-field surfaces. Using Schramm-Loewner (SLE) evolution, we numerically demonstrate that the ungated graphene has conformal invariance and the random zero-charge density contours are ${\mathrm{SLE}}_{\kappa }$ with $\kappa =1.8\pm 0.2$, consistent with $c=-3$ conformal field theory.

Based on previous studies in a single-particle system in both the integrable [Jarzynski, Quan, and Rahav, Phys. Rev. X 5, 031038 (2015)] and the chaotic systems [Zhu, Gong, Wu, and Quan, Phys. Rev. E 93, 062108 (2016)], we study the the correspondence principle between quantum and classical work distributions in a quantum many-body system. Even though the interaction and the indistinguishability of identical particles increase the complexity of the system, we find that for a quantum many-body system the quantum work distribution still converges to its classical counterpart in the semiclassical limit. Our results imply that there exists a correspondence principle between quantum and classical work distributions in an interacting quantum many-body system, especially in the large particle number limit, and further justify the definition of quantum work via two-point energy measurements in quantum many-body systems.

We verify the finite-time fluctuation theorem for a linear Ising chain in contact with heat reservoirs at its ends. Analytic results are derived for a chain consisting of two spins. The system can be mapped onto a model for particle transport, namely, the symmetric exclusion process in contact with thermal and particle reservoirs. We modify the symmetric exclusion process to represent a thermal engine and reproduce universal features of the efficiency at maximum power.

We revisit the problem of deriving the mean-field values of avalanche exponents in systems with absorbing states. These are well known to coincide with those of unbiased branching processes. Here we show that for at least four different universality classes (directed percolation, dynamical percolation, the voter model or compact directed percolation class, and the Manna class of stochastic sandpiles) this common result can be obtained by mapping the corresponding Langevin equations describing each of them into a random walker confined to the origin by a logarithmic potential. We report on the emergence of nonuniversal continuously varying exponent values stemming from the presence of small external driving – that might induce avalanche merging – that, to the best of our knowledge, has not been noticed in the past. Many of the other results derived here appear in the literature as independently derived for individual universality classes or for the branching process itself. Still, we believe that a simple and unified perspective as the one presented here can help (1) clarify the overall picture, (2) underline the superuniversality of the behavior as well as the dependence on external driving, and (3) avoid the common existing confusion between unbiased branching processes (equivalent to a random walker in a balanced logarithmic potential) and standard (unconfined) random walkers.

We develop an approach to liquid thermodynamics based on collective modes. We perform extensive molecular-dynamics simulations of noble, molecular, and metallic liquids, and we provide direct evidence that liquid energy and specific heat are well-described by the temperature dependence of the Frenkel (hopping) frequency. The agreement between predicted and calculated thermodynamic properties is seen in the notably wide range of temperature spanning tens of thousands of Kelvin. The range includes both subcritical liquids and supercritical fluids. We discuss the structural crossover and interrelationships between the structure, dynamics, and thermodynamics of liquids and supercritical fluids.

We investigate the stationary-state fluctuations of a growing one-dimensional interface described by the Kardar-Parisi-Zhang (KPZ) dynamics with a noise featuring smooth spatial correlations of characteristic range $\xi$. We employ nonperturbative functional renormalization group methods to resolve the properties of the system at all scales. We show that the physics of the standard (uncorrelated) KPZ equation emerges on large scales independently of $\xi$. Moreover, the renormalization group flow is followed from the initial condition to the fixed point, that is, from the microscopic dynamics to the large-distance properties. This provides access to the small-scale features (and their dependence on the details of the noise correlations) as well as to the universal large-scale physics. In particular, we compute the kinetic energy spectrum of the stationary state as well as its nonuniversal amplitude. The latter is experimentally accessible by measurements at large scales and retains a signature of the microscopic noise correlations. Our results are compared to previous analytical and numerical results from independent approaches. They are in agreement with direct numerical simulations for the kinetic energy spectrum as well as with the prediction, obtained with the replica trick by Gaussian variational method, of a crossover in $\xi$ of the nonuniversal amplitude of this spectrum.

Chimeras, namely coexisting desynchronous and synchronized dynamics, are formed in an ensemble of identically coupled identical chaotic oscillators when the coupling induces multiple stable attractors, and further when the basins of the different attractors are intertwined in a complex manner. When there is coupling-induced multistability, an ensemble of identical chaotic oscillators—with global coupling, or also under the influence of common noise or an external drive (chaotic, periodic, or quasiperiodic)—inevitably exhibits chimeric behavior. Induced multistability in the system leads to the formation of distinct subpopulations, one or more of which support synchronized dynamics, while in others the motion is asynchronous or incoherent. We study the mechanism for the emergence of such chimeric states, and we discuss the generality of our results.

System heterogeneities such as organelles, cells, and anatomical features strongly affect nonlinear wave patterns in biological systems. These effects are more readily studied in otherwise homogeneous chemical reactions that allow the introduction of tailored structures. Following this approach, we investigate the dynamics of three-dimensional excitation vortices pinned to inert sheets with circular holes arranged on a hexagonal lattice. Experiments with the Belousov-Zhabotinsky reaction and numerical simulations of an excitable reaction-diffusion model reveal vortex pinning that circumvents the rapid collapse of free vortex rings. The pinned scroll waves are affected by the topological mismatch between their looplike rotation backbone and the branched pinning structure. Depending on the initial condition, a multitude of stable vortex states exist, all of which obey topological constraints, suggesting spinlike states for the involved obstacle holes.

‘‘Three is a crowd” is an old proverb that applies as much to social interactions as it does to frustrated configurations in statistical physics models. Accordingly, social relations within a triangle deserve special attention. With this motivation, we explore the impact of topological frustration on the evolutionary dynamics of the snowdrift game on a triangular lattice. This topology provides an irreconcilable frustration, which prevents anticoordination of competing strategies that would be needed for an optimal outcome of the game. By using different strategy updating protocols, we observe complex spatial patterns in dependence on payoff values that are reminiscent to a honeycomb-like organization, which helps to minimize the negative consequence of the topological frustration. We relate the emergence of these patterns to the microscopic dynamics of the evolutionary process, both by means of mean-field approximations and Monte Carlo simulations. For comparison, we also consider the same evolutionary dynamics on the square lattice, where of course the topological frustration is absent. However, with the deletion of diagonal links of the triangular lattice, we can gradually bridge the gap to the square lattice. Interestingly, in this case the level of cooperation in the system is a direct indicator of the level of topological frustration, thus providing a method to determine frustration levels in an arbitrary interaction network.

The spectral radius (i.e., the largest eigenvalue) of the adjacency matrices of complex networks is an important quantity that governs the behavior of many dynamic processes on the networks, such as synchronization and epidemics. Studies in the literature focused on bounding this quantity. In this paper, we investigate how to maximize the spectral radius of interdependent networks by optimally linking $k$ internetwork connections (or interconnections for short). We derive formulas for the estimation of the spectral radius of interdependent networks and employ these results to develop a suite of algorithms that are applicable to different parameter regimes. In particular, a simple algorithm is to link the $k$ nodes with the largest $k$ eigenvector centralities in one network to the node in the other network with a certain property related to both networks. We demonstrate the applicability of our algorithms via extensive simulations. We discuss the physical implications of the results, including how the optimal interconnections can more effectively decrease the threshold of epidemic spreading in the susceptible-infected-susceptible model and the threshold of synchronization of coupled Kuramoto oscillators.

We examine how the distribution of contour lengths and the high-stretch stiffening of individual chain segments affect the macroscopic shear modulus of flexible polymer gels, using a two-dimensional numerical model in which polymer segments form a triangular network and disorder is introduced by varying their contour lengths. We show that, in the relevant parameter range: (i) the nonaffine contribution to the shear modulus is negligible, i.e., the Born approximation is satisfactory, and (ii) the shear modulus is dominated by the contribution originating from equilibrium chain tensions. Moreover, mechanical equilibration at the nodes induces specific correlations between the end-to-end distances and contour lengths of chain segments, which must be properly accounted for to construct reasonable estimates of chain pressure and shear modulus.

The shear flow dynamics of linear and branched wormlike micellar systems based on cetylpyridinium chloride and sodium salicylate in brine solution is investigated through rheometric and scattering techniques. In particular, the flow and the structural flow response are explored via velocimetry measurements and rheological and rheometric small-angle neutron scattering (SANS) experiments, respectively. Although all micellar solutions display a similar shear thinning behavior in the nonlinear regime, the experimental results show that shear banding sets in only when the micelle contour length $\overline{L}$ is sufficiently long, independent of the nature of the micellar connections (either linear or branched micelles). Using rheometric SANS, we observe that the shear banding systems both show very similar orientational ordering as a function of Weissenberg number, while the short branched micelles manifest an unexpected increase of ordering at very low Weissenberg numbers. This suggests the presence of an additional flow-induced relaxation process that is peculiar for branched systems.

It has been recently shown that a colloidal monolayer, e.g., formed at a fluid interface or by means of a suitable confining potential, exhibits anomalous collective diffusion. This is a consequence of the hydrodynamic interactions mediated by the three-dimensional (3D) ambient fluid when the particles are confined to reside on a two-dimensional (2D) manifold. We study theoretically and with numerical simulations the crossover from normal to anomalous diffusion as the particles are, in real systems, confined by a 3D external potential and thus have the possibility to fluctuate out of the 2D manifold, thus forming a quasimonolayer.

We discuss the application of numerical linked cluster expansions (NLCEs) to study one dimensional lattice systems in thermal equilibrium and after quantum quenches from thermal equilibrium states. For the former, we calculate observables in the grand canonical ensemble, and for the latter we calculate observables in the diagonal ensemble. When converged, NLCEs provide results in the thermodynamic limit. We use two different NLCEs: a maximally connected expansion introduced in previous works and a site-based expansion. We compare the effectiveness of both NLCEs. The site-based NLCE is found to work best for systems in thermal equilibrium. However, in thermal equilibrium and after quantum quenches, the site-based NLCE can diverge when the maximally connected one converges. We relate this divergence to the exponentially large number of clusters in the site-based NLCE and the behavior of the weights of observables in those clusters. We discuss the effectiveness of resummations to cure the divergence. Our NLCE calculations are compared to exact diagonalization ones in lattices with periodic boundary conditions. NLCEs are found to outperform exact diagonalization in periodic systems for all quantities studied.

We study a frequency-dependent damping model of hyperdiffusion within the generalized Langevin equation. The model allows for the colored noise defined by its spectral density, assumed to be proportional to ${\omega }^{\delta -1}$ at low frequencies with $0<\delta <1$ (sub-Ohmic damping) or $1<\delta <2$ (super-Ohmic damping), where the frequency-dependent damping is deduced from the noise by means of the fluctuation-dissipation theorem. It is shown that for super-Ohmic damping and certain parameters, the diffusive process of the particle in a titled periodic potential undergos sequentially four time regimes: thermalization, hyperdiffusion, collapse, and asymptotical restoration. For analyzing transition phenomenon of multidiffusive states, we demonstrate that the first exist time of the particle escaping from the locked state into the running state abides by an exponential distribution. The concept of an equivalent velocity trap is introduced in the present model; moreover, reformation of ballistic diffusive system is also considered as a marginal situation but does not exhibit the collapsed state of diffusion.

We consider the exclusion process on a ring with time-dependent defective bonds at which the hopping rate periodically switches between zero and one. This system models main roads in city traffics, intersecting with perpendicular streets. We explore basic properties of the system, in particular dependence of the vehicular flow on the parameters of signalization as well as the system size and the car density. We investigate various types of the spatial distribution of the vehicular density, and show existence of a shock profile. We also measure waiting time behind traffic lights, and examine its relationship with the traffic flow.

Starting from a stochastic agent-based model to represent market exchange in a developing economy, we study time variations of the probability density function of income with simultaneous variation of the consumption deprivation (CD), where CD represents the shortfall in consumption from the saturation level of an essential commodity, cereal. Together, these two models combine income-expenditure-based market dynamics with time variations in consumption due to income. In this new unified theoretical structure, exchange of trade in assets is only allowed when the income exceeds consumption-deprivation while CD itself is endogenously obtained from a separate kinetic model. Our results reveal that the nature of time variation of the CD function leads to a downward trend in the threshold level of consumption of basic necessities, suggesting a possible dietary transition in terms of lower saturation level of food-grain consumption, possibly through an improvement in the level of living. The new poverty index, defined as CD, is amenable to approximate probabilistic prediction within a short time horizon. A major achievement of this work is the intrinsic independence of the poverty index from an exogenous poverty line, making it more objective for policy formulation as opposed to existing poverty indices in the literature.