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Gianmaria Falasco

Publications and source records attributed to Gianmaria Falasco.

At least 37 records · Page 2Linked to original sources

Active Brownian Heat Engines

When do non-equilibrium forms of disordered energy qualify as heat? \textcolor{blue}{We address this question in the context of cyclically operating heat engines in contact with a non-equilibrium energy reservoir that defies the zeroth law of thermodynamics. To consistently address the latter as a heat bath requires the existence of a precise mapping to an equivalent cycle with an equilibrium bath at a time-dependent effective temperature. We identify the most general setup for which this can generically be ascertained and thoroughly discuss an analytically tractable, experimentally relevant scenario}: a Brownian particle confined in a \textcolor{blue}{periodically} modulated harmonic potential and coupled to some non-equilibrium bath of variable activity. We deduce formal limitations for its thermodynamic performance, including maximum efficiency, efficiency at maximum power, and maximum efficiency at fixed power. They can guide the design of new micro-machines and clarify how much these can outperform passive-bath designs, which has been a debated issue for recent experimental realizations. To illustrate the general principles for practical quasi-static and finite-rate protocols, we further analyze a specific realization of such an active heat engine based on the paradigmatic Active Brownian Particle (ABP) model. This reveals some non-intuitive features of the explicitly computed dynamical effective temperature, illustrates various conceptual and practical limitations of the effective-equilibrium mapping, and clarifies the operational relevance of various coarse-grained measures of dissipation.

cond-mat.stat-mech↗

Jarzynski Equality for Soret Equilibria -- Virtues of Virtual Potentials

The Jarzynski equality relates the free energy difference between two equilibrium states to the fluctuating irreversible work afforded to switch between them. The prescribed fixed temperature for the equilibrium states implicitly constrains the dissipative switching process that can take the system far from equilibrium. Here, we demonstrate theoretically and experimentally that such a relation also holds for the nonisothermal case, where the initial stationary state is not in equilibrium and the switching is effected by dynamically changing temperature gradients instead of a conservative force. Our demonstration employs a single colloidal particle trapped by optically induced thermophoretic drift currents. It relies on identifying suitable equivalents of classical work and heat and our ability to measure their distributions and express them in terms of a virtual potential.

cond-mat.stat-mech↗

Thermodynamics of Non-Elementary Chemical Reaction Networks

We develop a thermodynamic framework for closed and open chemical networks applicable to non-elementary reactions that do not need to obey mass action kinetics. It only requires the knowledge of the kinetics and of the standard chemical potentials, and makes use of the topological properties of the network (conservation laws and cycles). Our approach is proven to be exact if the network results from a bigger network of elementary reactions where the fast-evolving species have been coarse grained. Our work should be particularly relevant for energetic considerations in biosystems where the characterization of the elementary dynamics is seldomly achieved.

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Stochastic thermodynamics of all-to-all interacting many-body systems

We provide a stochastic thermodynamic description across scales for $N$ identical units with all-to-all interactions that are driven away from equilibrium by different reservoirs and external forces. We start at the microscopic level with Poisson rates describing transitions between many-body states. We then identify an exact coarse graining leading to a mesoscopic description in terms of Poisson transitions between system occupations. We proceed studying macroscopic fluctuations using the Martin-Siggia-Rose formalism and large deviation theory. In the macroscopic limit ($N \to \infty$), we derive the exact nonlinear (mean-field) rate equation describing the deterministic dynamics of the most likely occupations. We identify the scaling of the energetics and kinetics ensuring thermodynamic consistency (including the detailed fluctuation theorem) across microscopic, mesoscopic and macroscopic scales. The conceptually different nature of the Shannon entropy (and of the ensuing stochastic thermodynamics) at different scales is also outlined. Macroscopic fluctuations are calculated semi-analytically in an out-of-equilibrium Ising model. Our work provides a powerful framework to study thermodynamics of nonequilibrium phase transitions.

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Strong current response to slow modulation: a metabolic case-study

We study the current response to periodic driving of a crucial biochemical reaction network, namely, substrate inhibition. We focus on the conversion rate of substrate into product under time-varying metabolic conditions, modeled by a periodic modulation of the product concentration. We find that the system exhibits a strong nonlinear response to small driving frequencies both for the mean time-averaged current and for the fluctuations. For the first, we obtain an analytic formula by coarse-graining the original model to a solvable one. The result is nonperturbative in the modulation amplitude and frequency. We then refine the picture by studying the stochastic dynamics of the full system using a large deviations approach, that allows to show the resonant effect at the level of the time-averaged variance and signal-to-noise ratio. Finally, we discuss how this nonequilibrium effect may play a role in metabolic and synthetic networks.

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The dissipation-time uncertainty relation

We show that the dissipation rate bounds the rate at which physical processes can be performed in stochastic systems far from equilibrium. Namely, for rare processes we prove the fundamental tradeoff $\langle \dot S_\text{e} \rangle \mathcal{T} \geq k_{\text{B}} $ between the entropy flow $\langle \dot S_\text{e} \rangle$ into the reservoirs and the mean time $\mathcal{T}$ to complete a process. This dissipation-time uncertainty relation is a novel form of speed limit: the smaller the dissipation, the larger the time to perform a process.

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Chemical Cloaking

Hiding an object in a chemical gradient requires to suppress the distortions it would naturally cause on it. To do so, we propose a strategy based on coating the object with a chemical reaction-diffusion network which can act as an active cloaking device. By controlling the concentration of some species in its immediate surrounding, the chemical reactions redirect the gradient as if the object was not there. We also show that a substantial fraction of the energy required to cloak can be extracted from the chemical gradient itself.

physics.chem-ph↗

Unifying Thermodynamic Uncertainty Relations

We introduce a new technique to bound the fluctuations exhibited by a physical system, based on the Euclidean geometry of the space of observables. Through a simple unifying argument, we derive a sweeping generalization of so-called Thermodynamic Uncertainty Relations (TURs). We not only strengthen the bounds but extend their realm of applicability and in many cases prove their optimality, without resorting to large deviation theory or information-theoretic techniques. In particular, we find the best TUR based on entropy production alone and also derive a novel bound for stationary Markov processes, which surpasses previous known bounds. Our results derive from the non-invariance of the system under a symmetry which can be other than time reversal and thus open a wide new spectrum of applications.

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Thermodynamics of Chemical Waves

Chemical waves constitute a known class of dissipative structures emerging in reaction-diffusion systems. They play a crucial role in biology, spreading information rapidly to synchronize and coordinate biological events. We develop a rigorous thermodynamic theory of reaction-diffusion systems to characterize chemical waves. Our main result is the definition of the proper thermodynamic potential of the local dynamics as a nonequilibrium free energy density and establishing its balance equation. This enables us to identify the dynamics of the free energy, of the dissipation, and of the work spent to sustain the wave propagation. Two prototypical classes of chemical waves are examined. From a thermodynamic perspective, the first is sustained by relaxation towards equilibrium and the second by nonconservative forces generated by chemostats. We analytically study step-like waves, called wavefronts, using the Fisher-Kolmogorov equation as representative of the first class and oscillating waves in the Brusselator model as representative of the second. Given the fundamental role of chemical waves as message carriers in biosystems, our thermodynamic theory constitutes an important step toward an understanding of information transfers and processing in biology.

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Large deviations and dynamical phase transitions in stochastic chemical networks

Chemical reaction networks offer a natural nonlinear generalisation of linear Markov jump processes on a finite state-space. In this paper, we analyse the dynamical large deviations of such models, starting from their microscopic version, the chemical master equation. By taking a large-volume limit, we show that those systems can be described by a path integral formalism over a Lagrangian functional of concentrations and chemical fluxes. This Lagrangian is dual to a Hamiltonian, whose trajectories correspond to the most likely evolution of the system given its boundary conditions. The same can be done for a system biased on time-averaged concentrations and currents, yielding a biased Hamiltonian whose trajectories are optimal paths conditioned on those observables. The appropriate boundary conditions turn out to be mixed, so that, in the long time limit, those trajectories converge to well-defined attractors. We are then able to identify the largest value that the Hamiltonian takes over those attractors with the scaled cumulant generating function of our observables, providing a non-linear equivalent to the well-known Donsker-Varadhan formula for jump processes. On that basis, we prove that chemical reaction networks that are deterministically multistable generically undergo first-order dynamical phase transitions in the vicinity of zero bias. We illustrate that fact through a simple bistable model called the Schlögl model, as well as multistable and unstable generalisations of it, and we make a few surprising observations regarding the stability of deterministic fixed points, and the breaking of ergodicity in the large-volume limit.

cond-mat.stat-mech↗

Negative differential response in chemical reactions

Reaction currents in chemical networks usually increase when increasing their driving affinities. But far from equilibrium the opposite can also happen. We find that such negative differential response (NDR) occurs in reaction schemes of major biological relevance, namely, substrate inhibition and autocatalysis. We do so by deriving the full counting statistics of two minimal representative models using large deviation methods. We argue that NDR implies the existence of optimal affinities that maximize the robustness against environmental and intrinsic noise at intermediate values of dissipation. An analogous behavior is found in dissipative self-assembly, for which we identify the optimal working conditions set by NDR.

cond-mat.stat-mech↗

Information Thermodynamics of Turing Patterns

We set up a rigorous thermodynamic description of reaction-diffusion systems driven out of equilibrium by time-dependent space-distributed chemostats. Building on the assumption of local equilibrium, nonequilibrium thermodynamic potentials are constructed exploiting the symmetries of the chemical network topology. It is shown that the canonical (resp. semigrand canonical) nonequilibrium free energy works as a Lyapunov function in the relaxation to equilibrium of a closed (resp. open) system and its variation provides the minimum amount of work needed to manipulate the species concentrations. The theory is used to study analytically the Turing pattern formation in a prototypical reaction-diffusion system, the one-dimensional Brusselator model, and to classify it as a genuine thermodynamic nonequilibrium phase transition.

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Microscopic derivation of the hydrodynamics of active-Brownian-particle suspensions

We derive the hydrodynamic equations of motion for a fluid of active particles described by under- damped Langevin equations that reduce to the Active-Brownian-Particle model, in the overdamped limit. The contraction into the hydrodynamic description is performed by locally averaging the par- ticle dynamics with the non-equilibrium many-particle probability density, whose formal expression is found in the physically relevant limit of high-friction through a multiple-time-scale analysis. This approach permits to identify the conditions under which self-propulsion can be subsumed into the fluid stress tensor and thus to define systematically and unambiguously the local pressure of the active fluid.

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Interacting Brownian dynamics in a nonequilibrium particle bath

We set up a mesoscopic theory for interacting Brownian particles embedded in a nonequilibrium environment, starting from the microscopic interacting many-body theory. Using nonequilibrium linear response theory, we characterize the effective dynamical interactions on the mesoscopic scale and the statistics of the nonequilibrium environmental noise, arising upon integrating out the fast degrees of freedom. As hallmarks of nonequilibrium, the breakdown of the fluctuation-dissipation and action-reaction relations for Brownian degrees of freedom are exemplified with two prototypical models for the environment, namely, active Brownian particles and stirred colloids.

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A general fluctuation-response relation for noise variations and its application to driven hydrodynamic experiments

The effect of a change of noise amplitudes in overdamped diffusive systems is linked to their unperturbed behavior by means of a nonequilibrium fluctuation-response relation. This formula holds also for systems with state-independent nontrivial diffusivity matrices, as we show with an application to an experiment of two trapped and hydrodynamically coupled colloids, one of which is subject to an external random forcing that mimics an effective temperature. The nonequilibrium susceptibility of the energy to a variation of this driving is an example of our formulation, which improves an earlier version, as it does not depend on the time-discretization of the stochastic dynamics. This scheme holds for generic systems with additive noise and can be easily implemented numerically, thanks to matrix operations.

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Thermal response of nonequilibrium RC-circuits

We analyze experimental data obtained from an electrical circuit having components at different temperatures, showing how to predict its response to temperature variations. This illustrates in detail how to utilize a recent linear response theory for nonequilibrium overdamped stochastic systems. To validate these results, we introduce a reweighting procedure that mimics the actual realization of the perturbation and allows extracting the susceptibility of the system from steady state data. This procedure is closely related to other fluctuation-response relations based on the knowledge of the steady state probability distribution. As an example, we show that the nonequilibrium heat capacity in general does not correspond to the correlation between the energy of the system and the heat flowing into it. Rather, also non-dissipative aspects are relevant in the nonequilbrium fluctuation response relations.

cond-mat.stat-mech↗

Mesoscopic virial equation for nonequilibrium statistical mechanics

We derive a class of mesoscopic virial equations governing energy partition between conjugate position and momentum variables of individual degrees of freedom. They are shown to apply to a wide range of nonequilibrium steady states with stochastic (Langevin) and deterministic (Nosé--Hoover) dynamics, and to extend to collective modes for models of heat-conducting lattices. A generalised macroscopic virial theorem ensues upon summation over all degrees of freedom. This theorem allows for the derivation of nonequilibrium state equations that involve dissipative heat flows on the same footing with state variables, as exemplified for inertial Brownian motion with solid friction and overdamped active Brownian particles subject to inhomogeneous pressure.

cond-mat.stat-mech↗

Exact symmetries in the velocity fluctuations of a hot Brownian swimmer

Symmetries constrain dynamics. We test this fundamental physical principle, experimentally and by molecular dynamics simulations, for a hot Janus swimmer operating far from thermal equilibrium. Our results establish scalar and vectorial steady-state fluctuation theorems and a thermodynamic uncertainty relation that link the fluctuating particle current to its entropy production at an effective temperature. A Markovian minimal model elucidates the underlying non-equilbrium physics.

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