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Massimiliano Esposito

Publications and source records attributed to Massimiliano Esposito.

At least 73 records · Page 4Linked to original sources
arXiv2023

System-bath entanglement during Markovian relaxation of a fermionic impurity

We investigate the dynamics of entanglement between the system and the environment during thermalization of a noninteracting fermionic impurity coupled to a fermionic thermal bath. We show that transient entanglement can be observed even in the weak coupling regime, when the reduced dynamics and thermodynamics of the system can be well described by an effectively classical and Markovian master equation for the state populations. This entanglement vanishes for long times, but is preserved over timescales comparable to the relaxation time. Its magnitude depends only weakly on the system-environment coupling but instead strongly on the purity of the initial state of the system. We relate the presence of such transient entanglement to the unitary character of the system-bath dynamics underlying the reduced Markovian description.

quant-ph↗
arXiv2023

Characterizing the Conditions for Indefinite Growth in Open Chemical Reaction Networks

The thermodynamic and dynamical conditions necessary to observe indefinite growth in homogeneous open chemical reaction networks (CRNs) satisfying mass action kinetics were presented in Srinivas et al. (2023): Unimolecular CRNs can only accumulate equilibrium concentrations of species while multimolecular CRNs are needed to produce indefinite growth with nonequilibrium concentrations. Within multimolecular CRNs, pseudo-unimolecular CRNs produce nonequilibrium concentrations with zero efficiencies. Nonequilibrium growth with finite efficiencies requires dynamically nonlinear CRNs. In this paper, we provide a detailed analysis supporting these results. Mathematical proofs are provided for growth in unimolecular and pseudo-unimolecular CRNs. For multimolecular CRNs, four models displaying very distinctive topological properties are extensively studied, both numerically and partly analytically.

q-bio.MN↗
arXiv2023

Thermodynamics of Growth in Open Chemical Reaction Networks

We identify the thermodynamic conditions necessary to observe indefinite growth in homogeneous open chemical reaction networks (CRNs) satisfying mass action kinetics. We also characterize the thermodynamic efficiency of growth by considering the fraction of the chemical work supplied from the surroundings that is converted into CRN free energy. We find that indefinite growth cannot arise in CRNs chemostatted by fixing the concentration of some species at constant values, or in continuous-flow stirred tank reactors. Indefinite growth requires a constant net influx from the surroundings of at least one species. In this case, unimolecular CRNs always generate equilibrium linear growth, i.e., a continuous linear accumulation of species with equilibrium concentrations and efficiency one. Multimolecular CRNs are necessary to generate nonequilibrium growth, i.e., the continuous accumulation of species with nonequilibrium concentrations. Pseudo-unimolecular CRNs - a subclass of multimolecular CRNs - always generate asymptotic linear growth with zero efficiency. Our findings demonstrate the importance of the CRN topology and the chemostatting procedure in determining the dynamics and thermodynamics of growth.

q-bio.MN↗
arXiv2023

Nonideal Reaction-Diffusion Systems: Multiple Routes to Instability

We develop a general classification of the nature of the instabilities yielding spatial organization in open nonideal reaction-diffusion systems, based on linear stability analysis. This encompasses dynamics where chemical species diffuse, interact with each other, and undergo chemical reactions driven out of equilibrium by external chemostats. We find analytically that these instabilities can be of two types: instabilities caused by intermolecular energetic interactions (E type), and instabilities caused by multimolecular out-of-equilibrium chemical reactions (R type). Furthermore, we identify a class of chemical reaction networks, containing unimolecular networks but also extending beyond them, that can only undergo E-type instabilities. We illustrate our analytical findings with numerical simulations on two reaction-diffusion models, each displaying one of the two types of instability and generating stable patterns.

cond-mat.stat-mech↗
arXiv2023

A convenient Keldysh contour for thermodynamically consistent perturbative and semiclassical expansions

The work fluctuation theorem (FT) is a symmetry connecting the moment generating functions (MGFs) of the work extracted in a given process and in its time-reversed counterpart. We show that, equivalently, the FT for work in isolated quantum systems can be expressed as an invariance property of a modified Keldysh contour. Modified contours can be used as starting points of perturbative and path integral approaches to quantum thermodynamics, as recently pointed out in the literature. After reviewing the derivation of the contour-based perturbation theory, we use the symmetry of the modified contour to show that the theory satisfies the FT at every order. Furthermore, we extend textbook diagrammatic techniques to the computation of work MGFs, showing that the contributions of the different Feynman diagrams can be added to obtain a general expression of the work statistics in terms of a sum of independent rescaled Poisson processes. In this context, the FT takes the form of a detailed balance condition linking every Feynman diagram with its time-reversed variant. In the second part, we study path integral approaches to the calculation of the MGF, and discuss how the arbitrariness in the choice of the contour impacts the final form of the path integral action. In particular, we show how using a symmetrized contour makes it possible to easily generalize the Keldysh rotation in the context of work statistics, a procedure paving the way to a semiclassical expansion of the work MGF. Furthermore, we use our results to discuss a generalization of the detailed balance conditions at the level of the quantum trajectories.

quant-ph↗
arXiv2023

Nonequilibrium Response for Markov Jump Processes: Exact Results and Tight Bounds

Generalizing response theory of open systems far from equilibrium is a central quest of nonequilibrium statistical physics. Using stochastic thermodynamics, we develop an algebraic method to study the response of nonequilibrium steady state to arbitrary perturbations. This allows us to derive explicit expressions for the response of edge currents as well as traffic to perturbations in kinetic barriers and driving forces. We also show that these responses satisfy very simple bounds. For the response to energy perturbations, we straightforwardly recover results obtained using nontrivial graph-theoretical methods.

cond-mat.stat-mech↗
arXiv2023

Nonequilibrium calcium dynamics optimizes the energetic efficiency of mitochondrial metabolism

Living organisms continuously harness energy to perform complex functions for their adaptation and survival while part of that energy is dissipated in the form of heat or chemical waste. Determining the energetic cost and the efficiency of specific cellular processes remains a largely open problem. Here, we analyze the efficiency of mitochondrial adenosine triphosphate (ATP) production through the tricarboxylic acid (TCA) cycle and oxidative phosphorylation that generates most of the cellular chemical energy in eukaryotes. The regulation of this pathway by calcium signaling represents a well-characterized example of a regulatory cross-talk that can affect the energetic output of a metabolic pathway, but its concrete energetic impact remains elusive. On the one hand, calcium enhances ATP production by activating key enzymes of the TCA cycle, but on the other hand calcium homeostasis depends on ATP availability. To evaluate how calcium signaling impacts the efficiency of mitochondrial metabolism, we propose a detailed kinetic model describing the calcium-mitochondria cross-talk and we analyze it using a nonequilibrium thermodynamic approach: after identifying the effective reactions driving mitochondrial metabolism out of equilibrium, we quantify the thermodynamic efficiency of the metabolic machinery for different physiological conditions. We find that calcium oscillations increase the efficiency with a maximum close to substrate-limited conditions, suggesting a compensatory effect of calcium signaling on the energetics of mitochondrial metabolism.

q-bio.MN↗
arXiv2023

Quantum and classical contributions to entropy production in fermionic and bosonic Gaussian systems

As previously demonstrated, the entropy production -- a key quantity characterizing the irreversibility of thermodynamic processes -- is related to generation of correlations between degrees of freedom of the system and its thermal environment. This raises the question of whether such correlations are of a classical or quantum nature, namely, whether they are accessible through local measurements on the correlated degrees of freedom. We address this problem by considering fermionic and bosonic Gaussian systems. We show that for fermions the entropy production is mostly quantum due to the parity superselection rule which restricts the set of physically allowed measurements to projections on the Fock states, thus significantly limiting the amount of classically accessible correlations. In contrast, in bosonic systems a much larger amount of correlations can be accessed through Gaussian measurements. Specifically, while the quantum contribution may be important at low temperatures, in the high temperature limit the entropy production corresponds to purely classical position-momentum correlations. Our results demonstrate an important difference between fermionic and bosonic systems regarding the existence of a quantum-to-classical transition in the microscopic formulation of the entropy production. They also show that entropy production can be mainly caused by quantum correlations even in the weak coupling limit, which admits a description in terms of classical rate equations for state populations, as well as in the low particle density limit, where the transport properties of both bosons and fermions converge to those of classical particles.

quant-ph↗
arXiv2023

Deficiency, Kinetic Invertibility, and Catalysis in Stochastic Chemical Reaction Networks

Stochastic chemical processes are described by the chemical master equation satisfying the law of mass-action. We first ask whether the dual master equation, which has the same steady state as the chemical master equation, but with inverted reaction currents, satisfies the law of mass-action, namely, still describes a chemical process. We prove that the answer depends on the topological property of the underlying chemical reaction network known as deficiency. The answer is yes only for deficiency-zero networks. It is no for all other networks, implying that their steady-state currents cannot be inverted by controlling the kinetic constants of the reactions. Hence, the network deficiency imposes a form of non-invertibility to the chemical dynamics. We then ask whether catalytic chemical networks are deficiency-zero. We prove that the answer is no when they are driven out of equilibrium due to the exchange of some species with the environment.

cond-mat.stat-mech↗
arXiv2023

Ensemble dependence of information-theoretic contributions to the entropy production

The entropy production of an open system coupled to a reservoir initialized in a canonical state can be expressed as a sum of two microscopic information-theoretic contributions: the system-bath mutual information and the relative entropy measuring the displacement of the environment from equilibrium. We investigate whether this result can be generalized to situations where the reservoir is initialized in a microcanonical or in a certain pure state (e.g., an eigenstate of a nonintegrable system), such that the reduced dynamics and thermodynamics of the system are the same as for the thermal bath. We show that while in such a case the entropy production can still be expressed as a sum of the mutual information between the system and the bath and a properly redefined displacement term, the relative weight of those contributions depends on the initial state of the reservoir. In other words, different statistical ensembles for the environment predicting the same reduced dynamics for the system give rise to the same total entropy production but to different information-theoretic contributions to the entropy production.

cond-mat.stat-mech↗
arXiv2023

Thermalization and dephasing in collisional reservoirs

We introduce a wide class of quantum maps that arise in collisional reservoirs and are able to thermalize a system if they operate in conjunction with an additional dephasing mechanism. These maps describe the effect of collisions and induce transitions between populations that obey detailed balance, but also create coherences that prevent the system from thermalizing. We combine these maps with a unitary evolution acting during random Poissonian times between collisions and causing dephasing. We find that, at a low collision rate, the nontrivial combination of these two effects causes thermalization in the system. This scenario is suitable for modeling collisional reservoirs at equilibrium. We justify this claim by identifying the conditions for such maps to arise within a scattering theory approach and provide a thorough characterization of the resulting thermalization process.

quant-ph↗
arXiv2023

A [3]-catenane non-autonomous molecular motor model: geometric phase, no-pumping theorem, and energy transduction

We study a model of synthetic molecular motor - a [3]-catenane consisting of two small macrocycles mechanically interlocked with a bigger one - subjected to a time-dependent driving using stochastic thermodynamics. The model presents nontrivial features due to the two interacting small macrocycles, but is simple enough to be treated analytically in limiting regimes. Among the results obtained, we find a mapping into an equivalent [2]-catenane that reveals the implications of the no-pumping theorem stating that to generate net motion of the small macrocycles, both energies and barriers need to change. In the adiabatic limit (slow driving), we fully characterize the motor's dynamics and show that the net motion of the small macrocycles is expressed as a surface integral in parameter space which corrects previous erroneous results. We also analyze the performance of the motor subjected to a step-wise driving protocols in absence and in presence of an applied load. Optimization strategies for generating large currents and maximizing free-energy transduction are proposed. This simple model provides interesting clues into the working principles of non-autonomous molecular motors and their optimization.

cond-mat.stat-mech↗
arXiv2023

Fermionic one-body entanglement as a thermodynamic resource

There is ongoing controversy about whether a coherent superposition of the occupied states of two fermionic modes should be regarded entangled or not, that is, whether its intrinsic quantum correlations are operationally accessible and useful as a resource. This has been questioned on the basis that such an entanglement cannot be accessed by local operations on individual modes due to the parity superselection rule which constrains the set of physical observables. In other words, one cannot observe violations of Bell's inequality. Here we show, however, that entanglement of a two-mode fermionic state can be used as a genuine quantum resource in open-system thermodynamic processes, enabling one to perform tasks forbidden for separable states. We thus demonstrate that quantum thermodynamics can shed light on the nature of fermionic entanglement and the operational meaning of the different notions used to define it.

quant-ph↗
arXiv2023

Landau theory for finite-time dynamical phase transitions

We study the time evolution of thermodynamic observables that characterise the dissipative nature of thermal relaxation after an instantaneous temperature quench. Combining tools from stochastic thermodynamics and large-deviation theory, we develop a powerful theory for computing the large-deviation statistics of such observables. Our method naturally leads to a description in terms of a dynamical Landau theory, a versatile tool for the analysis of finite-time dynamical phase transitions. The topology of the associated Landau potential allows for an unambiguous identification of the dynamical order parameter and of the phase diagram. As an immediate application of our method, we show that the probability distribution of the heat exchanged between a mean-field spin model and the environment exhibits a singular point, a kink, caused by a finite-time dynamical phase transition. Using our Landau theory, we conduct a detailed study of the phase transition. Although the manifestation of the new transition is similar to that of a previously found finite-time transition in the magnetisation, the properties and the dynamical origins of the two turn out to be very different.

cond-mat.stat-mech↗
arXiv2023

Circuit Theory for Chemical Reaction Networks

We lay the foundation of a circuit theory for chemical reaction networks. Chemical reactions are grouped into chemical modules solely characterized by their current-concentration characteristic, as electrical devices by their current-voltage (I-V) curve in electronic circuit theory. This, combined with the chemical analog of Kirchhoff's current and voltage laws, provides a powerful tool to predict reaction currents and dissipation across complex chemical networks. The theory can serve to build accurate reduced models of complex networks as well as to design networks performing desired tasks.

q-bio.MN↗
arXiv2022

Information flows in macroscopic Maxwell's demons

A CMOS-based implementation of an autonomous Maxwell's demon was recently proposed (Phys. Rev. Lett. 129, 120602) to demonstrate that a Maxwell demon can still work at macroscopic scales, provided that its power supply is scaled appropriately. Here, we first provide a full analytical characterization of the non-autonomous version of that model. We then study system-demon information flows within generic autonomous bipartite setups displaying a macroscopic limit. By doing so, we can study the thermodynamic efficiency of both the measurement and the feedback process performed by the demon. We find that the information flow is an intensive quantity and that, as a consequence, any Maxwell's demon is bound to stop working above a finite scale if all parameters but the scale are fixed. However, this can be prevented by appropriately scaling the thermodynamic forces. These general results are applied to the autonomous CMOS-based demon.

cond-mat.stat-mech↗
arXiv2022

Information Thermodynamics for Deterministic Chemical Reaction Networks

Information thermodynamics relates the rate of change of mutual information between two interacting subsystems to their thermodynamics when the joined system is described by a bipartite stochastic dynamics satisfying local detailed balance. Here, we expand the scope of information thermodynamics to deterministic bipartite chemical reaction networks, namely, composed of two coupled subnetworks sharing species, but not reactions. We do so by introducing a meaningful notion of mutual information between different molecular features, that we express in terms of deterministic concentrations. This allows us to formulate separate second laws for each subnetwork, which account for their energy and information exchanges, in complete analogy with stochastic systems. We then use our framework to investigate the working mechanisms of a model of chemically-driven self-assembly and an experimental light-driven bimolecular motor. We show that both systems are constituted by two coupled subnetworks of chemical reactions. One subnetwork is maintained out of equilibrium by external reservoirs (chemostats or light sources) and powers the other via energy and information flows. In doing so, we clarify that the information flow is precisely the thermodynamic counterpart of an information ratchet mechanism only when no energy flow is involved.

cond-mat.stat-mech↗
arXiv2022

Thermodynamic consistency of quantum master equations

Starting from a microscopic system-baths description, we derive the general conditions for a time-local quantum master equation (QME) to satisfy the first and second law of thermodynamics at the fluctuating level. Using counting statistics, we show that the fluctuating second law can be rephrased as a Generalized Quantum Detailed Balance condition (GQDB), i.e., a symmetry of the time-local generators which ensures the validity of the fluctuation theorem. When requiring in addition a strict system-bath energy conservation, the GQDB reduces to the usual notion of detailed balance which ensures QMEs with Gibbsian steady states. However, if energy conservation is only required on average, QMEs with non Gibbsian steady states can still maintain a certain level of thermodynamic consistency. Applying our theory to commonly used QMEs, we show that the Redfield equation breaks the GQDB, and that some recently derived approximation schemes based on the Redfield equation (which hold beyond the secular approximation and allow to derive a QME of Lindblad form) satisfy the GQDB and the average first law. We find that performing the secular approximation is the only way to ensure the first and second law at the fluctuating level.

quant-ph↗