arXiv subjects

Gian Paolo Beretta

Publications and source records attributed to Gian Paolo Beretta.

At least 19 recordsLinked to original sources

arXiv2026

Evolution of Hypoequilibrium States in Steepest Entropy Ascent Models for Nonequilibrium Quantum Thermodynamics

A formal development of the hypoequilibrium (HE) state concept within the Steepest-Entropy-Ascent Quantum Thermodynamics (SEAQT) framework is presented, emphasizing its rigorous mathematical formulation. Using a general decomposition of the Hilbert space, HE states are defined in operator language and the reduced evolution of the associated intensive parameters for the regime where the dissipative dynamics commutes with the Hamiltonian is derived. It is proved that the $M$-th order HE family (where $M$ is the number of spectral sectors) constitutes an invariant manifold under the SEAQT equation of motion, ensuring that states initially representing a ``mixture of canonicals'' maintain this structure throughout their evolution. Furthermore, a formal connection is established between the HE ansatz and the rate-controlled constrained equilibrium (RCCE) method, identifying HE variables as constraint potentials. Finally, the model is extended to non-Hamiltonian SEAQT (NH-SEAQT) interactions to describe thermodynamically consistent energy and entropy exchanges between subsystems and heat baths. This work provides the formal foundation for reduced-order modeling of far-from-equilibrium relaxation and transport processes, and supports a methodology previously applied across various physical and chemical systems.

quant-ph↗

arXiv2026

Universal Foundations of Thermodynamics: Entropy and Energy Beyond Equilibrium and Without Extensivity

Thermodynamics is commonly presented as a theory of macroscopic systems in stable equilibrium, built upon assumptions of extensivity and scaling with system size. In this paper, we present a universal formulation of the elementary foundations of thermodynamics, in which entropy and energy are defined and employed beyond equilibrium and without assuming extensivity. The formulation applies to all systems -- large and small, with many or few particles -- and to all states, whether equilibrium or nonequilibrium, by relying on carefully stated operational definitions and existence principles rather than macroscopic idealizations. Key thermodynamic concepts, including adiabatic availability and available energy, are developed and illustrated using the energy-entropy diagram representation of nonequilibrium states, which provides geometric insight into irreversibility and the limits of work extraction for systems of any size. A substantial part of the paper is devoted to the analysis of entropy transfer in non-work interactions, leading to precise definitions of heat interactions and heat-and-diffusion interactions of central importance in mesoscopic continuum theories of nonequilibrium behavior in simple and complex solids and fluids. As a direct consequence of this analysis, Clausius inequalities and the Clausius statement of the second law are derived in forms explicitly extended to nonequilibrium processes. The resulting framework presents thermodynamics as a universal theory whose concepts apply uniformly to all systems, large and small, and provides a coherent foundation for both teaching and modern applications.

quant-ph↗

arXiv2025

No-Signaling in Steepest Entropy Ascent: A Nonlinear Non-local Non-equilibrium Quantum Dynamics of Composite Systems

The Lindbladian formalism models open quantum systems using a 'bottom-up' approach, deriving linear dynamics from system-environment interactions. We present a 'top-down' approach starting with phenomenological constraints, focusing on system's structure, subsystems' interactions, environmental effects, and often using a non-equilibrium variational principle designed to enforce strict thermodynamic consistency. However, incorporating the second law's requirement -- that Gibbs states are the sole stable equilibria -- necessitates nonlinear dynamics, challenging no-signaling principles in composite systems. We reintroduce 'local perception operators' and show that they allow to model signaling-free non-local effects. Using the steepest-entropy-ascent variational principle as an example, we demonstrate the validity of the 'top-down' approach for integrating quantum mechanics and thermodynamics in phenomenological models, with potential applications in quantum computing and resource theories.

quant-ph↗

arXiv2019

The fourth law of thermodynamics: steepest entropy ascent

When thermodynamics is understood as the science (or art) of constructing effective models of natural phenomena by choosing a minimal level of description capable of capturing the essential features of the physical reality of interest, the scientific community has identified a set of general rules that the model must incorporate if it aspires to be consistent with the body of known experimental evidence. Some of these rules are believed to be so general that we think of them as laws of Nature, such as the great conservation principles, whose "greatness" derives from their generality, as masterfully explained by Feynman in one of his legendary lectures. The second law of thermodynamics is universally contemplated among the great laws of Nature. In this paper we show that, in the past four decades, an enormous body of scientific research devoted to modeling the essential features of nonequilibrium natural phenomena has converged from many different directions and frameworks towards the general recognition (albeit still expressed in different but equivalent forms and language) that another rule is also indispensable and reveals another great law of Nature that we propose to call the \caporali{fourth law of thermodynamics}. We state it as follows: every nonequilibrium state of a system or local subsystem for which entropy is well-defined must be equipped with a metric in state space with respect to which the irreversible component of its time evolution is in the direction of steepest entropy ascent compatible with the conservation constraints. To illustrate the power of the fourth law, we derive (nonlinear) extensions of Onsager reciprocity and fluctuation-dissipation relations to the far-nonequilibrium realm within the framework of the rate-controlled constrained-equilibrium (RCCE) approximation (also known as the quasi-equilibrium approximation).

cond-mat.stat-mech↗

arXiv2019

New definitions of thermodynamic temperature and entropy not based on the concepts of heat and thermal reservoir

From a new rigorous formulation of the general axiomatic foundations of thermodynamics we derive an operational definition of entropy that responds to the emergent need in many technological frameworks to understand and deploy thermodynamic entropy well beyond the traditional realm of equilibrium states of macroscopic systems. The new treatment starts from a previously developed set of carefully worded operational definitions for all the necessary basic concepts, and is not based on the traditional ones of "heat" and of "thermal reservoir." It is achieved in three steps. First, a new definition of thermodynamic temperature is stated, for any stable equilibrium state. Then, by employing this definition, a measurement procedure is developed which defines uniquely the property entropy in a broad domain of states, which could include \textit{in principle}, even some non-equilibrium states of few-particle systems, provided they are separable and uncorrelated. Finally, the domain of validity of the definition is extended, possibly to every state of every system, by a different procedure, based on the preceding one, which associates a range of entropy values to any state not included in the previous domain. The principle of entropy non-decrease and the additivity of entropy are proved in both the domains considered.

quant-ph↗

arXiv2019

Time-Energy and Time-Entropy Uncertainty Relations in Nonequilibrium Quantum Thermodynamics under Steepest-Entropy-Ascent Nonlinear Master Equations

In the domain of nondissipative unitary Hamiltonian dynamics, the well-known Mandelstam-Tamm-Messiah time-energy uncertainty relation $τ_{F}Δ_H\ge \hbar/2$ provides a general lower bound to the characteristic time $τ_F =Δ_F/|{\rm d} \langle F\rangle/dt|$ with which the mean value of a generic quantum observable $F$ can change with respect to the width $Δ_F$ of its uncertainty distribution (square root of $F$ fluctuations). A useful practical consequence is that in unitary dynamics the states with longer lifetimes are those with smaller energy uncertainty $Δ_H$ (square root of energy fluctuations). Here we show that when unitary evolution is complemented with a steepest-entropy-ascent model of dissipation, the resulting nonlinear master equation entails that these lower bounds get modified and depend also on the entropy uncertainty $Δ_S$ (square root of entropy fluctuations). For example, we obtain the time-energy--and--time-entropy uncertainty relation $(2τ_{F}Δ_H/ \hbar)^2+(τ_{F}Δ_S/{k_{\rm\scriptscriptstyle B}}τ)^2 \ge 1$ where $τ$ is a characteristic dissipation time functional that for each given state defines the strength of the nonunitary, steepest-entropy-ascent part of the assumed master equation. For purely dissipative dynamics this reduces to the time-entropy uncertainty relation $τ_{F}Δ_S\ge {k_{\rm\scriptscriptstyle B}}τ$, meaning that the nonequilibrium dissipative states with longer lifetime are those with smaller entropy uncertainty $Δ_S$.

quant-ph↗

arXiv2016

Steepest-entropy-ascent quantum thermodynamic framework for describing the non-equilibrium behavior of a chemically reactive system at an atomistic level

Steepest-Entropy-Ascent Quantum Thermodynamics (SEAQT) provides a general framework for the description of non-equilibrium phenomena at any level, particularly the atomistic one. This theory and its dynamical postulate are used here to develop a general mathematical framework, which at an atomistic level, in particular, can be used to predict the non-equilibrium evolution in state of a closed, chemically reactive mixture such as the one examined here, i.e., a mixture of hydrogen (H2) and flourine (F) contained in an isolated tank of fixed volume. The general framework provided, however, is written for a reactive system subject to multiple reaction mechanisms. To predict this evolution in state, both the energy and particle number eigenvalue problems for a dilute gas are set up and solved analytically. Wall and non-ideal-gas behavior effects are neglected, although the extension to dense gases is straightforward but left for a future paper. The system-level energy and particle number eigenvalues and eigenstates found are used in the nonlinear equation of motion of SEAQT to determine the time evolution of the thermodynamic state of the system, thus, effectively describing the reaction kinetics of the reaction and the system's relaxation to stable equilibrium. The predicted time evolution is then compared to the results of a standard detailed kinetic model used, in the near-equilibrium limit, to extract the single time constant needed by the SEAQT equation of motion.

physics.chem-ph↗

arXiv2015

Essential equivalence of the GENERIC and Steepest Entropy Ascent models of dissipation for non-equilibrium thermodynamics

By reformulating the Steepest-Entropy-Ascent (SEA) dynamical model for non-equilibrium thermodynamics in the mathematical language of Differential Geometry, we compare it with the primitive formulation of the GENERIC model and discuss the main technical differences of the two approaches. In both dynamical models the description of dissipation is of the "entropy-gradient" type. SEA focuses only onto the irreversible component of the time evolution, chooses a sub-Riemannian metric tensor as dissipative structure, and uses the local entropy density field as potential. GENERIC emphasizes the coupling between the reversible and irreversible components of the time evolution, chooses two compatible degenerate structures (Poisson and degenerate co-Riemannian), and uses the global energy and entropy functionals as potentials. As an illustration, we rewrite the known GENERIC formulation of the Boltzmann Equation in terms of the square-root of the distribution function adopted by the SEA formulation. We then provide a formal proof that in more general frameworks, whenever all degeneracies in the GENERIC framework are related to conservation laws, the SEA and GENERIC models of the irreversible component of the dynamics are essentially interchangeable, provided of course they assume the same kinematics. As part of the discussion, we note that equipping the dissipative structure of GENERIC with the Leibniz identity makes it automatically SEA on metric leaves.

cond-mat.stat-mech↗

arXiv2014

A definition of thermodynamic entropy valid for non-equilibrium states and few-particle systems

From a new rigorous formulation of the general axiomatic foundations of thermodynamics we derive an operational definition of entropy that responds to the emergent need in many technological frameworks to understand and deploy thermodynamic entropy well beyond the traditional realm of equilibrium states of macroscopic systems. The new definition is achieved by avoiding to resort to the traditional concepts of "heat" (which restricts $a$ $priori$ the traditional definitions of entropy to the equilibrium domain) and of "thermal reservoir" (which restricts $in$ $practice$ our previous definitions of non-equilibrium entropy to the many-particle domain). The measurement procedure that defines entropy is free from intrinsic limitations and can be applied, $in$ $principle$, even to non-equilibrium states of few-particle systems, provided they are separable and uncorrelated. The construction starts from a previously developed set of carefully worded operational definitions for all the basic concepts. Then, through a new set of fully spelled-out fundamental hypotheses (four postulates and five assumptions) we derive the definitions of energy and entropy of any state, and of temperature of any stable equilibrium state. Finally, we prove the principle of entropy non-decrease, the additivity of entropy differences, the maximum entropy principle, and the impossibility of existence of a thermal reservoir.

math-ph↗

arXiv2014

Steepest Entropy Ascent Model for Far-Non-Equilibrium Thermodynamics. Unified Implementation of the Maximum Entropy Production Principle

By suitable reformulations, we cast the mathematical frameworks of several well-known different approaches to the description of non-equilibrium dynamics into a unified formulation, which extends to such frameworks the concept of Steepest Entropy Ascent (SEA) dynamics introduced by the present author in previous works on quantum thermodynamics. The present formulation constitutes a generalization also for the quantum thermodynamics framework. In the SEA modeling principle a key role is played by the geometrical metric with respect to which to measure the length of a trajectory in state space. In the near equilibrium limit, the metric tensor is related to the Onsager's generalized resistivity tensor. Therefore, through the identification of a suitable metric field which generalizes the Onsager generalized resistance to the arbitrarily far non-equilibrium domain, most of the existing theories of non-equilibrium thermodynamics can be cast in such a way that the state exhibits a spontaneous tendency to evolve in state space along the path of SEA compatible with the conservation constraints and the boundary conditions. The resulting unified family of SEA dynamical models is intrinsically and strongly consistent with the second law of thermodynamics. Non-negativity of the entropy production is a readily proved general feature of SEA dynamics. In several of the different approaches to non-equilibrium description we consider here, the SEA concept has not been investigated before. We believe it defines the precise meaning and the domain of general validity of the so-called Maximum Entropy Production Principle. It is hoped that the present unifying approach may prove useful in providing a fresh basis for effective, thermodynamically consistent, numerical models and theoretical treatments of irreversible conservative relaxation towards equilibrium from far non-equilibrium states.

cond-mat.stat-mech↗

arXiv2014

Recent Progress in the Definition of Thermodynamic Entropy

The principal methods for the definition of thermodynamic entropy are discussed with special reference to those developed by Carathéodory, the Keenan School, Lieb and Yngvason, and the present authors. An improvement of the latter method is then presented. Seven basic axioms are employed: three Postulates, which are considered as having a quite general validity, and four Assumptions, which identify the domains of validity of the definitions of energy (Assumption 1) and entropy (Assumptions 2, 3, 4). The domain of validity of the present definition of entropy is not restricted to stable equilibrium states. For collections of simple systems, it coincides with that of the proof of existence and uniqueness of an entropy function which characterizes the relation of adiabatic accessibility proposed by Lieb and Yngvason. However, our treatment does not require the formation of scaled copies so that it applies not only to collections of simple systems, but also to systems contained in electric or magnetic fields and to small and few-particle systems.

math-ph↗

arXiv2013

Steepest entropy ascent paths towards the Max-Ent distribution

With reference to two general probabilistic description frameworks, Information Theory and Classical Statistical Mechanics, we discuss the geometrical reasoning and mathematical formalism leading to the differential equation that defines in probability space the smooth path of Steepest Entropy Ascent (SEA) connecting an arbitrary initial probability distribution to the unique Maximum Entropy (MaxEnt) distribution with the same mean values of a set of constraints. The SEA path is relative to a metric chosen to measure distances in square-root probability distribution space. Along the resulting SAE path, the metric turns out to be proportional to the concept of Onsager resistivity generalized to the far non-equilibrium domain. The length of the SEA path to MaxEnt provides a novel global measure of degree of disequilibrium (DoD) of the initial probability distribution, whereas a local measure of DoD is given by the norm of a novel generalized concept of non-equilibrium affinity.

math-ph↗

arXiv2013

Steepest-Entropy-Ascent and Maximal-Entropy-Production Dynamical Models of Irreversible Relaxation to Stable Equilibrium from Any Non-Equilibrium State. Unified Treatment for Six Non-Equilibrium Frameworks

By suitable reformulations, we review the mathematical frameworks of six different approaches to the description of non-equilibrium dynamics with the purpose to set up a unified formulation of the Maximum Entropy Production (MEP) principle valid in all these contexts. In this way, we extend to such frameworks the concept of Steepest Entropy Ascent dynamics introduced by the present author in previous work on quantum thermodynamics. Actually, the present formulation constitutes a generalization also in the quantum thermodynamics framework. The analysis emphasizes that in the SEA-inspired implementation of the MEP principle, a key role is played by the geometrical metric with respect to which to measure the length of a trajectory in state space. The metric tensor turns out to be directly related to the inverse of the Onsager's generalized conductivity tensor. We conclude that in most of the existing theories of non-equilibrium the time evolution of the state representative can be seen to actually follow in state space the path of SEA with respect to a suitable metric connected with the generalized conductivities. The resulting unified family of SAE/MEP dynamical models are all intrinsically consistent with the second law of thermodynamics. The nonnegativity of the entropy production is a general and readily proved feature of SEA dynamics. In several of the different approaches to non-equilibrium description we consider here, the SEA concept has not been investigated before. Therefore, it is hoped that the present unifying approach may prove useful in providing a fresh basis for effective, thermodynamically consistent, numerical models and theoretical treatments of irreversible conservative relaxation towards equilibrium from far non-equilibrium states.

cond-mat.stat-mech↗

arXiv2010

Rigorous and General Definition of Thermodynamic Entropy

The physical foundations of a variety of emerging technologies --- ranging from the applications of quantum entanglement in quantum information to the applications of nonequilibrium bulk and interface phenomena in microfluidics, biology, materials science, energy engineering, etc. --- require understanding thermodynamic entropy beyond the equilibrium realm of its traditional definition. This paper presents a rigorous logical scheme that provides a generalized definition of entropy free of the usual unnecessary assumptions which constrain the theory to the equilibrium domain. The scheme is based on carefully worded operative definitions for all the fundamental concepts employed, including those of system, property, state, isolated system, environment, process, separable system, system uncorrelated from its environment, and parameters of a system. The treatment considers also systems with movable internal walls and/or semipermeable walls, with chemical reactions and/or external force fields, and with small numbers of particles. The definition of reversible process is revised by introducing the new concept of scenario. The definition of entropy involves neither the concept of heat nor that of quasistatic process; it applies to both equilibrium and nonequilibrium states. The role of correlations on the domain of definition and on the additivity of energy and entropy is discussed: it is proved that energy is defined and additive for all separable systems, while entropy is defined and additive only for separable systems uncorrelated from their environment; decorrelation entropy is defined. The definitions of energy and entropy are extended rigorously to open systems. Finally, to complete the discussion, the existence of the fundamental relation for stable equilibrium states is proved, in our context, for both closed and open systems.

quant-ph↗

arXiv2009

Nonlinear Quantum Evolution Equations to Model Irreversible Adiabatic Relaxation with Maximal Entropy Production and Other Nonunitary Processes

We first discuss the geometrical construction and the main mathematical features of the maximum-entropy-production/steepest-entropy-ascent nonlinear evolution equation proposed long ago by this author in the framework of a fully quantum theory of irreversibility and thermodynamics for a single isolated or adiabatic particle, qubit, or qudit, and recently rediscovered by other authors. The nonlinear equation generates a dynamical group, not just a semigroup, providing a deterministic description of irreversible conservative relaxation towards equilibrium from any non-equilibrium density operator. It satisfies a very restrictive stability requirement equivalent to the Hatsopoulos-Keenan statement of the second law of thermodynamics. We then examine the form of the evolution equation we proposed to describe multipartite isolated or adiabatic systems. This hinges on novel nonlinear projections defining local operators that we interpret as ``local perceptions'' of the overall system's energy and entropy. Each component particle contributes an independent local tendency along the direction of steepest increase of the locally perceived entropy at constant locally perceived energy. It conserves both the locally-perceived energies and the overall energy, and meets strong separability and non-signaling conditions, even though the local evolutions are not independent of existing correlations. We finally show how the geometrical construction can readily lead to other thermodynamically relevant models, such as of the nonunitary isoentropic evolution needed for full extraction of a system's adiabatic availability.

quant-ph↗

arXiv2007

Nonlinear Dynamical Equation for Irreversible, Steepest-Entropy-Ascent Relaxation to Stable Equilibrium

We discuss the structure and main features of the nonlinear evolution equation proposed by this author as the fundamental dynamical law within the framework of Quantum Thermodynamics. The nonlinear equation generates a dynamical group providing a unique deterministic description of irreversible, conservative relaxation towards equilibrium from any non-equilibrium state, and satisfies a very restrictive stability requirement equivalent to Hatsopoulos-Keenan statement of the second law of thermodynamics. Here, we emphasize its mathematical structure and its applicability also within other contexts, such as Classical and Quantum Statistical Mechanics, and Information Theory.

quant-ph↗

arXiv2007

Quantum thermodynamic Carnot and Otto-like cycles for a two-level system

From the thermodynamic equilibrium properties of a two-level system with variable energy-level gap $Δ$, and a careful distinction between the Gibbs relation $dE = T dS + (E/Δ) dΔ$ and the energy balance equation $dE = δQ^\leftarrow - δW^\to$, we infer some important aspects of the second law of thermodynamics and, contrary to a recent suggestion based on the analysis of an Otto-like thermodynamic cycle between two values of $Δ$ of a spin-1/2 system, we show that a quantum thermodynamic Carnot cycle, with the celebrated optimal efficiency $1 - (T_{low}/T_{high})$, is possible in principle with no need of an infinite number of infinitesimal processes, provided we cycle smoothly over at least three (in general four) values of $Δ$, and we change $Δ$ not only along the isoentropics, but also along the isotherms, e.g., by use of the recently suggested maser-laser tandem technique. We derive general bounds to the net-work to high-temperature-heat ratio for a Carnot cycle and for the 'inscribed' Otto-like cycle, and represent these cycles on useful thermodynamic diagrams.

quant-ph↗

arXiv2006

Positive Nonlinear Dynamical Group Uniting Quantum Mechanics and Thermodynamics

We discuss and motivate the form of the generator of a nonlinear quantum dynamical group 'designed' so as to accomplish a unification of quantum mechanics (QM) and thermodynamics. We call this nonrelativistic theory Quantum Thermodynamics (QT). Its conceptual foundations differ from those of (von Neumann) quantum statistical mechanics (QSM) and (Jaynes) quantum information theory (QIT), but for thermodynamic equilibrium (TE) states it reduces to the same mathematics, and for zero entropy states it reduces to standard unitary QM. The nonlinear dynamical group of QT is construed so that the second law emerges as a theorem of existence and uniqueness of a stable equilibrium state for each set of mean values of the energy and the number of constituents. It implements two fundamental ansatzs. The first is that in addition to the standard QM states described by idempotent density operators (zero entropy), a strictly isolated system admits also states that must be described by non-idempotent density operators (nonzero entropy). The second is that for such additional states the law of causal evolution is determined by the simultaneous action of a Schroedinger-von Neumann-type Hamiltonian generator and a nonlinear dissipative generator which conserves the mean values of the energy and the number of constituents, and (in forward time) drives any density operator, no matter how far from TE, in the 'direction' of steepest entropy ascent (maximal entropy increase). The equation of motion can be solved not only in forward time, to describe relaxation towards TE, but also backwards in time, to reconstruct the 'ancestral' or primordial lowest entropy state or limit cycle from which the system originates.

quant-ph↗