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arXiv:2512.22011 · Journal of Chemical Sciences

Fluctuations and Irreversibility: Historical and Modern Perspectives

Sounak Bandyopadhyay, Arnab Ghosh

quant-phSubmitted Dec 26, 2025• Announced Dec 29, 2025• 0 citations• Revised Dec 29, 2025 (v2)
v1 · Dec 26, 2025v2 · Dec 29, 2025
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Abstract

This article traces the development of fluctuation theory and its deep connection to irreversibility, from equilibrium to near-equilibrium, and finally to far-from-equilibrium systems. Classical fluctuation theorems, which capture the statistical behaviour of thermodynamic systems far from equilibrium, are now well established. Their quantum counterparts, however, remain an active area of research. In this review, we highlight recent advances by linking quantum fluctuation theorems with linear response theory, offering new insights into the nature of quantum fluctuations and irreversibility in the near-equilibrium regime. Particular emphasis is placed on dissipated work in quantum systems as a pathway to observing non-classical effects in quantum thermodynamics. Understanding quantum fluctuations is not only essential for clarifying the foundations of irreversibility but also crucial for the development of novel quantum technologies, including quantum computers, sensors, and metrological devices.

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This article traces the development of fluctuation theory and its deep connection to irreversibility, from equilibrium to near-equilibrium, and finally to far-from-equilibrium systems. Classical fluctuation theorems, which capture the statistical behaviour of thermodynamic systems far from equilibrium, are now well established. Their quantum counterparts, however, remain an active area of research. In this review, we highlight recent advances by linking quantum fluctuation theorems with linear response theory, offering new insights into the nature of quantum fluctuations and irreversibility in the near-equilibrium regime. Particular emphasis is placed on dissipated work in quantum systems as a pathway to observing non-classical effects in quantum thermodynamics. Understanding quantum fluctuations is not only essential for clarifying the foundations of irreversibility but also crucial for the development of novel quantum technologies, including quantum computers, sensors, and metrological devices.
Abstract We have previously developed this framework in the context of static response, here we will generalize this perspective to dynamic response, and the evolution between distinct thermal equilibrium states. Of particular importance will be the derivation of the fluctuation-dissipation theorem, which relates the response of a system to its time dependent fluctuations, clarifying an equivalence between how a system responds to a small perturbation and how it regresses back to equilibrium in the absence of a perturbation. With this framework we can develop linear models of relaxation, classically and quantum mechanically, and derive equa- tions of motion suitable for describing the dynamics of thermal ensembles held at fixed temperature rather than fixed energy. These models are Gaussian, and approximate the dynamical correlations of interacting systems. These effective equations of motion are rendered stochastic due to the incomplete description of the microscopic degrees of freedom that evolve the system.
The thermodynamics of quantum systems driven out of equilibrium has attracted increasing attention in the last decade, in connection with quantum information and statistical physics, and with a focus on non-classical signatures. While a first approach can deal with average thermodynamics quantities over ensembles, in order to establish the impact of quantum and environmental fluctuations during the evolution, a continuous quantum measurement of the open system is required. Here, we provide an introduction to the general theoretical framework to establish and interpret the thermodynamics for quantum systems whose nonequilibrium evolution is continuously monitored. We review the formalism of quantum trajectories and its consistent application to the thermodynamic scenario, where primary quantities such as work, heat, and entropy production can be defined at the stochastic level. The connection to irreversibility and fluctuation theorems is also discussed together with some recent developments, and we provide some simple examples to illustrate the general theoretical framework.
Abstract Processes at the nanoscale happen far away from the thermodynamic limit, far from equilibrium and are dominated by fluctuations and, perhaps, even quantum effects. This book establishes a consistent thermodynamic framework for such processes by combining tools from non-equilibrium statistical mechanics and the theory of open quantum systems. The book is accessible for graduate students and of interest to all researchers striving for a deeper understanding of the laws of thermodynamics beyond their traditional realm of applicability. It puts most emphasis on the microscopic derivation and understanding of key principles and concepts as well as their interrelation. The topics covered in this book include (quantum) stochastic processes, (quantum) master equations, local detailed balance, classical stochastic thermodynamics, (quantum) fluctuation theorems, strong coupling and non non-Markovian effects, thermodynamic uncertainty relations, operational approaches, Maxwell's demon and time-reversal symmetry, among other topics. Furthermore, the book treats a few applications in detail to illustrate the general theory and its potential for practical applications. These are single-molecule pulling experiments, quantum transport and thermoelectric effects in quantum dots, the micromaser and related set-ups in quantum optics.
This thesis is a study of non-equilibrium phenomena in quantum systems. Emphasis is given to the recently derived non-equilibrium fluctuation theorems, which relate the non-equilibrium response of a system to its equilibrium thermodynamic properties. We investigate the validity and importance of these theorems, from both a theoretical and experimental perspective, in systems ranging from a single atom to an ensemble of interacting particles. We also investigate the potential role of quantum dynamics in biological processes.
Of indisputable relevance for nonequilibrium thermodynamics, fluctuations theorems have been generalized to the framework of quantum thermodynamics, with the notion of work playing a key role in such contexts. The typical approach consists of treating work as a stochastic variable and the acting system as an eminently classical device with a deterministic dynamics. Inspired by technological advances in the field of quantum machines, here we look for corrections to work fluctuations theorems when the acting system is allowed to enter the quantum domain. This entails including the acting system in the dynamics and letting it share a nonclassical state with the system acted upon. Moreover, favoring a mechanical perspective to this program, we employ a concept of work observable. For simplicity, we choose as theoretical platform the autonomous dynamics of a two-particle system with an elastic coupling. For some specific processes, we derive several fluctuation theorems within both the quantum and classical statistical arenas. In the quantum results, we find that, along with entanglement and quantum coherence, aspects of inertia also play a significant role since they regulate the route to mechanical equilibrium.
Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed.