arXiv subjects

Shiling Liang

Publications and source records attributed to Shiling Liang.

11 recordsLinked to original sources

arXiv2026

Exact First-Passage Time Response Theory from Steady-State Response

The mean first-passage time (MFPT) provides a universal temporal measure of transport, reaction, search, and switching processes in physical, chemical, and biological systems. Understanding how MFPTs respond to perturbations is therefore crucial for prediction and control, yet a systematic theory has been lacking. We establish a compact theoretical framework for linear and nonlinear MFPT response in continuous-time Markov processes. The key tool is an exact correspondence that maps the intrinsically transient response of MFPTs onto the steady-state response of an auxiliary system. This correspondence yields exact and universal response relations for MFPTs between arbitrary state pairs, expressed entirely in terms of unperturbed MFPTs and steady-state probabilities. We then obtain a factorized physical decomposition of the MFPT response into linear upstream, linear downstream, and nonlinear contributions. Further corollaries include response-curve inference rules, fundamental bounds on MFPT responses, analytical expressions for higher-order responses of MFPTs and steady-state probabilities, and multi-rate response formulas. Additionally, our result offers computational advantages in calculating both MFPTs and steady-state distributions. Finally, a biologically motivated folding network is analyzed, and a recently reported paradox on MFPT is clarified.

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arXiv2026

A Universal Control Budget for First-Passage Kinetics

The first-passage time is the natural observable of reaction completion, yet how its mean responds to a rate change has lacked a general constraint. We show that the logarithmic sensitivity of the mean first-passage time of any finite Markov chain to any rate is bounded by one in magnitude, and that these sensitivities sum to -1. Together the two laws form a conserved control budget: speeding completion through some transitions must be paid for by others, and a coordinated change shifts the completion time only as far as the budget allows. Raising an activation barrier or shifting the depth of a well moves many rates at once, yet neither can shift the completion time further than a single rate could. The budget caps kinetic-proofreading discrimination at the checkpoint count, and prices it in sensitivity to substrate concentration.

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arXiv2026

Non-equilibrium symmetry of cyclic first-passage times

We study the sum of first passage times along an arbitrary cycle made up of N>2 states of a small physical system. We show that, if the system is at thermodynamic equilibrium, this sum follows the same probability distribution regardless of whether the cycle is explored clockwise or counterclockwise. Out of equilibrium, the distributions of clockwise and counterclockwise cyclic first passage times are related by a detailed fluctuation theorem. This result descends from a symmetry of clockwise and counterclockwise trajectories, which combines time reversal with swapping portions of the trajectories. We then relate the entropy produced along the cycle with the entropy production of the whole system using large deviation theory. Our results reveal a novel symmetry in stochastic systems, of potential broad applicability in non-equilibrium physics.

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arXiv2024

Nonlinear Response Identities and Bounds for Nonequilibrium Steady States

Understanding how systems respond to external perturbations is fundamental to statistical physics. For systems far from equilibrium, a general framework for response remains elusive. While progress has been made on the linear response of nonequilibrium systems, a theory for the nonlinear regime under finite perturbations has been lacking. Here, building on a novel connection between response and mean first-passage times in continuous-time Markov chains, we derive a comprehensive theory for the nonlinear response to archetypal local perturbations. We establish an exact identity that universally connects the nonlinear response of any observable to its linear counterpart via a simple scaling factor. This identity directly yields universal bounds on the response magnitude. Furthermore, we establish a universal bound on response resolution -- an inequality constraining an observable's change by its intrinsic fluctuations -- thereby setting a fundamental limit on signal-to-noise ratio. These results provide a rigorous and general framework for analyzing nonlinear response far from equilibrium, which we illustrate with an application to transcriptional regulation.

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arXiv2024

Thermodynamic Space of Chemical Reaction Networks

Living systems operate out of equilibrium, continuously consuming energy to sustain organised, functional states. Their emergent behaviour usually relies on a set of interconnected chemical reaction networks (CRNs) driven by external fluxes that keep some species at fixed concentrations. Hence, uncovering the principles governing the functioning of these CRNs is crucial to understand how living systems generate and regulate complexity. While kinetics plays a key role in shaping detailed dynamical phenomena, the range of operations of a CRN is fundamentally constrained by thermodynamics. Here, we introduce and analytically derive the "thermodynamic space" of a CRN, i.e., the range of accessible stationary concentrations that can be realized under a given energetic budget. We establish analogous bounds for reaction affinities, shedding light on how global thermodynamic properties, such as the total non-equilibrium driving, can limit local non-equilibrium quantities. We illustrate our results in various paradigmatic examples, demonstrating how the onset of complex behaviors is intimately tangled with the presence of non-equilibrium conditions. By providing a general tool for analysing CRNs, the presented framework constitutes a stepping stone to deepen our ability to predict complex out-of-equilibrium phenomena and design artificial chemical systems, starting from the sole knowledge of the underlying thermodynamic properties.

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arXiv2023

A Minimal Model for Carnot Efficiency at Maximum Power

Carnot efficiency sets a fundamental upper bound on the heat engine efficiency, attainable in the quasi-static limit, albeit at the cost of completely sacrificing power output. In this Letter, we present a minimal heat engine model that can attain Carnot efficiency while achieving maximum power output. We unveil the potential of intrinsic divergent physical quantities within the working substance, such as degeneracy, as promising thermodynamic resources to break through the universal power-efficiency trade-off imposed by nonequilibrium thermodynamics for conventional heat engines. Our findings provide novel insights into the collective advantage in harnessing energy of many-body interacting systems.

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arXiv2023

Thermodynamic bounds on time-reversal asymmetry

Quantifying irreversibility of a system using finite information constitutes a major challenge in stochastic thermodynamics. We introduce an observable that measures the time-reversal asymmetry between two states after a given time lag. Our central result is a bound on the time-reversal asymmetry in terms of the total cycle affinity driving the system out of equilibrium. This result leads to further thermodynamic bounds on the asymmetry of directed fluxes; on the asymmetry of finite-time cross-correlations; and on the cycle affinity of coarse-grained dynamics.

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arXiv2022

Thermodynamic Bounds on Symmetry Breaking in Linear and Catalytic Biochemical Systems

Living systems are maintained out-of-equilibrium by external driving forces. At stationarity, they exhibit emergent selection phenomena that break equilibrium symmetries and originate from the expansion of the accessible chemical space due to non-equilibrium conditions. Here, we use the matrix-tree theorem to derive upper and lower thermodynamic bounds on these symmetry-breaking features in linear and catalytic biochemical systems. Our bounds are independent of the kinetics and hold for both closed and open reaction networks. We also extend our results to master equations in the chemical space. Using our framework, we recover the thermodynamic constraints in kinetic proofreading. Finally, we show that the contrast of reaction-diffusion patterns can be bounded only by the non-equilibrium driving force. Our results provide a general framework for understanding the role of non-equilibrium conditions in shaping the steady-state properties of biochemical systems.

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arXiv2021

Dissipation-driven selection under finite diffusion: hints from equilibrium and separation of time-scales

When exposed to a thermal gradient, reaction networks can convert thermal energy into the chemical selection of states that would be unfavourable at equilibrium. The kinetics of reaction paths, and thus how fast they dissipate available energy, might be dominant in dictating the stationary populations of all chemical states out-of-equilibrium. This phenomenology has been theoretically explored mainly in the infinite diffusion limit. Here, we show that the regime in which the diffusion rate is finite, and also slower than some chemical reactions, might give birth to interesting features, as the maximization of selection, or the switch of the selected state at stationarity. We introduce a framework, rooted in a time-scale separation analysis, which is able to capture leading non-equilibrium features using only equilibrium arguments under well-defined conditions. In particular, it is possible to identify fast-dissipation subnetworks of reactions whose Boltzmann equilibrium dominates the steady-state of the entire system as a whole. Finally, we also show that the dissipated heat (and so the entropy production) can be estimated, under some approximations, through the heat capacity of fast-dissipation subnetworks. This work provides a tool to develop an intuitive equilibrium-based grasp on complex non-isothermal reaction networks, which are important paradigms to understand the emergence of complex structures from basic building blocks.

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arXiv2021

The intrinsic non-equilibrium nature of thermophoresis

Exposing a solution to a temperature gradient can lead to the accumulation of particles on either the cold or warm side. This phenomenon, known as thermophoresis, has been discovered more than a century ago, and yet its microscopic origin is still debated. Here, we show that thermophoresis can be observed in any system such that the transitions between different internal states are modulated by temperature and such that different internal states have different transport properties. We establish thermophoresis as a genuine non-equilibrium effect, whereby a system of currents in real and internal space that is consistent with the thermodynamic necessity of transporting heat from warm to cold regions. Our approach also provides an expression for the Soret coefficient, which decides whether particles accumulate on the cold or on the warm side, that is associated with the correlation between the energies of the internal states and their transport properties, that instead remain system-specific quantities. Finally, we connect our results to previous approaches based on close-to-equilibrium energetics. Our thermodynamically consistent approach thus encompasses and generalizes previous findings.

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arXiv2020

Equilibrium and non-equilibrium furanose selection in the ribose isomerisation network

The exclusive presence of $\beta$-D-ribofuranose in nucleic acids is still a conundrum in prebiotic chemistry, given that pyranose species are substantially more stable at equilibrium. However, a precise characterisation of the relative furanose/pyranose fraction at temperatures higher than about 50$^{\,\rm o}$C is still lacking. Here, we employ a combination of NMR measurements and statistical mechanics modelling to predict a population inversion between furanose and pyranose at equilibrium at high temperatures. More importantly, we show that a steady temperature gradient may steer an open isomerisation network into a non-equilibrium steady state where furanose is boosted beyond the limits set by equilibrium thermodynamics. Moreover, we demonstrate that nonequilibrium selection of furanose is maximum at optimal dissipation, as gauged by the temperature gradient and energy barriers for isomerisation. The predicted optimum is compatible with temperature drops found in hydrothermal vents associated with extremely fresh lava flows on the seafloor.

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