Thermodynamics

Before a machine learning model can learn a thermodynamic equation of state, it must discover what its measurements represent: which channels scale with system size, which are intensive conjugates, how sectors pair through contact, and which potential governs stability. When sensors expose only an unknown linear mixture of extensive states and intensive responses, passive observations cannot disentangle physical quantities from coordinate artifacts. We formulate the problem of discovering this hidden thermodynamic ontology directly from anonymous controlled experiments. We present an operational identifiability theory and a constructive polynomial-time algorithm that extracts extensive and intensive scaling sectors from replication contrasts, recovers their dual cotangent pairing from thermal contact and reciprocity, verifies a globally admissible concave potential via discrete cyclic concavity, and determines an invariant matroid of reservoir ensembles. We prove that the residual observational equivalence is strictly (x, lambda) ~ (A x, a A^{-T} lambda + beta), establishing the sharp observational limit that no permitted experiment can break. Blind evaluations on van der Waals fluids and Curie-Weiss magnets confirm robust recovery under ill-conditioned mixing, correctly resolving anonymous Maxwell tie-lines while rejecting non-equilibrium continuations. External validation across six real fluids from the NIST WebBook demonstrates that operational ontology discovery transfers across real physical substances without coordinate leakage.

The last decade has seen the development of powerful methods for learning complex structure from high-dimensional data. These advances have brought to the foreground fundamental connections between subdisciplines of physics, applied mathematics, and machine learning. In this review, we bring together some of these ideas, often expressed in different languages, to highlight a conceptual thread that links five distinct fields: control theory, optimal transport, probabilistic inference, non-equilibrium thermodynamics, and machine learning. A common theme is the optimization of free-energy-like functionals under dynamical or statistical constraints. We offer a guided tour through this thread and present selected applications in reinforcement learning, variational inference, and generative modeling. The review does not assume prior familiarity with these topics, and begins with principles originating from physics.

Generative thermodynamic computers turn thermal noise into structured data through Langevin dynamics. We train these systems with a local update at each integration step. The reverse-path Onsager-Machlup objective yields a coupling gradient that is a symmetric sum of local residual-state correlations. We apply this gradient immediately rather than accumulating it over a full trajectory. In digital simulations using MNIST prototypes, online and trajectory-batch training reach similar validation losses on fixed noising paths. Models trained online release less heat on average in all five independently seeded pairs, with both models' parameters held fixed during sampling. Auxiliary classifier and nearest-prototype measures change modestly, while pairwise diversity decreases. The response to noise depends strongly on where the errors enter: independent zero-mean errors in the formed updates produce little heat change over a finite range of noise amplitudes, whereas residual offset and temporal correlation have much larger effects. Storing trained couplings requires substantially less precision than resolving deterministic updates during training. Together, these results establish a local online training method and show how update timing, noise structure, and precision affect generative thermodynamic computing.

The concept of Markov chain Monte Carlo (MCMC) cycles, an analogy to cyclic processes in heat engines, is presented in order to examine Bayesian inference problems. In this effort, we develop adaptive ensemble schedulers that allow the tuning of external parameters of a Bayesian canonical ensemble during an MCMC run, realising the MCMC cycles in practice. We run these cycles on different statistical models. As a fundamental insight, we find (both theoretically and in practice) that such systems can produce a non-zero net work output if and only if the considered model is non-Gaussian. As such, they may serve as a measure of non-Gaussianity in Bayesian inference, which we test on an example from supernova cosmology.

The recently proposed Microcanonical Hamiltonian Monte Carlo algorithm has not yet been studied in detail from a thermodynamic point of view; this work aims to fill that gap. We demonstrate how thermodynamical state variables and potentials can be derived and thereby demonstrate that the construction of the algorithm formally represents a microcanonical thermodynamic ensemble. In particular, we demonstrate (analytically and numerically) that the algorithm fulfils the Helmholtz theorem, an alternative formulation of the first law of thermodynamics. Furthermore, we construct a new sampling algorithm that extends the original to lower-dimensional inference problems. Finally, we argue that canonical Markov Chain Monte Carlo algorithms are more natural than Microcanonical Hamiltonian Monte Carlo from the thermodynamic and information-theoretic point of view.

Thermodynamic computers are stochastic physical devices designed to perform calculations at the thermal energy scale. Their operation is constrained by the equations of stochastic thermodynamics, among which are a set of bounds, known as speed limits, that relate a thermodynamic computer's run time to its computational progress and the heat it dissipates. Using the Wasserstein speed limit we assess the thermodynamic efficiency of a simulation model of a thermodynamic computer trained to perform a standard machine-learning classification task. On this task the thermodynamic computer is as capable as a simple multilayer perceptron. We show that different inference protocols allow the computer to operate within 40% of the thermodynamic limit of efficiency without loss of accuracy, or to perform inference increasingly rapidly at fixed accuracy and thermodynamic efficiency. These results indicate that a thermodynamic computer designed for a particular task retains considerable freedom in its thermodynamic operation.

What a finite learning device has recorded and what will hold value for it on future tasks are not the same quantity. We develop a typed accounting for finite-state learning devices that separates four components: a training-side fit functional $Φ_{\mathrm{fit}}$, the record-correlation stock $J_{D}=I(M;D)$, an update-side search ledger $σ_{M}$, and an operational capital value $V(M;T,b)$. This value is the work gap between an informed protocol class and a blind class obtained by deleting the memory-read port and re-optimizing from scratch. (I) Separation: for every $n$, there is a device family on which record correlation and world correlation grow by $n\ln 2$ while the capital gain is exactly zero. In the $\mathrm{flat}^{*}$ regime, data-free updates never increase $V$. (II) Capitalization ledger: an exact $\mathrm{flat}^{*}$ extraction identity and a universal ledger identity give, for (F5$'$)-stable $M$-local updates under a no-discarded-record-correlation condition (f), the bound $η_{\mathrm{cap}}\le 1$ for the capitalization efficiency $η_{\mathrm{cap}}=ΔV/(k T\,σ_{M})$, together with necessary and sufficient conditions for equality. (III) Value retention: for the retention gap $L_{\mathrm{gen}}$ and retention ratio $ρ_{\mathrm{gen}}$ (the former carries no sign constraint; the latter is defined for positive training-side value and is not confined to $[0,1]$) we give a two-layer alignment domain: an exact exchange rate between value and the side-information-adjusted record fit $I(M';D\mid Y)$ without any record-side-information independence assumption, and a raw record-stock exchange rate under a joint side-information neutrality condition $(M,D)\perp Y$, whose boundary is marked by an explicit one-time-pad witness. These are statements about finite-device value retention under task-distribution shift, not a theory of statistical generalization.

Enterprises increasingly seek to query data lakes using natural language via AI-driven tools like semantic operators or deep research agents. However, the latter operates as an opaque black box, hiding its intermediate reasoning and data retrieval steps, and failing to expose controls for managing API costs and execution latency. Meanwhile, the former can be prohibitively expensive for enterprise-scale data lakes. Consequently, analysts using these systems lack the agency to intercept hallucinated premises, verify intermediate results, or correct the system's trajectory. We present Carnot, an interactive execution engine for AI-driven analytics. Carnot compiles natural language requests into physical execution graphs and surfaces them through an interactive notebook interface. Rather than waiting blindly for a final output, users can critique the plan, incrementally execute operators, inspect intermediate data, or directly edit the underlying code or semantic operator instructions. Carnot's query optimizer will optimize the query with respect to cost or latency constraints provided by the user. Our demo will showcase how Carnot helps users achieve efficient and verifiable insights on workloads motivated by real enterprise use cases.

We present a set of tools for mapping general stochastic programs to thermodynamic hardware designed for energy-efficient stochastic sampling. Given a target stochastic program expressed as a Directed Factor Graph (DFG) of stochastic channels, or equivalently as a Parametrized Stochastic Circuit (PSC), we first introduce a method to approximately compile each factor in the DFG to an Energy-Based Model (EBM) that is native to the hardware. We then analyze how the error of the compiled DFG accumulates from the per-factor errors, and introduce two training refinements, context matching and trajectory-level REINFORCE post-training, which can reduce the residual error left by training each factor in isolation. The \texttt{thermalizers} framework takes a stochastic program expressed in the \texttt{torx} library and replaces its factors with thermodynamic kernels implemented and sampled using the \texttt{thrml} library. We demonstrate it on several example applications, including a market simulator that learns the joint day-to-day dynamics of a panel of financial time series from recorded market history alone, a probabilistic model from mathematical ecology, Gibbs sampling of an EBM the hardware cannot natively express, and a sequential Bayesian design loop over a Gaussian stochastic circuit.

Thermodynamic computing is an emerging hardware paradigm, in which stochastic physical dynamics serve as the direct computational primitive. The recent explosion of generative AI has only sharpened the search for alternative approaches to compute, and, as we show in this work, thermodynamic computing turns out to be well suited to this space. An important class of methods realises a function as the stationary expectation of an ergodic stochastic process: the answer is encoded in the time-averaged statistics of an equilibrating trajectory. To date, this equilibration-style class has been formulated exclusively through Langevin dynamics, restricting its implementations to analogue substrates and the engineering challenges those bring. In this work, we propose a substrate-independent formalisation of the equilibration-style formulation, in which the only object of design is the dynamical generator L* of an arbitrary ergodic process. The formalisation makes three hardware-level properties of the formulation explicit: the precision of a result is a knob set by how long the dynamics are run, sample averages decompose across independent trajectories, and dependent stages of a computation operate concurrently rather than serially, a property we call sequential parallelism. We instantiate the formalisation by fabricating a prototype digital thermodynamic computing chip, named CN101, that implements the formulation through discrete accumulator dynamics on standard CMOS using stochastic computing principles. We characterise CN101's success across conventional generative AI workloads in the form of VAEs and flow matching, applied to both image generation and scientific problems. Together, the formalisation and its digital instantiation show that the equilibration-style formulation is substrate-independent, and that its computational properties can be exploited on standard digital hardware.

Real-fluid thermodynamic property evaluation is a major computational cost in supercritical combustion simulations. In the enthalpy-based pressure-correction formulation, the closure evaluates temperature T, density $ρ$, and compressibility coefficient $ψ$ from the solver state (h,p,Y) through enthalpy-temperature inversion and repeated real-fluid equation-of-state evaluations. Neural-network surrogates offer fixed-cost inference, but direct mapping from (h,p,Y) to $(T,ρ,ψ)$ must capture the enthalpy-temperature relation and non-ideal equation-of-state response, resulting in a complex regression problem. This work introduces a thermodynamics-informed input reparameterization strategy, termed target-aligned input reparameterization (TAIR). TAIR replaces the raw enthalpy coordinate of each property network with a target-matched thermodynamic coordinate: the temperature network uses a temperature estimate obtained by inverting a constant-$c_p$ ideal-gas mixture enthalpy approximation, whereas the density and compressibility networks use an ideal-gas density estimate. These algebraic transformations use only solver-available variables and species constants, guiding the networks to learn real-fluid departures from ideal-gas baselines rather than reconstructing the full closure from raw enthalpy. The method is assessed using supercritical methane-oxygen counterflow flame data against a raw-input baseline and target-inconsistent cross-reparameterization controls. TAIR reduces held-out RMSE by factors of about 1.5, 2.0, and 7.5 for T, $ρ$, and $ψ$, respectively. For an unseen strain-rate flame within the augmented thermodynamic envelope, the corresponding factors are 3.6, 14.5, and 6.0. The target-inconsistent controls perform worse, indicating that the gains arise from thermodynamically matched input design rather than generic preprocessing.

We present a continuous geometric framework that models the discrete algebraic operations of the Transformer architecture as an integro-differential equation (IDE) on a semantic fiber bundle $\calE = \calM \times \R^d$. Beginning from a single geometric axiom -- that the token sequence forms a discrete $1$-manifold equipped with a canonical measure lattice -- we translate every core component of the modern Transformer (RMSNorm, RoPE, Softmax Attention, FFN, Residual Stream, SGD, Weight Decay) into a cohesive vocabulary of differential geometry, measure theory, and stochastic calculus. The resulting framework yields quantitative predictions spanning entropic optimal transport (Attention as a Schrödinger bridge) and non-equilibrium thermodynamics (SGD as Itô diffusion violating detailed balance). We conduct a six-part experimental campaign across five architectures (Qwen3, LLaMA\nobreakdash-3.1, Gemma\nobreakdash-3, GPT-2, Mistral) spanning $124$M to $8$B parameters. The empirical observables are quantitatively consistent with the geometric predictions: the $ε^{-1/2}$ Lipschitz scaling calibration at machine precision ($R^2 = 1.000$), the Lie--Trotter operator-splitting torsion, the symmetric ablation instability confirming the Dual-Law of Topological Stability, the $\calO(1/\sqrt{k})$ thermodynamic suppression of Poincaré recurrence on the RoPE torus, the thermodynamic context-limit phase transition, and the Non-Equilibrium Steady State parameter vortex -- verified across two optimizers (AdamW and Pure SGD) to exclude momentum artifacts. The results demonstrate that analyzing Transformers through the lens of continuous stochastic differential geometry provides a predictive descriptive vocabulary for the stability limits, context bounds, and optimization dynamics of Large Language Models.

To address the escalating energy and latency demands of machine-learning workloads, we introduce a blueprint for an energy-efficient and fast thermodynamic computing stack that leverages stochastic analog processes in physical hardware. In this work, we focus on energy-based thermodynamic computing where the stochastic process is well described by Langevin dynamics with tunable energy potentials. The implementation of such potentials in physical hardware enables us to generate and sample from basic parameterized energy-based models. We demonstrate how to construct and train popular classes of machine learning models based on these hardware-native energy-based models, using the framework of probabilistic graphical models. We analyze the runtime and energy consumption of different models in this thermodynamic paradigm based on theoretical considerations and numerical studies. As a preliminary experimental realization of such hardware, we present our stochastic analog superconducting circuits driven by thermal noise. Together, these results outline a path toward energy-efficient thermodynamic hardware for probabilistic machine learning.

Nonlinear thermodynamic computers based on Langevin dynamics exploit thermal fluctuations as a physical substrate for computation. Recent work has shown that quartic-confined fluctuating degrees of freedom can act as thermodynamic neurons capable of nonlinear function approximation at finite observation times. Here we extend this paradigm from mean-only readout to moment-resolved readout. Instead of representing each driven reservoir solely by its first moment, we construct a response vector from the elementwise raw polynomial moments $\mathbb{E}[\bm{x}]$, $\mathbb{E}[\bm{x}^{\odot 2}]$, and $\mathbb{E}[\bm{x}^{\odot 4}]$. These observables combine displacement and central-shape contributions and are naturally aligned with the linear, quadratic, and quartic terms of the local driven dynamics. We further introduce a heterogeneous multi-reservoir architecture in which three reservoirs with distinct initialization and training histories form a joint $2304$-dimensional response representation. Under the fixed MNIST $60000/10000$ reproduction protocol, feature-level fusion achieves the best observed accuracy of $9695/10000=96.95\%$, compared with $9682/10000=96.82\%$ for the strongest single-reservoir model and $9684/10000=96.84\%$ for equal-weight logit averaging. An exact paired McNemar test does not establish a statistically significant improvement over the strongest single reservoir, but the ablation and wrong-set overlap results provide suggestive evidence of complementary classification errors. These results motivate higher-order polynomial-moment readout and reservoir heterogeneity as candidate design principles for finite-time Langevin computing.

The alignment of language models is typically studied through the lens of capability benchmarks, but the dynamics of how models change during post-training remain poorly understood. We argue that the physical sciences, and thermodynamic phase-transition theory in particular, offer a principled and underexplored vocabulary for reasoning about these dynamics. As a case study, we instantiate this position through the lens of material Crystallization, which is a well-studied thermodynamic phase transition. For tasks like random number generation, this breaks into 3 phases: (1) the high entropy liquid phase in the pretrained model, with many distinct sampling distributions promptable from the model; (2) the nucleation phase caused by supervised finetuning, in which behavior collapses onto a single seed distribution present in the pretrained LLM; and (3) a settling phase in which reinforcement learning techniques redistribute probability of the collapsed distribution, but largely keep it concentrated on the same options as the seed distribution. We propose intuitive metrics to verify the transitions between these phases, and validate the idea across a range of random tasks. Crystallization is one instance of a broader class of physical frameworks we believe alignment research should import to answer questions about where alignment-induced structure comes from, why it converges where it does, and what it fundamentally cannot change.

Diffusion models are increasingly utilized for modeling molecular structures and conformational ensembles, yet the thermodynamic meaning of their learned representations and scores remains elusive. To resolve this ambiguity, we introduce a mathematically consistent action-operator framework natively compatible with diffusion models. By defining a fixed molecular environment as a base action $S_0(x)$ and an alchemical perturbation as an operator $O(x)$, standard diffusion noising induces effective noised actions and operators whose gradients and alchemical derivatives are directly represented by the model's learned fields. This rigorous self-consistency enables a ``noisy operator bridge'' capable of reading out free-energy differences ($ΔF$) from endpoint ensembles and per-frame evaluations. In controlled experiments on alanine dipeptide systems, we show that incorporating physical inductive biases enables partial recovery of the base action and perturbation operator. When applied to a challenging C6-H to C6-F ligand-pocket nonbonded perturbation (185L/IND) with negligible phase-space overlap, our supervised bridge estimates the alchemical $ΔF$ within approximately $1\ k_\mathrm{B}T$ of a stable 19-state MBAR reference. Finally, we demonstrate that endpoint coordinates and binary labels alone are sufficient to partially recover the operator shape and a centered free-energy scale without any force or action supervision. This work provides a rigorous path toward transforming generative molecular diffusion models from black-box coordinate samplers into auditable thermodynamic estimators.

We develop a quantitative theory of the Random Language Model (RLM), an ensemble of stochastic context-free grammars, in a scaling limit where the number of hidden symbols $N \to \infty$ while the grammar temperature $\tildeε_d \to 0$ at fixed $x = {\tildeε}_d \log N$. In this limit, the model admits a controlled description based on a large-deviation principle over rule-usage patterns. A semi-annealed approximation maps the problem to a class of Random Energy Models with nontrivial combinatorics. We show that the RLM exhibits a condensation transition at a critical value $x_c=1/8$, below which rule usage concentrates and language statistics acquire a nontrivial dependence on corpus length. A second characteristic scale at $x=1/2$ marks the onset of entropy reduction from its maximal value. Across these regimes, we derive explicit scaling laws for the number of distinct rules, entropy, and related observables, identifying distinct scaling, saturation, and critical regimes controlled by the interplay of grammar size, corpus length, and temperature. The theory resolves previous ambiguities regarding the existence of a thermodynamic transition and explains the slow approach to the large-$N$ limit as a consequence of the dependence on $\log N$. It further provides a unified framework in which universal statistical properties of language emerge from typical realizations of generative grammars, with implications for both natural language statistics and the behavior of large language models.

Can intelligence be measured? We propose that intelligence can be defined as the lawful amplification of rare but valid futures: a system increases the probability of outcomes that would be unlikely under passive dynamics but remain admissible under the constraints of the domain. We start with the premise that an intelligent system must model the world and its own place within it. Because the system is part of the world it models, this leads naturally to recursive self-simulation: the system represents futures in which its own actions are part of the trajectory. Our central results give a necessity statement and a conditional near-sufficiency statement connecting this architecture to a precise thermodynamic measure of lawful amplification of rare-valid futures: high rare-valid lift is impossible unless the internal simulation identifies rare-valid futures with high fidelity; conversely, when rare-valid fidelity is high and the simulation contains an effective policy, the achievable lift approaches the actuation-limited optimum. Thus recursive self-simulation is not merely a plausible feature of intelligence but, under the stated assumptions, is necessary and nearly sufficient for high thermodynamic intelligence. The resulting framework makes intelligence measurable on a universal scale, from passive matter and feedback controllers, large language models, and humans as text generators to Maxwell-demon-like information engines.

Hallucination detection in large language models (LLMs) is deployment-critical, and recent work shows that the spectrum of attention-derived graph Laplacians carries strong signal about reasoning quality. Prior spectral diagnostics, however, summarize the Laplacian spectrum by a handful of eigenvalues or hand-picked scalars, leaving most of its structure unused. We propose Free-Energy Signatures (Fes), a spectral descriptor that treats each layer's attention Laplacian as a Hamiltonian and extracts its thermodynamic potentials partition function, free energy, spectral entropy, heat capacity together with the random-matrix-theory (RMT) spectral form factor. We prove three results: (i)~Lipschitz stability of Fes under attention perturbation; (ii)~an expressiveness result showing that Fes enriches finite spectral summaries and approximates moment-derived spectral functionals under explicit regularity and grid-resolution assumptions; and (iii)~a finite-sample PAC bound on the AUROC of a training-free detector built from Fes. Empirically, across six open-weight LLMs and six benchmarks, a lightweight probe on Fes descriptors achieves the strongest aggregate AUROC among attention-spectral baselines, improving over LapEig by $+6.5$ AUROC points and over GoR-4 by $+2.4$ points on average, while requiring no update to the underlying LLM. In the fully unsupervised setting, an RMT-deviation score achieves mean AUROC $0.71$, providing a label-free but weaker detector. A complementary RMT analysis shows that correct generations exhibit more Wigner-Dyson like spectral statistics, whereas hallucinations exhibit more Poisson-like statistics. The anonymized code and config are provided in the supplementary material.

The growing energy demand for computation is becoming increasingly unsustainable. Thermodynamic computing, which harnesses physical thermal fluctuations as a computational resource rather than suppressing them, offers orders-of-magnitude energy savings for probabilistic and combinatorial tasks. Pharmaceutical R&D, heavily reliant on computational optimization and sampling, is a natural application domain. Here we present what is, to our knowledge, the first concrete pharmaceutical application mapped to thermodynamic hardware with energy estimates grounded in prototype measurements. We reduce mRNA codon optimization, a combinatorial problem routinely solved in drug development, to sampling from an Ising model, making it directly executable on a thermodynamic sampling unit (TSU). Benchmarking three approaches (Potts sampling, Ising sampling, and a genetic algorithm baseline) on the SARS-CoV-2 spike protein, we find that all achieve comparable optimization quality (scores ~234-240), but energy estimates based on validated hardware models indicate that a TSU could solve this problem using approximately 10e6 times less energy than a conventional GPU. All code is released under an open-source license.

Constitutive modeling of the relationship between process-imposed material states and fundamental material properties is critical to control of material microstructure in manufacturing processes. The limited accuracy resulting from the typical reliance on fallible human expertise and intuition for postulation and revision of the models functional form results in incremental and time consuming model discovery. Conventional Machine Learning (ML) incurs significant cost and time of data generation. Model discovery using Large Language Models (LLMs) suffers from the above issues and/or ignores the inviolability of fundamental thermodynamics laws. This work creates a novel GPT-Micro paradigm for autonomous, data sparse, and thermodynamics-compliant discovery of de-novo constitutive models. This framework seamlessly integrates semantic knowledge extraction from literature, enforcement of thermodynamics-based conservation laws, and sparse datasets, with LLM-driven generation and refinement of model hypotheses. Validation is performed for a long-intractable constitutive modeling problem in a printed electronics process testbed. This reveals significant and simultaneous advantages over the state-of-the-art including: (a) More than 70 percent reduction in data burden relative to ML-based modeling without loss in accuracy; (b) 400X reduction in discovery time after data generation, from months to hours, relative to human-driven modeling; (c) Discovery of models with novel functional forms without subjective human choice of a starting hypothesis; (d) Enhanced physics-rooted trustworthiness, human interpretability, and mechanistic insight via synthesis of compact, conservation-compliant, and physically complete analytical models. The potential of GPT-Micro to realize rapid, low-cost, physically trustworthy, and interpretable microstructure modeling across the manufacturing landscape is discussed.

Entropy production governs irreversibility and uncertainty in both physical and information-theoretic systems. While Physics-Informed Neural Networks (PINNs) successfully solve differential equations, current architectures remain inherently domain-specific. The extraction of domain-invariant entropy representations across fundamentally different physical laws remains unexplored. This paper introduces a unified Physics-Informed Deep Learning (PIDL) framework that simultaneously enforces differential equation residuals and information-theoretic bounds within a single neural architecture. We demonstrate this framework via two canonical studies: (i) a thermodynamic continuous stirred-tank reactor (CSTR) model solving governing ODEs, where a Softplus constraint strictly enforces the Second Law of Thermodynamics; and (ii) an information-theoretic financial market model solving the inverse Fokker-Planck PDE to infer latent drift and diffusion coefficients, guaranteeing diffusion positivity via a Softplus constraint while naturally inducing Shannon entropy. Three model variants are evaluated: two domain-specific baselines and one shared-encoder architecture. The PIDL framework guarantees absolute thermodynamic admissibility with zero Second-Law violations and exhibits exceptional data efficiency, retaining >90% predictive accuracy using merely 30% of available training data. Furthermore, a post-hoc Ruppeiner Riemannian geometric analysis of the learned entropy surface successfully identifies thermodynamic phase instabilities. This methodology provides a robust, domain-agnostic architecture for physics-constrained entropy modeling, advancing applications in sustainable process design and quantitative financial risk assessment.

Modern generative machine learning (ML) models can propose novel inorganic crystalline materials with targeted properties; however, synthesis planning of these materials remains difficult due to the complexity of the associated physical processes and limited availability of computational tools. We introduce a novel hybrid framework to evaluate Large Language Models (LLMs) in inorganic synthesis planning by combining thermodynamic databases with simplified kinetics models to approximate realistic synthesis conditions. As a case study, we focus on the niobium-oxygen system, which features multiple industrially relevant oxide phases with well-characterized data. In computational simulations, we compare LLM-generated synthesis routes with classical path-planning algorithms, showing that the implicit priors in LLMs can yield more viable strategies. In our evaluation setting, classical search methods serve primarily as a foil rather than a direct competitor. This illustrates the relative complexity of the problem and highlights where the LLM's implicit priors add value.

Constitutive laws for inelastic materials must satisfy strict thermodynamic admissibility requirements, yet current data-driven approaches sacrifice interpretability, even when formal guarantees are provided by physics-encoded architectures. We propose a symbolic regression framework for the data-driven discovery of dissipation potentials governing the evolution of internal variables within the Generalized Standard Materials (GSM) formalism. Starting from the Clausius--Duhem inequality, we enforce the thermodynamic requirements, convexity and non-negativity, that the dual dissipation potential must satisfy to guarantee non-negative mechanical dissipation. These requirements are formulated in the general subdifferential setting, encompassing rate-dependent (viscoelastic) and viscoplastic dissipative mechanisms, including potentials with genuine elastic domains, within a unified framework. Candidate potentials are generated by a composition-extended convexity-preserving grammar that guarantees thermodynamic admissibility \emph{by construction}. The framework is validated on synthetic datasets spanning Newtonian, power-law, and Bingham viscoplastic ground truths under process and measurement noise, and on experimental oscillatory shear measurements of a synthetic elastomer across multiple strain amplitudes and frequencies, where the discovered potentials reproduce the amplitude-dependent softening of the dynamic moduli and outperform a calibrated linear Zener baseline.

Free energy estimation is a fundamental yet challenging problem, from physics to statistics. Classical approaches rely on thermodynamic transformations, ranging from direct estimation, quasistatic integration, to finite-time averaging. Recent work [He and Du et al., 2025] learns neural transports to significantly accelerate the efficiency in the finite-time regime. In this paper, we generalize this framework to arbitrary state spaces. Building on this view, we develop a generalized neural transport learning approach for efficient estimation. Experiments validate the effectiveness and efficiency of the proposed method beyond continuous settings, extending to discrete and multimodal spaces as well as autoregressive settings. Beyond free energy estimation, we establish algebraic identities and reveal a group-theoretic structure linking infinitesimal time reversal and generalized Doob's $h$-transforms, showing that their compositions form a generalized dihedral group.

In this article, we present an improved version of the PULSE method (Partition function Unsupervised Learning Sampling and Evaluation) for estimating the thermodynamic properties of chemically disordered compounds. The aim is to reduce the computational cost of Monte Carlo approaches for this type of material and to demonstrate that this generative tool can estimate thermodynamic properties by sampling and estimating the partition function of the system. To validate this innovative approach, we use the 2D Ising model as a benchmark. We demonstrate that our method accurately reproduces average properties with high precision and efficiency compared to traditional Monte Carlo sampling methods. Our results highlight the efficiency and adaptability of the PULSE method, making it a valuable tool for studying materials for which conventional methods are too inefficient to compute properties affected by chemical disorder at low cost.

The training algorithms for AI systems all introduce far-from-equilibrium dynamical processes, and understanding the irreversibility of these algorithms is a fundamental step towards understanding the learning dynamics of modern AI systems. In this work, we establish a general framework for defining and analyzing the irreversibility of training algorithms. We show that four different ways to characterize the irreversibility of dynamical processes are equivalent to leading order in the step size $η$: numerical backward error $φ_{\rm DE}$, time-renormalized correction $φ_{\rm TR}$, microscopic time reversal asymmetry $φ_{\rm TA}$, and the (regularized) stochastic-thermodynamic entropy production $φ_{\rm ST}$. The irreversibility gives rise to a time-reversal-symmetry-breaking emergent force that generically breaks non-isometric continuous reparametrization symmetries, preserves orthogonal symmetries, and leads to a universal preference for those learning trajectories that minimize the entropy production rate.

We introduce thermodynamic networks, a general framework for autonomous, physics-based computation using non-equilibrium steady states. These networks are modeled as a collection of finite-size reservoirs that exchange conserved quantities--such as electric charge or molecular number--while relaxing to a non-equilibrium steady state, which encodes the solution of a computational problem. We identify Negative Differential Conductance (NDC) as the critical physical property governing the computational expressivity of the thermodynamic network. While networks lacking NDC are restricted to computing monotonic functions, the presence of NDC enables universal function approximation. For the training of the network, we use protocols that take advantage of the natural tendency of the system to equilibrate. We illustrate the versatility of our approach via two different platforms: quantum dot networks and enzymatic reaction networks. Both systems can be engineered to have NDC, enabling high performance in standard benchmarks, including sine function approximation and MNIST digit classification. Overall, our work establishes a rigorous link between non-equilibrium steady states and computational expressivity.

Free energy profiles serve as a fundamental bridge between microscopic atomic fluctuations and macroscopic thermodynamic observables. Estimating the free energy profile along a reaction coordinate, referred to as the potential of mean force (PMF), with density functional theory (DFT) accuracy is computationally expensive. Universal machine learning interatomic potentials (MLIPs) drastically reduce this cost, but their accuracy is strongly determined by their training data and hence can be uncertain for a given system. In this work, we present a systematic and scalable framework for reweighting PMFs, initially sampled with a single 'source' MLIP, across a representative suite of target MLIPs. Because traditional direct exponential reweighting fails for large system sizes due to low phase-space overlap between potentials, we deploy robust analytical corrections. Applying this to a complex 601-atom system of Li$^+$ transport in a nanoconfined electrolyte, we demonstrate that a mean energy-gap approximation effectively bypasses statistical collapse, producing a highly stable PMF matching the target PMF. Using this approach, we recover high-fidelity target thermodynamics across multiple DFT reference levels (PBE+D3, PBE-sol, r$^2$SCAN,r$^2$SCAN-D4) at a fraction of the computational cost of full simulations. Furthermore, thermodynamic analysis reveals that the studied MLIPs partition into two distinct clusters driven by their training data. Our reweighting framework successfully recovers target thermodynamic properties--specifically, reaction and activation free energies--even when the phase-space overlap between potentials is critically low. Ultimately, this approach establishes a vital diagnostic protocol to achieve affordable cross-model consensus on materials chemistry properties without redundant, resource-intensive simulations.

We introduce Nonlinear GENERIC Informed Neural Networks (N-GINNs), a deep learning framework for discovering evolution equations of systems governed by the nonlinear GENERIC formalism (General Equation for Non-Equilibrium Reversible-Irreversible Coupling). Such systems exhibit coupled conservative and dissipative dynamics, and can be described via the superposition of a Hamiltonian flow and a generalized gradient flow. In contrast to existing approaches, our formulation incorporates generalized gradient flows via convex dissipation potentials, enabling the identification of a broader class of thermodynamically consistent dynamics, including systems with non-quadratic dissipation potentials. Thermodynamic structure is strongly enforced by construction through suitable reparameterizations of both the bivector operator and the dissipation potential, ensuring exact compliance with the first and second laws of thermodynamics. We validate the proposed approach on three representative examples: a harmonic oscillator coupled to a heat bath, an idealized chemical motor, and a one-dimensional viscoplastic model of Perzyna type. These results demonstrate the method's ability to accurately infer thermodynamically consistent models from data for systems incorporating both conservative and nonlinear dissipative dynamics.

The current catalyst discovery and development pipeline for energy-intensive applications like methane conversion remains bottlenecked by expensive trial-and-error experimentation, irreproducible chemical intuition, and a lack of frameworks linking complex catalytic design spaces to performance. This work presents an interpretable machine learning framework that integrates SHAP-based feature importance analysis (Explainable AI) with tree-based ensembles (Random Forest and Bayesian-optimized CatBoost) to characterize Fe-zeolite and oxide-supported catalysts for the partial oxidation of methane (POM). Despite limited data, the framework decodes complex structure-performance relationships by identifying and ranking thermodynamic, structural, and geometric microdescriptors that influence the electronic band gap and govern macroscale performance metrics such as selectivity, activity, and stability. This work explicitly demonstrates that thermodynamic lattice stability and geometric factors are the primary drivers of electronic band gap (a critical proxy for redox reactivity) rather than bulk stoichiometry. Non-linear models achieve an R2 of 0.61 - 0.77, significantly outperforming traditional linear baselines (R2 = 0.32). This workflow provides both a light-weight generalizable methodology and a prioritized list of physical features for accelerated catalyst screening - and these features can subsequently be integrated into microkinetic and reaction engineering models to create digital twins of complex reactor systems and to enable predictive optimization in autonomous R&D laboratories.

The development of accurate exchange-correlation (XC) functionals remains a longstanding challenge in density functional theory (DFT). The vast majority of XC functionals have been hand designed by human researchers combining physical insight, exact constraints, and empirical fitting. Recent advances in large language models enable a systematic, automated alternative to this human-driven design loop. This report presents an agentic search system in which an LLM proposes structured functional-form changes guided by evolutionary history. The system attempts to improve functional performance through an iterative plan-execute-summarize loop, where improvements are measurable by optimizing functional parameters against a standard thermochemistry dataset, then evaluating performance on a held-out subset. The strongest discovered functional, SAFS26-a (Seed Agentic Functional Search 2026), improves upon the gold-standard ωB97M-V baseline by ~9%. These results also surface a cautionary lesson for AI-assisted science: models powerful enough to discover genuine improvements are equally capable of exploiting unphysical shortcuts to game the benchmark; domain expertise translated into explicitly enforced constraints remains essential to keeping results scientifically grounded.

Collective intelligence emerges across biological, physical, and artificial systems without central coordination, yet a unifying principle governing such behaviour remains elusive. The Free Energy Principle explains how individual agents adapt through variational inference, while game theory formalises strategic interactions. Here we introduce the Game-Theoretic Free Energy Principle, a unified framework showing that multi-agent systems performing local free-energy minimisation implicitly implement a stochastic game. We prove that, under bounded rationality and local information constraints, stationary points of collective free energy correspond to approximate Nash equilibria of an induced game. Conversely, a broad class of cooperative games admits a variational representation in which equilibria arise as Gibbs distributions over coalitions, establishing a bridge between Bayesian inference and strategic interaction. To characterise higher-order effects, we introduce a free-energy formulation of the Harsanyi dividend, isolating irreducible multi-agent synergy. This yields a predictive theory of cooperation, including a falsifiable non-monotonic relationship between sensory precision and agent influence. We validate this prediction across neural, biological, and artificial multi-agent systems. These results identify a common variational principle underlying inference, thermodynamics, and game-theoretic equilibrium.

The second-order harmonic (2f) component generated by twin-rotary compressor is a dominant low-frequency noise source of variable refrigerant flow (VRF) outdoor units, yet its amplitude fluctuates strongly with environmental thermal load and valve opening, making it difficult to assess accurately using conventional mechanism-based models. This paper proposes an unsupervised transfer learning method based on Domain-invariant Partial Least Squares (Di-PLS) to accurately predict 2f noise levels under new conditions using different signals. Prediction models utilizing thermodynamic signals and acceleration signals are constructed respectively, and the generalization performance of the proposed Di-PLS is systematically compared with traditional Partial Least Squares (PLS). Results demonstrate that Di-PLS significantly outperforms PLS by extracting cross-condition common features and minimizing the distribution discrepancy between the source and target domains. Specifically, the acceleration-based Di-PLS model achieves the best performance, maintaining prediction errors within 3 dB for all test cases. This superiority over thermodynamic-based models highlights a physical insight: while thermodynamic states drive dynamic changes, structural vibration possesses a stronger and more direct causal link to acoustic radiation.

Runtime monitoring of stochastic systems must distinguish nominal distributional relaxation from regime departure while controlling repeated-test false alarms under explicit validity assumptions. This paper links relative-entropy dissipation, information geometry, and sequential inference in a bounded first-passage monitoring architecture. For reversible Fokker--Planck dynamics, relative entropy to an invariant density is non-increasing; under exogenous forcing, its derivative decomposes into nominal dissipation and an information-space forcing term. The runtime layer uses Gaussian window surrogates, nominal-relative covariance shrinkage, a coordinate-consistent relative precision diagnostic, and randomized conformal ranks aggregated by a mixture power-martingale process. Analytical Ornstein--Uhlenbeck validation gives zero positive nominal Kullback--Leibler increments, forcing-identity residuals below 3.31 x 10^-6, and coordinate-invariance errors at numerical roundoff. On NSL-KDD, the monitor yields 0/100 alarms on internal nominal streams but 63/100 on official test-normal streams; post-change detection is 99.0% for seen and 98.53% for test-only attack types with median one-window delay. On UNSW-NB15, internal-null alarms are 0/100, whereas official test-normal alarms rise to 90/100; post-change detection is 81.33%, with 18.67% pre-change alarms. In these evaluations, calibration transport emerges as a major deployment constraint. No universal benchmark superiority, causal inference, or physical-work interpretation is claimed.

We develop a thermodynamic theory of algorithmic catalysis within the watts per intelligence framework, identifying reusable computational structures that reduce irreversible operations for a task class while satisfying bounded restoration and structural selectivity constraints. We prove that any class specific speed-up is upper-bounded by the algorithmic mutual information between the substrate and the class descriptor, and that encoding this information incurs a minimum thermodynamic cost via Landauer erasure. Combining these results yields a coupling theorem that lower-bounds the deployment horizon required for an algorithmic catalyst to be energetically favourable. The framework is illustrated on an affine SAT class and situates contemporary learned systems within an information thermodynamic constraint on intelligent computation.

The pseudoknot secondary structure in SARS-CoV-2 RNA is essential for regulating protein synthesis through $-$1 programmed ribosomal frameshifting ($-1$ PRF), a mechanism that allows the virus to generate both structural and non-structural proteins from overlapping reading frames. This pseudoknot exhibits both threaded and unthreaded long-lived topologies. The influence of ligand binding on its folding is a process critical for the development of $-$1 PRF small-molecule inhibitors. Understanding this process through unbiased molecular dynamics (MD) simulations can be facilitated by introducing collective variables (CVs) that capture the corresponding slowest dynamical modes. Here, we use spectral map (SM), a thermodynamics-driven machine learning technique, to learn such CVs directly from all-atom MD trajectories of the SARS-CoV-2 RNA pseudoknot in complex with the $-$1 PRF inhibitor merafloxacin and its two structural analogs in neutral and ionized forms. Free-energy landscapes (FELs) derived from the learned CVs indicate that ligand-induced destabilization is topology-selective. In the threaded pseudoknot, the inhibitors destabilize the S2 stem, while in the unthreaded pseudoknot, destabilization occurs in the S1 and S3 stems. Furthermore, the extent to which each ligand reshapes the FEL matches experimentally reported antiviral potency, whereas the protonation state qualitatively alters dynamics within the same RNA topology. Overall, our results show how pseudoknot topology, ligand type, and protonation state collectively influence the slow conformational dynamics of viral RNA and establish physiological protonation as a critical factor for modeling RNA-targeted drug action.

Landauer's principle bounds the heat generated by logical operations, but in practice the thermodynamic cost of computation is dominated by the control systems that implement logic. CMOS gates dissipate energy far above the Landauer bound, while laboratory demonstrations of near-Landauer erasure rely on external measurement or feedback systems whose energy costs exceed that of the logic operation by many orders of magnitude. Here we use simulations to show that a genetic algorithm can program a thermodynamic computer to implement logic operations in which the total heat emitted by the control system is of a similar order of magnitude to that of the information-bearing degrees of freedom. Moreover, the computer can be programmed so that heat is drawn away from the information-bearing degrees of freedom and dissipated within the control unit, suggesting the possibility of computing architectures in which heat management is an integral part of the program design.

Understanding the training dynamics of deep neural networks remains a major open problem, with physics-inspired approaches offering promising insights. Building on this perspective, we develop a thermodynamic framework to describe the stationary distributions of stochastic gradient descent (SGD) with weight decay for scale-invariant neural networks, a setting that both reflects practical architectures with normalization layers and permits theoretical analysis. We establish analogies between training hyperparameters (e.g., learning rate, weight decay) and thermodynamic variables such as temperature, pressure, and volume. Starting with a simplified isotropic noise model, we uncover a close correspondence between SGD dynamics and ideal gas behavior, validated through theory and simulation. Extending to training of neural networks, we show that key predictions of the framework, including the behavior of stationary entropy, align closely with experimental observations. This framework provides a principled foundation for interpreting training dynamics and may guide future work on hyperparameter tuning and the design of learning rate schedulers.

According to E.T. Jaynes and E.P. Wigner, entropy is an anthropomorphic concept in the sense that in a physical system correspond many thermodynamic systems. The physical system can be examined from many points of view each time examining different variables and calculating entropy differently. In this paper we discuss how this concept may be applied in information entropy; how Shannon's definition of entropy can fit in Jayne's and Wigner's statement. This is achieved by generalizing Shannon's notion of information entropy and this is the main contribution of the paper. Then we discuss how entropy under these considerations may be used for the comparison of password complexity and as a measure of diversity useful in the analysis of the behavior of genetic algorithms.