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Results for “Thermodynamic uncertainty relations”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Tightening the thermodynamic uncertainty relations with null-entropy events: What we learn when nothing happens

Fluctuation theorems establish that thermodynamic processes at the microscale can occasionally result in negative entropy production. At the microscale, another distinct possibility becomes more likely: processes where no entropy is produced overall. In this work, we explore the constraints imposed by such null-entropy events on the fluctuations of thermodynamic currents. By incorporating the probability of null-entropy events, we obtain tighter bounds on finite-time thermodynamic uncertainty relations derived from fluctuation theorems. We validate this framework using an example of a qudit SWAP engine.

FOS: Physical sciences↗
DOE OSTI2023

Colloidal superionic conductors

Nanoparticles with highly asymmetric sizes and charges that self-assemble into crystals via electrostatics may exhibit behaviors reminiscent of those of metals or superionic materials. Here, we use coarse-grained molecular simulations with underdamped Langevin dynamics to explore how a binary charged colloidal crystal reacts to an external electric field. As the field strength increases, we find transitions from insulator (ionic state), to superionic (conductive state), to laning, to complete melting (liquid state). In the superionic state, the resistivity decreases with increasing temperature, which is contrary to metals, yet the increment decreases as the electric field becomes stronger. Additionally, we verify that the dissipation of the system and the fluctuation of charge currents obey recently developed thermodynamic uncertainty relation. Our results describe charge transport mechanisms in colloidal superionic conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Learning thermodynamically constrained equations of state with uncertainty

Numerical simulations of high energy-density experiments require equation of state (EOS) models that relate a material’s thermodynamic state variables—specifically pressure, volume/density, energy, and temperature. EOS models are typically constructed using a semi-empirical parametric methodology, which assumes a physics-informed functional form with many tunable parameters calibrated using experimental/simulation data. Since there are inherent uncertainties in the calibration data (parametric uncertainty) and the assumed functional EOS form (model uncertainty), it is essential to perform uncertainty quantification (UQ) to improve confidence in EOS predictions. Model uncertainty is challenging for UQ studies since it requires exploring the space of all possible physically consistent functional forms. Thus, it is often neglected in favor of parametric uncertainty, which is easier to quantify without violating thermodynamic laws. This work presents a data-driven machine learning approach to constructing EOS models that naturally captures model uncertainty while satisfying the necessary thermodynamic consistency and stability constraints. We propose a novel framework based on physics-informed Gaussian process regression (GPR) that automatically captures total uncertainty in the EOS and can be jointly trained on both simulation and experimental data sources. A GPR model for the shock Hugoniot is derived, and its uncertainties are quantified using the proposed framework. We apply the proposed model to learn the EOS for the diamond solid state of carbon using both density functional theory data and experimental shock Hugoniot data to train the model and show that the prediction uncertainty is reduced by considering thermodynamic constraints.

Sharma, Himanshu (ORCID:000900050235718X)↗
DOE OSTI2025

Simultaneous inference of equation of state parameters and unknown data errors with uncertainty quantification via hierarchical Bayesian posterior maximization

Equations of state (EOSs) are a key component in running hydrodynamic simulations as they relate the thermodynamic states for the material. The Davis reactants EOS is commonly used for modeling high explosives (HEs), and the EOS model parameters are calibrated using material specific data. The calibrations are often performed with uncertainty quantification via Bayesian inference to account for uncertainty in the data and generate ensembles of likely parameters. However, there are relatively few HE data sets to use for calibration and many are historical and lack error information. In this work, we simultaneously calibrate the Davis reactants EOS model parameters and unknown data error terms for the high explosive PBX 9501. To quantify the uncertainty in the models and the data, we use a Bayesian framework for the calibration and compute the hierarchical Bayesian posterior distribution with both a posteriori maximization approach and Markov Chain Monte Carlo. In general, we find that, given our assumptions, the two approaches result in similar calibrated parameters, posterior covariance matrices, and insights about the parameters but that the posterior maximization requires far less computational resources.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Probabilistic and maximum entropy modeling of chemical reaction systems: Characteristics and comparisons to mass action kinetic models

We demonstrate and characterize a first-principles approach to modeling the mass action dynamics of metabolism. Starting from a basic definition of entropy expressed as a multinomial probability density using Boltzmann probabilities with standard chemical potentials, we derive and compare the free energy dissipation and the entropy production rates. We express the relation between entropy production and the chemical master equation for modeling metabolism, which unifies chemical kinetics and chemical thermodynamics. Because prediction uncertainty with respect to parameter variability is frequently a concern with mass action models utilizing rate constants, we compare and contrast the maximum entropy model, which has its own set of rate parameters, to a population of standard mass action models in which the rate constants are randomly chosen. We show that a maximum entropy model is characterized by a high probability of free energy dissipation rate and likewise entropy production rate, relative to other models. We then characterize the variability of the maximum entropy model predictions with respect to uncertainties in parameters (standard free energies of formation) and with respect to ionic strengths typically found in a cell.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Solar oscillations and the equation of state

The dependence of frequencies of solar oscillations on the thermodynamic state of the sun is considered. On the basis of an analysis of the equations of stellar structure, as well as the relevant aspects of the properties of the oscillations, it is argued that in the convection zone, information about the equation of state which is relatively unaffected by other uncertainties in the physics of the solar interior can be isolated. The different treatments that have been employed to describe the thermodynamics of stellar plasmas are reviewed. Through application of several of these treatments to the computation of models of the solar envelope, it is demonstrated that the sensitivity of the observed frequencies is in fact sufficient to distinguish even quite subtle features of the physics of solar matter.

Christensen-Dalsgaard, Jorgen↗
DOE OSTI2023

Uncertainty quantification for equations of state: copper as an example

Equations of state are essential for providing a fundamental description of materials properties in thermodynamic equilibrium and are used to provide closure relations for hydrodynamics simulations. Generally, equations of state rely on simple physics-based parameterized materials models to inform on the free energy of a material through out a given thermodynamic state space. Historically the parameters of these models have been tuned by hand to fit various experimental data. However, modern optimization and uncertainty quantification techniques allow us to quickly test thousands of parameter combinations and obtain meaningful uncertainty estimates on the parameters, opening opportunities for assessing systematic uncertainties in experiments, assessing model adequacy, and more. In this report, we use Bayesian inference to fit the solid (fcc) equation of state of copper. We focus on fitting five different experimental datasets, including the isobaric density, isobaric heat capacity, room temperature isotherm, principal isentrope, and principal Hugoniot. We fit all five data types simultaneously, and then explore the extent to which combinations of 2 subsets of the 5 datasets can constrain the EOS parameters, as compared to the fit to all 5. This information is useful for investigating the extent to which different datasets can con strain EOS models and thereby help guide experimental investigations in order to best constrain the EOS. We also discuss ways that the methodologies can be used to investigate systematic discrepancies between experiments, as well as how the methods can be used to assess model uncertainty. The framework we develop is general, in that it can be used with a variety of optimization or uncertainty quantification techniques and with a variety of data sources, including both experimental and ab-inito data.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

Sources of error in detonation calorimeters and error analysis for neat 2,4,6-triamino-1,3,5- trinitrobenzene (TATB)

Here, a calorimeter for measuring heats of detonation at Lawrence Livermore National Laboratory is described. A calibration precision of 0.2 % at the 95 % confidence interval (CI) is reported. Sources of uncertainty are discussed, including nonequivalent sources, which are those arising from differences between calibration and experimental tests. The systematic error due to nonequivalent sources is bounded to 0.19–0.22 % of the measured heat for a standard detonation test where the confinement material is gold. The recommendation is to correct for the systematic error by adding 0.19 % to the reported value and adding 0.03 % to the uncertainty. It is demonstrated that the precision of a detonation test is variable with testing duration because a source of uncertainty resides in the thermodynamic correction factor k6, which accounts for the contribution to heat by stirring; the generated power is additive and therefore highly impacted by total test time. The relative proportion also varies with the magnitude of heat release and sample size, adding variance to the weight of the error arising from the correction factor. A full error analysis based on the described sources of uncertainty is developed. The methodology is applied to a test series on neat 2,4,6-triamino-1,3,5- trinitrobenzene (TATB), demonstrating an ultimate precision of 0.7 % (single test) for materials testing and a relative standard deviation of 1.8 %.

47 OTHER INSTRUMENTATION↗
NASA NTRS2015

Global Ocean Evaporation: How Well Can We Estimate Interannual to Decadal Variability?

Evaporation from the world's oceans constitutes the largest component of the global water balance. It is important not only as the ultimate source of moisture that is tied to the radiative processes determining Earth's energy balance but also to freshwater availability over land, governing habitability of the planet. Here we focus on variability of ocean evaporation on scales from interannual to decadal by appealing to three sources of data: the new MERRA-2 (Modern-Era Retrospective analysis for Research and Applications -2); climate models run with historical sea-surface temperatures, ice and atmospheric constituents (so-called AMIP experiments); and state-of-the-art satellite retrievals from the Seaflux and HOAPS (Hamburg Ocean-Atmosphere Parameters and Fluxes from Satellite) projects. Each of these sources has distinct advantages as well as drawbacks. MERRA-2, like other reanalyses, synthesizes evaporation estimates consistent with observationally constrained physical and dynamical models-but data stream discontinuities are a major problem for interpreting multi-decadal records. The climate models used in data assimilation can also be run with lesser constraints such as with SSTs and sea-ice (i.e. AMIPs) or with additional, minimal observations of surface pressure and marine observations that have longer and less fragmentary observational records. We use the new ERA-20C reanalysis produced by ECMWF embodying the latter methodology. Still, the model physics biases in climate models and the lack of a predicted surface energy balance are of concern. Satellite retrievals and comparisons to ship-based measurements offer the most observationally-based estimates, but sensor inter-calibration, algorithm retrieval assumptions, and short records are dominant issues. Our strategy depends on maximizing the advantages of these combined records. The primary diagnostic tool used here is an analysis of bulk aerodynamic computations produced by these sources and uses a first-order Taylor series analysis of wind speed, SST, near-surface stability and relative humidity variations around climatology to gauge the importance of these components. We find that the MERRA-2 evaporation record is strongly influenced by the availability of wind speed and humidity from passive microwave imagers beginning in the late 1980s as well as by the SST record. The trend over the period 1980 to present is nearly 10%. AMIP or the ERA-20C trends are much smaller. We find that ENSO-related signals involving both wind speed and thermodynamic variability remain the primary signal in the latter and are confirmed by satellite retrievals. We present uncertainty estimates based on the various data sources and discuss the implications for GEWEX water and energy budget science challenges.

Robertson, Franklin R.↗
DOE OSTI2026

Gradient-informed Hamiltonian Monte Carlo for multicomponent CALPHAD model optimization and uncertainty quantification

CALPHAD model parameter optimization is inherently challenging due to non-smooth objective functions, high-dimensional parameter spaces, and the need for uncertainty quantification (UQ). Traditional weighted nonlinear least squares approaches are computationally efficient but local, whereas black-box global optimizers and ensemble Markov Chain Monte Carlo (MCMC) methods provide broader exploration at substantial computational cost. The objective of this work is to combine the global exploration capability of gradient-informed Hamiltonian Monte Carlo – specifically the No-U-Turn Sampler (NUTS) – with local deterministic refinement using BFGS to efficiently optimize multicomponent CALPHAD models with minimal manual intervention. Analytic gradients are computed via the Jansson derivative framework. The methodology is demonstrated on the Cr—Fe binary system and extended to the Cr—Fe—Ni ternary system with 32 degrees of freedom. For Cr—Fe, NUTS achieves comparable or superior optimality relative to ensemble MCMC while requiring over an order-of-magnitude fewer likelihood evaluations. Parameter uncertainties are quantified through NUTS sampling and propagated to thermodynamic observables using local expansion, demonstrating a novel modular approach that combines binary and ternary parameter subsets without requiring global relaxation. These results establish gradient-informed exploration as a scalable strategy for multicomponent CALPHAD optimization and provide a practical route towards efficient higher-order database development with quantified uncertainty.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Effects of Urbanization in China on the East Asian Summer Monsoon as Revealed by Two Global Climate Models

Abstract The East Asian summer monsoon (EASM), vulnerable to anthropogenic activities, exerts profound impacts on precipitation in East Asia. In recent decades, China has been experiencing rapid urbanization. It has not yet reached a consensus on its influences on EASM. Here, we introduce satellite‐derived urban impervious areas of China during 1985–2017 into two global climate models with contrasting biases of climatological EASM simulation. Both models consistently show that urbanization weakens EASM by increasing surface friction drag. The increased surface roughness reduces climatological southerly winds in the concentrated urbanization area. As a result, moisture convergence occurs south of the concentrated urbanization area with ascending motion, while moisture divergence with descending motion appears to the north, resulting in the precipitation anomalies of “southern flood and northern drought.” The dominant role of urban dynamic forcing in regulating EASM is confirmed by reducing urban roughness to the level of croplands in sensitivity experiments. As urban dynamic forcing is largely mitigated, the urbanization impact mainly driven by urban thermal forcing conversely strengthens EASM due to enhanced land‐sea thermal contrast via urbanization‐induced warming. Spatial patterns and magnitudes of the urbanization‐induced EASM weakening vary between the two models due to disparities in their simulations of urban thermodynamic forcing and atmospheric adjustments. These results underscore the robust weakening effect of urbanization on EASM by urban friction drag and document uncertainties in the related spatial pattern and magnitude resulting from model discrepancies.

Meteorology & Atmospheric Sciences↗
DOE OSTI2024

Deep energy-pressure regression for a thermodynamically consistent EOS model

Abstract In this paper, we aim to explore novel machine learning (ML) techniques to facilitate and accelerate the construction of universal equation-Of-State (EOS) models with a high accuracy while ensuring important thermodynamic consistency. When applying ML to fit a universal EOS model, there are two key requirements: (1) a high prediction accuracy to ensure precise estimation of relevant physics properties and (2) physical interpretability to support important physics-related downstream applications. We first identify a set of fundamental challenges from the accuracy perspective, including an extremely wide range of input/output space and highly sparse training data. We demonstrate that while a neural network (NN) model may fit the EOS data well, the black-box nature makes it difficult to provide physically interpretable results, leading to weak accountability of prediction results outside the training range and lack of guarantee to meet important thermodynamic consistency constraints. To this end, we propose a principled deep regression model that can be trained following a meta-learning style to predict the desired quantities with a high accuracy using scarce training data. We further introduce a uniquely designed kernel-based regularizer for accurate uncertainty quantification. An ensemble technique is leveraged to battle model overfitting with improved prediction stability. Auto-differentiation is conducted to verify that necessary thermodynamic consistency conditions are maintained. Our evaluation results show an excellent fit of the EOS table and the predicted values are ready to use for important physics-related tasks.

97 MATHEMATICS AND COMPUTING↗
NASA NTRSDate not supplied

Role of Arctic Low Clouds in the Arctic Climate System: Isolating the Surface Type Influence on Arctic Low-Clouds

Interactions between sea ice and clouds represent a mechanism through which sea ice influences climate. Understanding the cloud response to the rapidly changing Arctic surface properties is necessary for improving climate simulations and projection of future change inside and outside the Arctic. Towards the goal of understanding the cloud response to sea ice, we composite cloud properties for ice-free, marginal ice zone (MIZ), and ice-covered surfaces during MIZ crossing events to analyze the cloud property differences between surface types. Restricting the analysis to MIZ crossing events enables the isolation of the sea ice effect on clouds from meteorological factors. We find larger cloud fraction and total water concentration below ~1.5 km over ice-free relative to ice-covered surfaces during non-summer months. During summer, the results suggest larger cloud fraction and total water concentration over ice-free surfaces, however differences do not exceed observational uncertainty. Cloud property differences are linked to atmospheric thermodynamic profile differences, namely ice-free surfaces are warmer, moister, less stable, and have more positive surface turbulent fluxes than ice-covered surfaces. Ice-free minus ice-covered cloud property differences scale with surface temperature differences and are only found in the presence of a surface temperature difference. Our results suggest a 0.02 cloud fraction and 0.005 g m 3 total water concentration increase (~5%) at the level of maximum cloud fraction between 2000-2021 due to the observed Arctic sea ice decline in fall, corresponding to ~2 Wm 2 increase in the net surface radiative flux supporting a positive sea ice-cloud radiative feedback in fall and winter and a negative sea ice-cloud radiative feedback in spring. We propose an updated conceptual model where the average surface type influence on cloud properties is mediated by surface temperature differences between ice-free and ice-covered surfaces.

Arctic climate↗
DOE OSTI2023

Understanding uncertainties in projections of western North Pacific tropical cyclogenesis

Reliable projections of tropical cyclone (TC) activities in the western North Pacific (WNP) are crucial for climate policy-making in densely-populated coastal Asia. Existing projections, however, exhibit considerable uncertainties with unclear sources. Here, based on future projections by the latest Coupled Model Intercomparison Project Phase 6 climate models, we identify a new and prevailing source of uncertainty arising from different TC identification schemes. Notable differences in projections of detected TCs and empirical genesis potential indices are found to be caused by inconsistent changes in dynamic and thermodynamic environmental factors affecting TC formations. While model uncertainty holds the secondary importance, we show large potential in reducing it through improved model simulations of present-day TC characteristics. Internal variability noticeably impacts near-term projections of the WNP tropical cyclogenesis, while the relative contribution of scenario uncertainty remains small. Our findings provide valuable insights into model development and TC projections, thereby aiding in adaptation decisions.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1974

Irreversibility

The principles of thermodynamics in relation to the irreversibility of real processes in nature are examined, taking into account an analogy used by Gibbs to present a picture concerning the time evolution of a complicated dynamical system. The significance of quantum-mechanics relations with respect to irreversibility considerations is explored. It is shown that quantum mechanical uncertainties are not necessarily required to obtain irreversibility.

Lamb, W. E., Jr.↗
NASA NTRS1979

New method for determining relative oscillator strengths of atoms through combined absorption and emission measurements - Application to titanium /Ti I/

The paper introduces a procedure that combines measurements of absorption and emission by atoms to obtain relative oscillator strengths that are independent of temperature determination in the sources and of assumptions regarding local thermodynamic equilibrium. The experimental observations are formed into sets of transitions and required to satisfy defined ratios. The procedure is illustrated with the published data of Whaling et al. and Smith and Kuehne for 16 transitions in Ti I. It is shown that the relative oscillator strengths resulting from this procedure have calculated uncertainties between 5 and 17% (about 95% confidence level). Evidence is presented to suggest that these uncertainties have been overestimated.

Cardon, B. L.↗
NASA NTRS1995

Stellar oxygen abundances. 4: Systematic effects on oxygen abundances derived from the 6300 A (O I) and 7774 A O I lines

We consider potential systematic effects on oxygen abundances derived from the 6300 A (OI) line and the 7774 A OI triplet. Our solar intensity spectra of the 7774 A triplet confirm previous results which indicate a discrepancy between the observed equivalent widths of Altrock (1968) and the values predicted by Local Thermodynamic Equilibrium (LTE) and recent NLTE models. However, this disagreement (at low micron(s)) does not seem to affect the solar O abundance as derived from flux spectra. We derive O abundances for a selection of relatively metal-rich F and G dwarfs from both the 6300 A (OI) line and 7774 A OI triplet and detail the various uncertainties which enter into the analyses. Minimizing possible systematic effects to the extent possible, we find for T(sub eff) approximately less than 6200-6300 K no systematic difference between the 6300 and 7774 A abundances. For T(sub eff) approximately greater than 6200-6300 K, however 7774 A abundances are substantially larger than the 6300 A abundances. This agreement in O abundances from the two features at cooler T(sub eff) conflicts with that of others and we suggest that the discrepancy may be due to the different model atmospheres utilized. If recently proposed, hotter T(sub eff) values for metal-poor dwarfs are correct, then there appears to be no discrepancy between the 6300 A abundances of metal-poor giants are correct, then there appears to be no discrepancy between the 6300 A abundances of metal-poor giants or dwarfs and the 7774 A abundances for dwarfs. This would seem to rule out substantial LTE departures or atmospheric inhomogeneity effects skewing metal-poor O abundances from the 7774 A triplet (for cooler stars having low metallicity anyway). Given the repeated inability of authors to reproduce each others' O abundances from the 6300 A (OI) line and the uncertainties in the solar equivalent width, we question the usual assumption that the 6300 A (OI) line and the uncertainties in the solar equivalent width, we question the usual assumption that the 6300 A (OI) abundances are more reliable than those from the permitted triplet.

King, Jeremy R.↗
DOE OSTI2023

Vapor and Liquid ( p –ρ– T–x ) Measurements of Binary Refrigerant Blends Containing R-32, R-152a, R-227ea, R-1234yf, and R-1234ze(E)

In this article, The pressure–density–temperature–composition (p–ρ–T–x) data of binary refrigerant mixtures containing R-32 (difluoromethane), R-152a (1,1,-difluoroethane), R-227ea (1,1,1,2,3,3,3-heptafluoropropane), R-1234yf (2,3,3,3-tetrafluoropropene), and R-1234ze(E) (trans-1,3,3,3-tetrafluoropropene) were measured in both the vapor and liquid phases using a two-sinker, magnetic suspension densimeter. The specific samples in this study comprised two compositions of approximately (0.3/0.7) and (0.7/0.3) mole fraction for each of the following four binary refrigerant blends: R-32 + R-1234yf, R-32 + R-1234ze(E), R-1234yf + R-152a, and R-1234ze(E) + R-227ea. Single-phase vapor densities were measured over a temperature range of approximately 253 to 293 K and pressures from 0.05 to 0.98 MPa. Single-phase liquid and supercritical densities were measured over a temperature range of approximately 230 to 400 K and pressures up to 22 MPa; for refrigerant blends containing R-1234yf, the maximum pressure was limited to 14 MPa. Overall relative combined, expanded (k = 2) uncertainties in density ranged from 0.025 to 0.191%, with an average uncertainty of approximately 0.05%. Here, we present measurement results, along with comparisons to available literature data and to default equations of state and mixture models included in REFPROP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗