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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Improving noisy free-energy measurements by adding more noise

Estimating free-energy differences using nonequilibrium work relations, such as the Jarzynski equality, is hindered by poor convergence when work fluctuations are large. For systems governed by overdamped Langevin dynamics, we propose the counterintuitive approach of adding noise in order to increase the precision of such calculations. Here, by introducing additional stochastic fluctuations to the system and rescaling its potential energy accordingly, we leave the thermodynamics of the system unchanged while increasing its relaxation rate. For a given time-dependent protocol this modification reduces the dissipated reduced work, leading to more accurate free-energy estimates. The method is designed to be used in experiment, and we illustrate its operation using computer simulations applied to two model systems. However, the regime of applicability of this strategy is likely limited, because it requires control of the system's potential energy in a way that is feasible in only a few experimental settings.

Whitelam, Stephen [Lawrence Berkeley National Labo↗
DOE OSTI2022

Molecular simulation of the structural and thermodynamic properties of n-alkane/brine interfacial systems with nonionic surfactants

All-atom molecular dynamics (MD) simulations are used to study the structural and thermodynamic properties of water + n-heptane interfacial systems in the presence of salinity (NaCl, NaI, KCl, and KI) and two different nonionic surfactants. Excellent qualitative and quantitative agreement with interfacial tension experimental data is obtained, but this requires applying a charge scaling factor to the ionic species, suggesting the likely role of polarizability effects. Tensoactive behavior is observed for the NaI and KI systems, coinciding with layering of the iodide species near the interface. Further, there are significant interaction differences between the surfactants and the different ionic species, but the structural and thermodynamic behavior of the surfactant molecules is relatively unaffected by the specific salt species. Our analysis suggest that the surfactant-surfactant interactions play a critical role in determining the interfacial behavior, with a much smaller impact associated with the composition of the brine phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Reconciling and Improving Formulations for Thermodynamics and Conservation Principles in Earth System Models (ESMs)

Abstract This paper provides a comprehensive derivation of the total energy equations for the atmospheric components of Earth System Models (ESMs). The assumptions and approximations made in this derivation are motivated and discussed. In particular, it is emphasized that closing the energy budget is conceptually challenging and hard to achieve in practice without resorting to ad hoc fixers. As a concrete example, the energy budget terms are diagnosed in a realistic climate simulation using a global atmosphere model. The largest total energy errors in this example are spurious dynamical core energy dissipation, thermodynamic inconsistencies (e.g., coupling parameterizations with the host model) and missing processes/terms associated with falling precipitation and evaporation (e.g., enthalpy flux between components). The latter two errors are not, in general, reduced by increasing horizontal resolution. They are due to incomplete thermodynamic and dynamic formulations. Future research directions are proposed to reconcile and improve thermodynamics formulations and conservation principles.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Unified, Geometric Framework for Nonequilibrium Protocol Optimization

Controlling thermodynamic cycles to minimize the dissipated heat is a long-standing goal in thermodynamics, and more recently, a central challenge in stochastic thermodynamics for nanoscale systems. Here, we introduce a theoretical and computational framework for optimizing nonequilibrium control protocols that can transform a system between two distributions in a minimally dissipative fashion. These protocols optimally transport a system along paths through the space of probability distributions that minimize the dissipative cost of a transformation. Furthermore, we show that the thermodynamic metric—determined via a linear response approach—can be directly derived from the same objective function that is optimized in the optimal transport problem, thus providing a unified perspective on thermodynamic geometries. As a result, we investigate this unified geometric framework in two model systems and observe that our procedure for optimizing control protocols is robust beyond linear response.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Quantum Thermodynamics of Nonequilibrium Processes in Lattice Gauge Theories

A key objective in nuclear and high-energy physics is to describe nonequilibrium dynamics of matter, e.g., in the early Universe and in particle colliders, starting from the standard model of particle physics. Classical computing methods, via the framework of lattice gauge theory, have experienced limited success in this mission. Quantum simulation of lattice gauge theories holds promise for overcoming computational limitations. Because of local constraints (Gauss’s laws), lattice gauge theories have an intricate Hilbert-space structure. This structure complicates the definition of thermodynamic properties of systems coupled to reservoirs during equilibrium and nonequilibrium processes. We show how to define thermodynamic quantities such as work and heat using strong-coupling thermodynamics, a framework that has recently burgeoned within the field of quantum thermodynamics. Our definitions suit instantaneous quenches, simple nonequilibrium processes undertaken in quantum simulators. To illustrate our framework, we compute the work and heat exchanged during a quench in a Z 2 lattice gauge theory coupled to matter in 1+1 dimensions. Here, the thermodynamic quantities, as functions of the quench parameter, evidence a phase transition. For general thermal states, we derive a simple relation between a quantum many-body system’s entanglement Hamiltonian, measurable with quantum-information-processing tools, and the Hamiltonian of mean force, used to define strong-coupling thermodynamic quantities.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

First Principles Simulations of Electrified Interfaces in Electrochemistry

This chapter discusses some of the recent advances made in the first principles modeling of electrochemical catalysts. It also discusses the key development, namely the ability to explicitly treat the effects of surface electrification due to electrochemical processes and applied voltages in a computationally efficient manner. The chapter introduces the thermodynamics and statistical mechanics of electrified metal-solution interfaces. It then discusses the structure of the electrode-electrolyte interface and the effects of applied voltages, followed by an overview of the first-principles model and a motivating example. The chapter also provides a brief summary of classical thermodynamics and describes the basics of thermodynamic detour. It considers the thermodynamics of macroscopic systems and introduces several useful fundamental relations. Here, the chapter also considers a system to exist in a certain macrostate, which is a particular thermodynamic state specified by a set of fixed properties such as constant particle number, constant volume, and constant temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Verification Testing of OLI Systems Mixed Solvent Electrolyte Model for the Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 ) System to High Ionic Strength at 25°C

This technical report summarizes model verification results and summary statistics for 41 evaporite mineral solubility cases evaluated by Savannah River National Laboratory using OLI Systems’ aqueous electrolyte thermodynamic modeling software. The 41 verification cases containing a total of 60 solubility curves comprise mineral solubility data from low to high ionic strength at 25°C for the eight-component system Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 O as reported by Harvie et al. (1984). Thermodynamic calculations were executed using OLI Systems’ Stream Analyzer computation module within the OLI Studio software platform (Ver. 11.0, Rev. 11.0.1.9). The Mixed Solvent Electrolyte (MSE) thermodynamic framework was chosen for this investigation because of its superiority in modeling high ionic-strength inorganic salt solutions and actinide redox chemistry and solubility, both of which are relevant to the geological repository conditions at the Waste Isolation Pilot Plant in Carlsbad, New Mexico. Mineral solubility data in various inorganic salt solutions were digitized and extracted from figures generated by Harvie et al. (1984). For each of the 60 solubility curves, a case-specific chemistry model and input file were generated in OLI Studio using OLI Stream Analyzer and the MSE (H 3 O + ion) public databank provided by OLI Systems. Model simulation results were exported to Microsoft Excel to calculate summary statistics and to generate graphs comparing the OLI model predictions to the solubility data. Summary statistics include residuals (model – data) and concordance (accuracy × precision, where precision is indicated by the Pearson correlation coefficient and accuracy accounts for bias and scale differential). Private databanks were not developed, and activity coefficient model regressions were not performed to improve OLI model fits to the data. Of the 41 model verification plots, 83% have a mean of the percent residuals less than or equal to 25%. Similarly, 75% display a concordance greater than or equal to 0.75. Only seven of the 41 verification plots fail to show good agreement between the model and data. Of these seven, three are relevant to the WIPP repository because they involve the Mg-OH-Cl-SO 4 -CO 3 aqueous system. The remaining four address salt solubilities at the pH extremes (strong acid and strong base). It should be noted that in two of the three Mg-OH-Cl-SO 4 -CO 3 system cases, the regressed Harvie et al. (1984) solubility curve also deviated from the data. Lack of agreement between the OLI model-predicted solubility curves and the data is attributable to one or more of the following: specific solid species are not included in the OLI MSE databank; there is significant variation among the different solubility datasets chosen by Harvie et al. (1984); the OLI MSE model’s thermodynamic parameters were determined using different solubility datasets; and the activity coefficient parameters for certain relevant ion-ion and ion-molecule pairs have not been optimized via data regression. Two recommendations for future work are to (1) evaluate solubility data for the Mg-OH-Cl-SO 4 -CO 3 system at high ionic strength and, if necessary, develop a private OLI MSE database that includes missing species and, where necessary, regressed standard state properties and interaction parameters; (2) perform similar verification testing of the OLI model for actinide solubility data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Modeling single-molecule stretching experiments using statistical thermodynamics

Single-molecule stretching experiments are widely utilized within the fields of physics and chemistry to characterize the mechanics of individual bonds or molecules, as well as chemical reactions. Analytic relations describing these experiments are valuable, and these relations can be obtained through the statistical thermodynamics of idealized model systems representing the experiments. Since the specific thermodynamic ensembles manifested by the experiments affect the outcome, primarily for small molecules, the stretching device must be included in the idealized model system. Though the model for the stretched molecule might be exactly solvable, including the device in the model often prevents analytic solutions. In the limit of large or small device stiffness, the isometric or isotensional ensembles can provide effective approximations, but the device effects are missing. Here a dual set of asymptotically correct statistical thermodynamic theories are applied to develop accurate approximations for the full model system that includes both the molecule and the device. In conclusion, the asymptotic theories are first demonstrated to be accurate using the freely jointed chain model and then using molecular dynamics calculations of a single polyethylene chain.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Guiding Principles for Geochemical/Thermodynamic Model Development and Validation in Nuclear Waste Disposal: A Close Examination of Recent Thermodynamic Models for H + —Nd 3+ —NO 3 - (—Oxalate) Systems

Development of a defensible source-term model (STM), usually a thermodynamical model for radionuclide solubility calculations, is critical to a performance assessment (PA) of a geologic repository for nuclear waste disposal. Such a model is generally subjected to rigorous regulatory scrutiny. In this article, we highlight key guiding principles for STM model development and validation in nuclear waste management. We illustrate these principles by closely examining three recently developed thermodynamic models with the Pitzer formulism for aqueous H + —Nd 3+ —NO 3 - (—oxalate) systems in a reverse alphabetical order of the authors: the XW model developed by Xiong and Wang, the OWC model developed by Oakes et al., and the GLC model developed by Guignot et al., among which the XW model deals with trace activity coefficients for Nd(III), while the OWC and GLC models are for concentrated Nd(NO 3 ) 3 electrolyte solutions. The principles highlighted include the following: (1) Principle 1. Validation against independent experimental data: A model should be validated against experimental data or field observations that have not been used in the original model parameterization. We tested the XW model against multiple independent experimental data sets including electromotive force (EMF), solubility, water vapor, and water activity measurements. The results show that the XW model is accurate and valid for its intended use for predicting trace activity coefficients and therefore Nd solubility in repository environments. (2) Principle 2. Testing for relevant and sensitive variables: Solution pH is such a variable for an STM and easily acquirable. All three models are checked for their ability to predict pH conditions in Nd(NO 3 ) 3 electrolyte solutions. The OWC model fails to provide a reasonable estimate for solution pH conditions, thus casting serious doubt on its validity for a source-term calculation. In contrast, both the XW and GLC models predict close-to-neutral pH values, in agreement with experimental measurements. (3) Principle 3. Honoring physical constraints: Upon close examination, it is found that the Nd(III)-NO 3 association schema in the OWC model suffers from two shortcomings. Firstly, its second stepwise stability constant for Nd(NO 3 ) 2+ (log K 2 ) is much higher than the first stepwise stability constant for NdNO 3 2+ (log K 1 ), thus violating the general rule of (log K 2 –log K 1 ) < 0, or $\frac{K1}{K2}$>1. Secondly, the OWC model predicts abnormally high activity coefficients for Nd(NO 3 ) 2 + (up to ~900) as the concentration increases. (4) Principle 4. Minimizing degrees of freedom for model fitting: The OWC model with nine fitted parameters is compared with the GLC model with five fitted parameters, as both models apply to the concentrated region for Nd(NO 3 ) 3 electrolyte solutions. The latter appears superior to the former because the latter can fit osmotic coefficient data equally well with fewer model parameters. The work presented here thus illustrates the salient points of geochemical model development, selection, and validation in nuclear waste management.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Dispatch optimization of electric thermal energy storage within System Advisor Model

A stand-alone electric thermal energy storage (ETES) system converts low-value electricity into heat using resistance heating elements. During periods of high-value electricity, an ETES system uses a thermodynamic power cycle to convert stored thermal energy back to electricity. These dispatchable systems derive value from their ability to store energy when prices are low and generate electricity when prices are favorable, i.e., energy arbitrage. Consequently, dispatch optimization of system operations, through maximizing revenue subject to system constraints, is essential to evaluate the economic value of a particular system design. While stand-alone ETES systems offer potential advantages as dispatchable grid storage technologies, there is a lack of a neutral third-party, publicly available, open-source model to evaluate the performance, dispatch, and financial viability of these systems. To address this problem, we have developed a techno-economic model for stand-alone ETES systems, within National Renewable Energy Laboratory's (NREL's) System Advisor Model (SAM). We implement a mixed-integer linear program to determine an ETES optimal operating schedule that maximizes electricity sales less maintenance costs caused by operation and cycling given temporal-varying grid electricity prices. Our contributions include a mixed-integer linear program for energy arbitrage of an ETES system, an ETES performance model through a publicly-available software (i.e., SAM), and an exercise of our model through case studies that compare ETES operational strategies and annual financial metrics. With our dispatch optimization model, we were able to improve revenue by 20% compared to a myopic heuristic while reducing the operational cost of the ETES system through decreases in cycle starts, cycles per day, and heater starts.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2021

Development and Test Progress Towards a Supercritical Carbon Dioxide-Based Gas Turbine Waste Heat Recovery System

Supercritical carbon dioxide systems are the focus of significant recent research efforts and promise compact, high-efficiency architecture for gas turbine waste heat recovery for pipeline gas turbines. The waste heat recovery system improves operating efficiency by converting waste heat to additional electric power, which increases overall system efficiency by 35% at the design point, and also significantly improves part-load performance. This paper describes the system design and component selection for a 5.7 MWe waste heat recovery system based on an integrally-geared compressor-expander architecture, including the thermodynamic cycle development, system architecture and component trade studies, and final selection. Validation test results for critical first-of-a-kind compressor and turbine component technologies are also presented, demonstrating full-pressure performance and progress towards commercialization.

wilkes, Jason↗
DOE OSTI2020

M4SF-20LL010301042: Updated Thermodynamic Database for Use in Generic Disposal System Assessment

This progress report (Level 4 Milestone Number M4SF-20LL010301042) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Argillite Activity Number SF-20LL010301041. LLNL is leading efforts in the development of thermodynamic databases in support of the Spent Fuel and Waste Science Technology (SFWST) program. Thermodynamic models provide the basis for understanding the stability of solid phases and speciation of aqueous species and modeling the evolution of repository conditions. The LLNL effort is being performed in coordination with other US database development efforts. The effort includes a review of available thermochemical databases and a path forward for database integration. International coordination with the NEA-TDB is supported through crystalline international work package.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Enabling High Capacity and Coulombic Efficiency for Li-NCM811 Cells Using a Highly Concentrated Electrolyte

Lithium metal batteries suffer from dendrite formation and the associated safety hazards of thermal runaway reactions. In this study, we report the performances of a highly concentrated electrolyte (HCE) and a dilute LiPF6 electrolyte in lithium metal cells using LiNi 0.8 Co 0.1 Mn0.1O 2 . While the HCE exhibits lower bulk ionic conductivity than the dilute LiPF6 electrolyte, the cell conductivity is higher for the HCE system, indicating higher thermodynamic stability of the electrolyte against the electrodes. Full cell cycling demonstrates higher capacity for the HCE system, which declines as a function of cycle number due to the formation of decomposition products, similar to the dilute LiPF 6 system. The origin of the enhanced performance is the higher stability of the HCE against a Li metal anode as compared to the dilute LiPF 6 electrolyte. Cycling at higher temperatures further enhances the performance of the HCE, which is more thermally stable than the dilute LiPF 6 electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2025

Dissipative Phase Transition in the Two-Photon Dicke Model

We explore the dissipative phase transition of the two-photon Dicke model, a topic that has garnered significant attention recently. Our analysis reveals that while single-photon loss does not stabilize the intrinsic instability in the model, the inclusion of two-photon loss restores stability, leading to the emergence of superradiant states, which coexist with the normal vacuum states. Using a second-order cumulant expansion for the photons, we derive an analytical description of the system in the thermodynamic limit, which agrees well with the exact calculation results. Additionally, we present the Wigner function for the system, shedding light on the breaking of the 𝑍4 symmetry inherent in the model. These findings offer valuable insights into stabilization mechanisms in open quantum systems and pave the way for exploring complex nonlinear dynamics in two-photon Dicke models.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Leveraging slow $\mathrm{DOTA}$ f-element complexation kinetics to enable separations by kinetic design

The design of metal-concerned solvent extraction systems frequently leverages thermodynamically derived differences in selectivity. An alternative approach, leveraging kinetic control, has been considered much less seriously. Our recent manuscript describing DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) complexation kinetics across the lanthanide series shows the observed rate constant steadily increases across the series, with some non-monotonic behavior observed at terbium and thulium. This contrasts the thermodynamic stability constant trend, where lanthanide-DOTA stability constants initially increase and then plateau as a function of ionic radii after samarium. To leverage the kinetic differences of DOTA with the lanthanides across the series, kinetically based separations must be utilized. Since DOTA has very slow complexation kinetics, a separations system must expedite DOTA-metal complexation to allow a separation approximating practical application. Here in this report, a DOTA-based solvent extraction system, where DOTA is the aqueous holdback reagent and bis-2,4,4-trimethylpentylphosphinic acid (Cyanex 272) is the organic phase extractant, is demonstrated and compares the separations chemistry of Nd, Eu and Am. The slowness of DOTA complexation was addressed by heating the system. Results showed, in general, separation between metals is better during early phase contact, and diminishes under longer contact times. Under all conditions, separations are better than would be predicted based on a thermodynamic basis. This report suggests that while slowly complexing ligands classically used for biological applications may not be appropriate for thermodynamically designed metal separations, their use for kinetically based systems may be appropriate and enable a new design basis for f-element separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Overcoming time and complexity limitations in molecular dynamics investigations of equilibrium melting

Abstract A hybrid Monte-Carlo molecular-dynamics method for determining solidus and liquidus compositions in multicomponent systems is presented that overcomes both the time limitations in conventional molecular dynamics that prevent the evolution of distinct solid and liquid compositions via diffusion and the complexity challenge that prevents use of thermodynamic assessment in systems of many components. This hybrid method is validated in the Cu–Ni system against an independent assessment of solidus and liquidus compositions based on the regular solution model. Strategies for efficient mapping of different phase diagrams, based on the thermodynamic parameter T 0 , the temperature at which two phases of the composition X 0 have equal free energies, are presented and then demonstrated for the copper-nickel fully miscible system and the gold–silicon eutectic system. A calculation of the solidus and liquidus sampled during the equilibrium melting of equiatomic CrMnFeCoNi is performed, indicating that this method has potential to be extended to the study of many component alloys.

Au-Si↗