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At least 235 records · Page 13

Model comparisons for two-temperature plasma equations of state

When a plasma is generated in the laboratory, energy is often deposited preferentially into either the electrons or the ions, giving rise to a quasiequilibrium state in which the two species, electrons and ions, are well described by two effective temperatures, T e and T i . Accurate hydrodynamic modeling of such a two-temperature plasma requires an equation of state that captures the relevant many-body physics without assuming a strict local thermodynamic equilibrium. Several models have been proposed within the literature, which extend conventional statistical approaches, each employing a different combination of assumptions for modifying the equilibrium equations. Here, in this work, we compare the predictions for several models, presenting derivations of the internal energy and pressure for each microscopic model within a unified framework so that the assumptions of each model may be more easily compared to one another. We find that for sufficiently weak coupling, all models agree with one another. However, as the coupling strength is increased, the disagreement between the models becomes more pronounced. Moreover, the relative sizes of the corrections predicted by each model depend on which species has the higher temperature, T e >T i vs T e < T i .

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

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↗

Prediction of hydration energies of adsorbates at Pt(111) and liquid water interfaces using machine learning

Aqueous phase heterogeneous catalysis is important to various industrial processes, including biomass conversion, Fischer–Tropsch synthesis, and electrocatalysis. Accurate calculation of solvation thermodynamic properties is essential for modeling the performance of catalysts for these processes. Explicit solvation methods employing multiscale modeling, e.g., involving density functional theory and molecular dynamics have emerged for this purpose. Although accurate, these methods are computationally intensive. This study introduces machine learning (ML) models to predict solvation thermodynamics for adsorbates on a Pt(111) surface, aiming to enhance computational efficiency without compromising accuracy. In particular, ML models are developed using a combination of molecular descriptors and fingerprints and trained on previously published water–adsorbate interaction energies, energies of solvation, and free energies of solvation of adsorbates bound to Pt(111). These models achieve root mean square error values of 0.09 eV for interaction energies, 0.04 eV for energies of solvation, and 0.06 eV for free energies of solvation, demonstrating accuracy within the standard error of multiscale modeling. Feature importance analysis reveals that hydrogen bonding, van der Waals interactions, and solvent density, together with the properties of the adsorbate, are critical factors influencing solvation thermodynamics. Furthermore, these findings suggest that ML models can provide rapid and reliable predictions of solvation properties. This approach not only reduces computational costs but also offers insights into the solvation characteristics of adsorbates at Pt(111)–water interfaces.

Adsorption↗

Large Scale Study of Ligand–Protein Relative Binding Free Energy Calculations: Actionable Predictions from Statistically Robust Protocols

The accurate and reliable prediction of protein–ligand binding affinities can play a central role in the drug discovery process as well as in personalized medicine. Of considerable importance during lead optimization are the alchemical free energy methods that furnish an estimation of relative binding free energies (RBFE) of similar molecules. Recent advances in these methods have increased their speed, accuracy, and precision. This is evident from the increasing number of retrospective as well as prospective studies employing them. However, such methods still have limited applicability in real-world scenarios due to a number of important yet unresolved issues. Here, we report the findings from a large data set comprising over 500 ligand transformations spanning over 300 ligands binding to a diverse set of 14 different protein targets which furnish statistically robust results on the accuracy, precision, and reproducibility of RBFE calculations. We use ensemble-based methods which are the only way to provide reliable uncertainty quantification given that the underlying molecular dynamics is chaotic. These are implemented using TIES (Thermodynamic Integration with Enhanced Sampling). Results achieve chemical accuracy in all cases. Ensemble simulations also furnish information on the statistical distributions of the free energy calculations which exhibit non-normal behavior. We find that the “enhanced sampling” method known as replica exchange with solute tempering degrades RBFE predictions. We also report definitively on numerous associated alchemical factors including the choice of ligand charge method, flexibility in ligand structure, and the size of the alchemical region including the number of atoms involved in transforming one ligand into another. Our findings provide a key set of recommendations that should be adopted for the reliable application of RBFE methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lagrange thermodynamic potential and intrinsic variables for He-3 He-4 dilute solutions

For a two-fluid model of dilute solutions of He-3 in liquid He-4, a thermodynamic potential is constructed that provides a Lagrangian for deriving equations of motion by a variational procedure. This Lagrangian is defined for uniform velocity fields as a (negative) Legendre transform of total internal energy, and its primary independent variables, together with their thermodynamic conjugates, are identified. Here, similarities between relations in classical physics and quantum statistical mechanics serve as a guide for developing an alternate expression for this function that reveals its character as the difference between apparent kinetic energy and intrinsic internal energy. When the He-3 concentration in the mixtures tends to zero, this expression reduces to Zilsel's formula for the Lagrangian for pure liquid He-4. An investigation of properties of the intrinsic internal energy leads to the introduction of intrinsic chemical potentials along with other intrinsic variables for the mixtures. Explicit formulas for these variables are derived for a noninteracting elementary excitation model of the fluid. Using these formulas and others also derived from quantum statistical mechanics, another equivalent expression for the Lagrangian is generated.

Jackson, H. W.↗

Estimation of Mesoscale Atmospheric Latent Heating Profiles from TRMM Rain Statistics Utilizing a Simple One-Dimensional Model

In this study, a model is developed to estimate mesoscale-resolution atmospheric latent heating (ALH) profiles. It utilizes rain statistics deduced from Tropical Rainfall Measuring Mission (TRMM) data, and cloud vertical velocity profiles and regional surface thermodynamic climatologies derived from other available data sources. From several rain events observed over tropical ocean and land, ALH profiles retrieved by this model in convective rain regions reveal strong warming throughout most of the troposphere, while in stratiform rain regions they usually show slight cooling below the freezing level and significant warming above. The mesoscale-average, or total, ALH profiles reveal a dominant stratiform character, because stratiform rain areas are usually much larger than convective rain areas. Sensitivity tests of the model show that total ALH at a given tropospheric level varies by less than +/- 10 % when convective and stratiform rain rates and mesoscale fractional rain areas are perturbed individually by 1 15 %. This is also found when the non-uniform convective vertical velocity profiles are replaced by one that is uniform. Larger variability of the total ALH profiles arises when climatological ocean- and land-surface temperatures (water vapor mixing ratios) are independently perturbed by +/- 1.0 K (+/- 5 %) and +/- 5.0 K (+/- 15 %), respectively. At a given tropospheric level, such perturbations can cause a +/- 25 % variation of total ALH over ocean, and a factor-of-two sensitivity over land. This sensitivity is reduced substantially if perturbations of surface thermodynamic variables do not change surface relative humidity, or are not extended throughout the entire model evaporation layer. The ALH profiles retrieved in this study agree qualitatively with tropical total diabatic heating profiles deduced in earlier studies. Also, from January and July 1999 ALH-profile climatologies generated separately with TRMM Microwave Imager and Precipitation Radar rain statistics, it is shown that ALH profiles can be retrieved utilizing diverse satellite-derived rain products that offer convective and stratiform discrimination. Therefore, the ALH retrieval model developed in this study can be used to make regional estimates of total diabatic heating profiles in the future Global Precipitation Measurement mission, and to assimilate these profiles into numerical weather forecast and climate models.

Iacovazzi, Robert A., Jr.↗

Estimation of Mesoscale Atmospheric Latent Heating Profiles from TRMM Rain Statistics Utilizing a Simple One-Dimensional Model

In this study, a model is developed to estimate mesoscale-resolution atmospheric latent heating (ALH) profiles. It utilizes rain statistics deduced from Tropical Rainfall Measuring Mission (TRMM) data, and cloud vertical velocity profiles and regional surface thermodynamic climatologies derived from other available data sources. From several rain events observed over tropical ocean and land, ALH profiles retrieved by this model in convective rain regions reveal strong warming throughout most of the troposphere, while in stratiform rain regions they usually show slight cooling below the freezing level and significant warming above. The mesoscale-average, or total, ALH profiles reveal a dominant stratiform character, because stratiform rain areas are usually much larger than convective rain areas. Sensitivity tests of the model show that total ALH at a given tropospheric level varies by less than +/- 10 % when convective and stratiform rain rates and mesoscale fractional rain areas are perturbed individually by +/- 15 %. This is also found when the non-uniform convective vertical velocity profiles are replaced by one that is uniform. Larger variability of the total ALH profiles arises when climatological ocean- and land-surface temperatures (water vapor mixing ratios) are independently perturbed by +/- 1.0 K (+/- 5%) and +/- 5.0 K (+/- 15%), respectively. At a given tropospheric level, such perturbations can cause a +/- 25% variation of total ALH over ocean, and a factor-of-two sensitivity over land. This sensitivity is reduced substantially if perturbations of surface thermodynamic variables do not change surface relative humidity, or are not extended throughout the entire model evaporation layer. The ALH profiles retrieved in this study agree qualitatively with tropical total diabatic heating profiles deduced in earlier studies. Also, from January and July 1999 ALH-profile climatologies generated separately with TRMM Microwave Imager and Precipitation Radar rain statistics, it is shown that ALH profiles can be retrieved utilizing diverse satellite-derived rain products that offer convective and stratiform discrimination. Therefore, the ALH retrieval model developed in this study can be used to make regional estimates of total diabatic heating profiles in the future Global Precipitation Measurement mission, and to assimilate these profiles into numerical weather forecast and climate models.

Iacovazzi, Robert A., Jr.↗

Resolving local ordering and structure in Mn x Ge 1- x Te alloys through thermodynamic ensembles of pair distribution functions

Characterizing local bonding environments in complex materials is essential for understanding and optimizing their properties. Equally as important is the ability to predict local motifs as a function of synthesis conditions, enhancing chemists’ ability to design properties into materials. In this study, we present an approach to leverage statistical mechanics to generate temperature- and energy-informed ensemble averaged pair distribution functions (PDFs). This method, which we have named Thermodynamic Ensemble Averages of PDFs for Ordering and Transformations (TEAPOT), utilizes density functional theory (DFT) to relax supercells while incorporating energetic penalties for local order, enabling accurate and computationally efficient analysis of local structure. We apply this method to the neutron PDF measurements of the pseudobinary MnTe–GeTe (MGT) alloy, demonstrating its capability to resolve complex local distortions and chemical ordering. Our results reveal detailed insights into phase transformations and local distortions driven by Mn substitution. For compositions that globally present as rock salt, our analysis reveals that Ge coordination geometry is heavily impacted by synthesis temperature. We propose that high temperature synthesis conditions promote a lowered Ge polyhedra distortion, promoting high charge carrier mobility due to the alignment of local and global structure. Incorporating statistical mechanics and computation into experimental analysis thus guides synthesis of tailored local structure.

36 MATERIALS SCIENCE↗

Origin of the Greenland Ice Sheet

A climate model resolving the seasonal cycle and the two horizontal dimensions was developed and applied to several problems of current interest. Models of this type are useful when for various reasons a general circulation model experiment is not warranted or not feasible. For example, in cases where the signal to natural variability is small it may be advantageous to first consider such a statistical dynamical model because extremely long runs may be necessary in the application. In this case the simpler statistical dynamical model serves as a pilot study device. The model developed is a thermodynamic model whose solution yields the equilibrium seasonal cycle for the surface temperature field over the globe. The model is essentially a statement of the conservation of heat energy for individual columns of the earth atmosphere system. Various terms such as the infrared radiation flux to space are parameterized with earth radiation budget data from satellites such as Nimbus 6. The primary agent modulating the seasonal cycle amplitude is the heat capacity per unit area which is a strong function of surface type -- ocean surface can store 60 times more heat per unit time than land. By adjusting its few empirical parameters the model can be brought into remarkable agreement with the observed seasonal cycle. The model is then very useful for looking at the dependence of the seasonal cycle of the temperature on such externally defined variables as the Earth's orbital elements (eccentricity, tilt, precession of equinoxes) or the configuration of land-sea geography which can be changed by continental drift.

North, G. R.↗

Atmospheric disturbance model for aircraft and space capable vehicles

An atmospheric disturbance model (ADM) is developed that considers the requirements of advanced aerospace vehicles and balances algorithmic assumptions with computational constraints. The requirements for an ADM include a realistic power spectrum, inhomogeneity, and the cross-correlation of atmospheric effects. The baseline models examined include the Global Reference Atmospheric Model Perturbation-Modeling Technique, the Dryden Small-Scale Turbulence Description, and the Patchiness Model. The Program to Enhance Random Turbulence (PERT) is developed based on the previous models but includes a revised formulation of large-scale atmospheric disturbance, an inhomogeneous Dryden filter, turbulence statistics, and the cross-correlation between Dryden Turbulence Filters and small-scale thermodynamics. Verification with the Monte Carlo approach demonstrates that the PERT software provides effective simulations of inhomogeneous atmospheric parameters.

Chimene, Beau C.↗

The metallicity of M4: Accurate spectroscopic fundamental parameters for four giants

High-quality spectra, covering the wavelength range 5480 to 7080 A, have been obtained for four giant stars in the intermediate-metallicity CN-bimodal globular cluster M4 (NGC 6121). We have employed a model atmosphere analysis that is entirely independent from cluster parameters, such as distance, age, and reddening, in order to derive accurate values for the stellar parameters effective temperature, surface gravity, and microturbulence, and for the abundance of iron relative to the Sun, (Fe/H), and of calcium, Ca/H, for each of the four stars. Detailed radiative transfer and statistical equilibrium calculations carried out for iron and calcium suggest that departures from local thermodynamic equilibrium are not significant for the purposes of our analysis. The spectroscopically derived effective temperatures for our program stars are hotter by about 200 K than existing photometric calibrations suggest. We conclude that this is due partly to the uncertain reddening of M4 and to the existing photometric temperature calibration for red giants being too cool by about 100 K. Comparison of our spectroscopic and existing photometric temperatures supports the prognosis of a significant east-west gradient in the reddening across M4. Our derived iron abundances are slightly higher than previous high-resolution studies suggested; the differences are most probably due to the different temperature scale and choice of microturbulent velocities adopted by earlier workers. The resulting value for the metallicity of M4 is (Fe/H )(sub M4) = -1.05 + or - 0.15. Based on this result, we suggest that metallicities derived in previous high-dispersion globular cluster abundance analyses could be too low by 0.2 to 0.3 dex. Our calcium abundances suggest an enhancement of calcium, an alpha element, over iron, relative to the Sun, in M4 of (Ca/H) = 0.23.

Drake, J. J.↗

Physics-informed machine learning of the correlation functions in bulk fluids

The Ornstein–Zernike (OZ) equation is the fundamental equation for pair correlation function computations in the modern integral equation theory for liquids. In this work, machine learning models, notably physics-informed neural networks and physics-informed neural operator networks, are explored to solve the OZ equation. The physics-informed machine learning models demonstrate great accuracy and high efficiency in solving the forward and inverse OZ problems of various bulk fluids. The results highlight the significant potential of physics-informed machine learning for applications in thermodynamic state theory.

97 MATHEMATICS AND COMPUTING↗

Modeling regional precipitation over the Indus River basin of Pakistan using statistical downscaling

Complex processes govern spatiotemporal distribution of precipitation within the high-mountainous headwater regions (commonly known as the upper Indus basin (UIB)), of the Indus River basin of Pakistan. Reliable precipitation simulations particularly over the UIB present a major scientific challenge due to regional complexity and inadequate observational coverage. Here, we present a statistical downscaling approach to model observed precipitation of the entire Indus basin, with a focus on UIB within available data constraints. Taking advantage of recent high altitude (HA) observatories, we perform precipitation regionalization using K-means cluster analysis to demonstrate effectiveness of low-altitude stations to provide useful precipitation inferences over more uncertain and hydrologically important HA of the UIB. We further employ generalized linear models (GLM) with gamma and Tweedie distributions to identify major dynamic and thermodynamic drivers from a reanalysis dataset within a robust cross-validation framework that explain observed spatiotemporal precipitation patterns across the Indus basin. Final statistical models demonstrate higher predictability to resolve precipitation variability over wetter southern Himalayans and different lower Indus regions, by mainly using different dynamic predictors. The modeling framework also shows an adequate performance over more complex and uncertain trans-Himalayans and the northwestern regions of the UIB, particularly during the seasons dominated by the westerly circulations. However, the cryosphere-dominated trans-Himalayan regions, which largely govern the basin hydrology, require relatively complex models that contain dynamic and thermodynamic circulations. Furthermore, we also analyzed relevant atmospheric circulations during precipitation anomalies over the UIB, to evaluate physical consistency of the statistical models, as an additional measure of reliability. Overall, our results suggest that such circulation-based statistical downscaling has the potential to improve our understanding towards distinct features of the regional-scale precipitation across the upper and lower Indus basin. Additionally, such understanding should help to assess the response of this complex, data-scarce, and climate-sensitive river basin amid future climatic changes, to serve communal and scientific interests.

54 ENVIRONMENTAL SCIENCES↗

Photon–photon chemical thermodynamics of frequency conversion processes in highly multimode systems

Abstract Frequency generation in highly multimode nonlinear optical systems is inherently a complex process, giving rise to an exceedingly convoluted landscape of evolution dynamics. While predicting and controlling the global conversion efficiencies in such nonlinear environments has long been considered impossible, here, we formally address this challenge even in scenarios involving a very large number of spatial modes. By utilizing fundamental notions from optical statistical mechanics, we develop a universal theoretical framework that effectively treats all frequency components as chemical reactants/products, capable of undergoing optical thermodynamic reactions facilitated by a variety of multi-wave mixing effects. These photon–photon reactions are governed by conservation laws that directly determine the optical temperatures and chemical potentials of the ensued chemical equilibria for each frequency species. In this context, we develop a comprehensive stoichiometric model and formally derive an expression that relates the chemical potentials to the optical stoichiometric coefficients, in a manner akin to atomic/molecular chemical reactions. This advancement unlocks new predictive capabilities that can facilitate the optimization of frequency generation in highly multimode photonic arrangements, surpassing the limitations of conventional schemes that rely exclusively on nonlinear optical dynamics. Notably, we identify a universal regime of Rayleigh–Jeans thermalization where an optical reaction at near-zero optical temperatures can promote the complete and entropically irreversible conversion of light to the fundamental mode at a target frequency. Our theoretical results are corroborated by numerical simulations in settings where second-harmonic generation, sum-frequency generation and four-wave mixing processes can manifest.

Optics↗

Plan Position Indicator Hydrometeor Field Statistics (PPIHYD) Evaluation Data Product Version 1.0

The PPIHYD evaluation data product provides distinct hydrometeor field statistics calculated from U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility scanning radar plan position indicator (PPI) scans. These statistics include the equivalent reflectivity factor and Doppler spectral width percentiles, min/max values, and first four moments (mean, standard deviation, skewness, and kurtosis) of distinct hydrometeor features (clustered hydrometeor fields). Statistics also include morphological properties, water content and precipitation rate parameterization-based estimates, and thermodynamic properties interpolated using the Interpolated Sonde value-added product (INTERPSONDE VAP). The data set is organized in tabular form and is accompanied by mask arrays with corresponding indices. This straightforward file structure simplifies scanning radar data processing and renders this data set useful for process understanding and model evaluation studies. This report describes the data set and its processing algorithm and provides some examples.

54 ENVIRONMENTAL SCIENCES↗

Airborne In Situ and Ground-based Polarimetric Radar Measurements of Tropical Convection in Support of CRYSTAL-FACE

This report describes the work performed by the University of North Dakota (UND) under NASA Grant NAG5-11509, titled Airborne In Situ and Ground-based Polarimetric Radar Measurements of Tropical Convection in Support of CRYSTAL-FACE. This work focused on the collection of data by two key platforms: the UND Citation II research aircraft and the NASA NPOL radar system. The CRYSTAL-FACE (C-F) mission addresses several key issues from the NASA Earth System Enterprise, including the variability of water in the atmosphere, the forcing provided by tropical cirrus and the response of the Earth system to this forcing. In situ measurements and radar observations of tropical convection, cirrus clouds and their environment are core elements of C-F. One of the primary issues that C-F is addressing is the relationship of tropical cirrus anvils to precipitating deep convection. The in situ measurements from C-F are being used to validate remote sensing of Earth-Atmosphere properties, increase our knowledge of upper tropospheric water vapor and its distribution, and increase our knowledge of tropical cirrus cloud morphology and composition. Radar measurements, especially polarimetric diversity observations available fiom the NASA NPOL radar, are providing essential information about the initiation, modulation, and dissipation of convective cores and the generation of associated anvils in tropical convection. Specifically, NPOL radar measurements contain information about convective intensity and its vertical structure for comparison with thermodynamic and kinematic environmental measurements observed from soundings. Because of the polarimetric diversity of MOL, statistics on bulk microphysical properties can be retrieved and compared to the other characteristics of convection and associated cirrus anvils. In summary, the central objectives of this proposal were to deploy the UND Citation research aircraft as an in situ sensing platform for this mission and to provide collaborative analyses of the recorded data and to deploy the NPOL radar to observe the characteristics of cirrus and parent convection.

Poellot, Michael R.↗

The Range Safety Debris Catalog Analysis in Preparation for the Pad Abort One Flight Test

The Pad Abort One flight test of the Orion Abort Flight Test Program is currently under development with the goal of demonstrating the capability of the Launch Abort System. In the event of a launch failure, this system will propel the Crew Exploration Vehicle to safety. An essential component of this flight test is range safety, which ensures the security of range assets and personnel. A debris catalog analysis was done as part of a range safety data package delivered to the White Sands Missile Range in New Mexico where the test will be conducted. The analysis discusses the consequences of an overpressurization of the Abort Motor. The resulting structural failure was assumed to create a debris field of vehicle fragments that could potentially pose a hazard to the range. A statistical model was used to assemble the debris catalog of potential propellant fragments. Then, a thermodynamic, energy balance model was applied to the system in order to determine the imparted velocity to these propellant fragments. This analysis was conducted at four points along the flight trajectory to better understand the failure consequences over the entire flight. The methods used to perform this analysis are outlined in detail and the corresponding results are presented and discussed.

Kutty, Prasad M.↗