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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Modeling Equilibrium Solid–Liquid Interfaces under Effective Constant Chemical Potential Using Machine Learning Interatomic Potentials

The chemical potential (μ) of species in solution is essential for understanding various chemical processes at interfaces. Molecular dynamics (MD) simulations, constrained by fixed compositions, cannot maintain constant chemical potential with reference to a targeted concentration or chemical potential under nonequilibrium or dynamic conditions, as solute species can migrate to the interface and deplete (or enrich) the bulk due to solute-interface interactions. In this study, we introduce a simple and computationally efficient approach named iterative quasi-constant chemical potential molecular dynamics (iqCμMD) simulation, which helps simulate targeted molar concentrations of species in solution. iqCμMD overcomes the limitations of conventional MD by adjusting the number of species in the solution to reach a target bulk concentration (chemical potential), which allows simulation of the interface under the bulk conditions comparable to experiment. We demonstrate our approach using machine learning interatomic potential (MLIP)-based MD simulations of the Na 2 SO 4,aq –graphene interface, and to show the transferability of our approach, we also perform classical force field-based MD simulations of NaCl aq –air and NaCl aq –graphite interfaces, which produce comparable results to previous CμMD simulations. Our results also show that the iqCμMD approach efficiently achieves the desired bulk ion concentration within two iterations, and by utilizing MLIPs, we can achieve converged results using relatively small-scale simulations compared to previous CμMD simulations. By combining iqCμMD with MLIP-driven simulations, solid–liquid interfaces can be modeled under an effective constant chemical potential with DFT-level accuracy. Here, we show that iqCμMD offers a robust and simple computational framework for constant chemical potential simulations, as its only requirement is to be able to converge interfacial simulations with a measurable bulk region.

Chemical structure↗
DOE OSTI2021

Spatial profiles of photon chemical potential in near-field thermophotovoltaic cells

Emitted photons stemming from the radiative recombination of electron–hole pairs carry chemical potential in radiative energy converters. This luminescent effect can substantially alter the local net photogeneration in near-field thermophotovoltaic cells. Several assumptions involving the luminescent effect are commonly made in modeling photovoltaic devices; in particular, the photon chemical potential is assumed to be zero or a constant prescribed by the bias voltage. The significance of photon chemical potential depends upon the emitter temperature, the semiconductor properties, and the injection level. Hence, these assumptions are questionable in near-field thermophotovoltaic devices with nanoscale separation distances between the emitter and the cell. In the present work, an iterative solver that combines fluctuational electrodynamics with the drift-diffusion model is developed to tackle the coupled photon and charge transport problem, enabling the determination of the spatial profile of photon chemical potential beyond the detailed balance approach. Here, the difference between the results obtained by allowing the photon chemical potential to vary spatially and by assuming a constant value demonstrates the limitations of the conventional approaches. This study is critically important for performance evaluation of near-field thermophotovoltaic systems with nanoscale vacuum gaps.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Predicting a Key Catalyst-Performance Descriptor for Supported Metal Nanoparticles: Metal Chemical Potential

The chemical potential of metal atoms in supported nanoparticles provides a convenient descriptor of their performance as heterogeneous catalysts that captures the effects of particle size, support and alloying. Based on microcalorimetric measurements, the chemical potential is shown in this work to be predictable as a function of monometallic particle diameter and the adhesion energy of the particle to the support, and, for oxide supports, this adhesion energy correlates predictably with metal oxophilicity. These correlations provide predictions of metal chemical potential that can enable catalyst design. They also suggest an improvement in the Gibbs-Thomson relation for free-standing nanoparticles, whether metals or molecular solids.

metal/oxide interface↗
DOE OSTI2020

Confirmation of the PPLB Derivative Discontinuity: Exact Chemical Potential at Finite Temperatures of a Model System

The landmark 1982 paper of Perdew, Parr, Levy, and Balduz (often called PPLB) laid the foundation for our modern understanding of the role of the derivative discontinuity in density functional theory, which drives much development to account for its effects. A simple model for the chemical potential at vanishing temperature played a crucial role in their argument. We investigate the validity of this model in the simplest non-trivial system to which it can be applied and which can be easily solved exactly, the Hubbard dimer. We find exact agreement in the crucial zero-temperature limit, and show the model remains accurate for a significant range of temperatures. We identify how this range depends on the strength of correlations. We extend the model to approximate free energies accounting for the derivative discontinuity, a feature missing in standard semilocal approximations. Here, we provide a correction to this approximation to yield even more accurate free energies. We discuss the relevance of these results for warm dense matter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Excess chemical potential of small solutes across water--membrane and water--hexane interfaces

The excess chemical potentials of five small, structurally related solutes, CH4, CH3F, CH2F2, CHF3, and CF4, across the water-glycerol 1-monooleate bilayer and water-hexane interfaces were calculated at 300, 310, and 340 K using the particle insertion method. The excess chemical potentials of nonpolar molecules (CH4 and CF4) decrease monotonically or nearly monotonically from water to a nonpolar phase. In contrast, for molecules that possess permanent dipole moments (CH3F, CH2F, and CHF3), the excess chemical potentials exhibit an interfacial minimum that arises from superposition of two monotonically and oppositely changing contributions: electrostatic and nonelectrostatic. The nonelectrostatic term, dominated by the reversible work of creating a cavity that accommodates the solute, decreases, whereas the electrostatic term increases across the interface from water to the membrane interior. In water, the dependence of this term on the dipole moment is accurately described by second order perturbation theory. To achieve the same accuracy at the interface, third order terms must also be included. In the interfacial region, the molecular structure of the solvent influences both the excess chemical potential and solute orientations. The excess chemical potential across the interface increases with temperature, but this effect is rather small. Our analysis indicates that a broad range of small, moderately polar molecules should be surface active at the water-membrane and water-oil interfaces. The biological and medical significance of this result, especially in relation to the mechanism of anesthetic action, is discussed.

NASA Center ARC↗
DOE OSTI2023

Selective permeation up a chemical potential gradient to enable an unusual solvent purification modality

The need for energy-efficient recovery of organic solutes from aqueous streams is becoming more urgent as chemical manufacturing transitions toward nonconventional and bio-based feedstocks and processes. In addition to this, many aqueous waste streams contain recalcitrant organic contaminants, such as pharmaceuticals, industrial solvents, and personal care products, that must be removed prior to reuse. We observe that rigid carbon membrane materials can remove and concentrate organic contaminants via an unusual liquid-phase membrane permeation modality. Surprisingly, detailed thermodynamic calculations on the chemical potential of the organic contaminant reveal that the organic species has a higher chemical potential on the permeate side of the membrane than on the feed side of the membrane. This unusual observation challenges conventional membrane transport theory that posits that all permeating species move from high chemical potential states to lower chemical potential states. Based on experimental measurements, we hypothesize that the organic is concentrated in the membrane relative to water via favorable binding interactions between the organic and the carbon membrane. The concentrated organic is then swept through the membrane via the bulk flow of water in a modality known as “sorp-vection.” We highlight via simplified nonequilibrium thermodynamic models that this “uphill” chemical potential permeation of the organic does not result in second-law violations and can be deduced via measurements of the organic and water sorption and diffusion rates into the carbon membrane. Moreover, this work identifies the need to consider such nonidealities when incorporating unique, rigid materials for the separations of aqueous waste streams.

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

Grand unification at the cosmological collider with chemical potential

We introduce a tree-level chemical potential mechanism for spin-1 particles within cosmological collider physics, allowing them to be detected in primordial non-Gaussianities for masses above the inflationary Hubble scale. We apply this mechanism to orbifold grand unification and the massive unification partners of the standard model gauge bosons. Our mechanism requires at least a pair of massive vector fields which are singlets of the standard model, a condition which is satisfied in the classic “trinification” scenario. Assuming that the gauge hierarchy problem is solved by supersymmetry, gauge coupling running points to unification partners at ~ 10$^{15}$ GeV. We show that, within high-scale inflation, chemical potential enhancement can lead to observably strong signals for trinification partners in future cosmological surveys.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1975

Chemical potential effects on neutrino diffusion in supernovae

The validity of imposing a zero chemical potential for neutrinos in hydrodynamic calculations of collapsing supernovae is investigated in the diffusion approximation of neutrino transport. A coupled system of equations is solved for neutrino and energy diffusion fluxes as well as lepton diffusion in a collapsing supernovae ambient medium, and the results indicate a substantial growth in the neutrino chemical potential for densities greater than 10 to the 12th power gm/cu cm. The rate of energy transport is shown to be significantly affected by increases in Fermi integrals and chemical-potential gradients accompanied by decreases in temperature, and the extent of neutrino particle/antiparticle reactions is found also to affect energy diffusion rates. It is concluded that the photon-like behavior usually assumed for neutrinos may be incorrect and that an extension of the Sn transport approximation to include lepton characteristics is necessary for a definitive answer to the question of neutrino transport in supernovae.

Mazurek, T. J.↗
DOE OSTI2025

Computing chemical potentials with machine-learning-accelerated simulations to accurately predict thermodynamic properties of molten salts

The successful design and deployment of next-generation nuclear technologies heavily rely on thermodynamic data for relevant molten salt systems. However, the lack of accurate force fields and efficient methods has limited the quality of thermodynamic predictions from atomistic simulations. Here we propose an efficient free energy framework for computing chemical potentials, which is the central free energy quantity behind many thermodynamic properties. We accelerate our simulations without sacrificing accuracy by using machine learning interatomic potentials trained on density functional theory (DFT) data. Using lithium chloride as our model system, we compute chemical potentials with DFT-accuracy for solid and liquid phases by transmuting ions into noninteracting particles. Notably, in the liquid phase, we demonstrate consistency whether we transmute one ion pair or the entire system into ideal gas particles. By locating the temperature where the chemical potential of solid and liquid phases cross, we predict a melting point of 880 ± 18 K for lithium chloride, which is remarkably close to the experimental value of 883 K. With this successful demonstration, we lay the foundation for high-throughput thermodynamic predictions of many properties that can be derived from the chemical potentials of the minority and majority components in molten salts.

Gibson, Luke D. [Oak Ridge National Laboratory (OR↗
DOE OSTI2023

Calorimetric Energies and Chemical Potentials of Metal Atoms in Catalytic Nanoparticles on Oxide and Carbon Supports: Improved Size Dependencies and Adhesion Energies

The chemical potential of metal atoms, μM, in supported metal nanoparticles is an important descriptor related to both the catalytic activity and the stability of the nanoparticles. Here, we derive an expression relating μM to the radius of the particle’s contact area with the support and the adhesion energy at the metal/support interface (E adh ) that assumes the particles have the shape of spherical caps but of arbitrary contact angle with the support (θ c ) and includes an empirical correction for the increase in metal surface energy and adhesion energy with decreasing radius of curvature. We then show that, at any assumed contact angle, we can simultaneously fit previously reported measurements of both calorimetric μ M (from heats of metal vapor adsorption during nanoparticle growth by vapor deposition) versus metal coverage data and the He + low-energy ion scattering (LEIS) intensities for the metal and/or support versus metal coverage (using our recently developed spherical cap model for quantitative LEIS intensities), to determine the particle size versus coverage and E adh . Only one choice of contact angle gives a pair of values for contact angle and E adh , which is consistent with the Young–Dupré equation for the equilibrium shape of a spherical particle. At this equilibrium shape, we then applied this spherical cap model (SCM) to reanalyze microcalorimetric metal chemical potentials and LEIS signals versus coverage data for nine metal/support combinations that were previously analyzed by assuming that the particles had the shape of hemispherical caps, i.e., with a contact angle of 90°. We show that this revised approach gives close agreement with the calorimetric and LEIS data; the best-fit contact angles vary from 64 to 84°, correcting the earlier assumption of 90°. Furthermore, these results provide significant accuracy improvements in particle size versus coverage, metal chemical potential versus size and coverage, metal/support adhesion energies and contact angles for Cu, Ag and Au on CeO 2 (111), Ni on MgO(100), Ag on Fe 3 O 4 (111) and TiO 2 (100), and Ag, Ni and Pd on Ni-supported graphene. This revised approach is much more broadly applicable than the earlier hemispherical cap model (HCM).

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2022

Dynamical tuning of the chemical potential to achieve a target particle number in grand canonical Monte Carlo simulations

We present a method to facilitate Monte Carlo simulations in the grand canonical ensemble given a target mean particle number. The method imposes a fictitious dynamics on the chemical potential, to be run concurrently with the Monte Carlo sampling of the physical system. Corrections to the chemical potential are made according to time-averaged estimates of the mean and variance of the particle number, with the latter being proportional to thermodynamic compressibility. Here, we perform a variety of tests, and in all cases find rapid convergence of the chemical potential—inexactness of the tuning algorithm contributes only a minor part of the total measurement error for realistic simulations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1976

Shielding, the bulk chemical potential, and cohesion in alloys

It is shown that the bulk chemical potential in alloys is intimately related to the spatial dependence of the shielding cloud that results when the electronic charge rearranges itself as one atom type is replaced by another at a given site. Such a relationship fixes the relative energy scale between the alloy and its pure constituents, important in determining the stability of alloys. A correct treatment of shielding is thus essential to quantitative calculations of alloy stability. A model calculation of the bulk chemical potential and cohesion of alloys in the tight-binding approximation is presented as a numerical example. In the course of this investigation a general invariant of an integral over the shielding cloud is derived.

Stern, E. A.↗
DOE OSTI2020

The role of chemical potential in compensation control in Si:AlGaN

Reduction in compensation in Si-doped Al-rich AlGaN is demonstrated via chemical potential control (CPC). The chemical potentials and the resulting formation energies of carbon on the nitrogen site (C N ) and cation vacancy complex with Si (V III + nSi III ) were related to growth variables through a thermodynamic supersaturation model, which quantitatively predicted the incorporation of C N and the generation of the V III + nSi III complex. The compensation “knee” behavior, i.e., decreasing conductivity with increasing Si incorporation beyond a certain concentration, was successfully controlled. The maximum free carrier concentration was improved by impeding the formation of V III + nSIi III complexes under III-richer conditions, while the impurity compensation by C N was reduced by making the growth environment N-richer. The results of Hall effect measurement and photoluminescence agreed well with quantitative theoretical predictions of the CPC model. Based on the developed model, the highest conductivity of 160 Ω -1 cm -1 with free carrier concentration of 3 × 10 19 cm -3 in Al 0.7 Ga 0.3 N ever reported was achieved on single crystal AlN substrates. The demonstrated predictive power of the CPC model should greatly reduce the empirical analysis or iterative experimentation that would otherwise be necessary.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Selectivity in Yttrium Manganese Oxide Synthesis via Local Chemical Potentials in Hyperdimensional Phase Space

In sharp contrast to molecular synthesis, materials synthesis is generally presumed to lack selectivity. The few known methods of designing selectivity in solid-state reactions have limited scope, such as topotactic reactions or strain stabilization. This contribution describes a general approach for searching large chemical spaces to identify selective reactions. This novel approach explains the ability of a nominally “innocent” Na 2 CO 3 precursor to enable the metathesis synthesis of single-phase Y 2 Mn 2 O 7 : an outcome that was previously only accomplished at extreme pressures and which cannot be achieved with closely related precursors of Li 2 CO 3 and K 2 CO 3 under identical conditions. By calculating the required change in chemical potential across all possible reactant-product interfaces in an expanded chemical space including Y, Mn, O, alkali metals, and halogens, using thermodynamic parameters obtained from density functional theory calculations, we identify reactions that minimize the thermodynamic competition from intermediates. In this manner, only the Na-based intermediates minimize the distance in the hyperdimensional chemical potential space to Y 2 Mn 2 O 7 , thus providing selective access to a phase which was previously thought to be metastable. Experimental evidence validating this mechanism for pathway-dependent selectivity is provided by intermediates identified from in situ synchrotron-based crystallographic analysis. Finally, this approach of calculating chemical potential distances in hyperdimensional compositional spaces provides a general method for designing selective solid-state syntheses that will be useful for gaining access to metastable phases and for identifying reaction pathways that can reduce the synthesis temperature, and cost, of technological materials.

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

QCD material parameters at zero and non-zero chemical potential from the lattice

Using an eighth-order Taylor expansion in baryon-chemical potential, we recently obtained the (2+1) flavor QCD equation of state (EoS) at non zero conserved charge chemical potentials from the lattice. We focused on strangeness-neutral, isospin-symmetric QCD matter, which closely resembles the situation encountered in heavy-ion collision experiments. Using this EoS, we present here results on various QCD material parameters; in particular we compute the specific heat, speed of sound, and compressibility along appropriate lines of constant physics.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Enhanced contribution of the pairing gap to the QCD equation of state at large isospin chemical potential

In this paper QCD at large isospin density is studied, which is known to be in the superfluid state with Cooper pairs carrying the same quantum number as pions. The gap equation derived from the perturbation theory up to the next-to-leading-order corrections is solved. The pairing gap at large isospin chemical potential is found to be enhanced compared to the color-superconducting gap at large baryon chemical potential due to the 2 difference in the exponent arising from the stronger attraction in one-gluon exchange in the singlet channel. Then, using the gap function, the contribution of the condensation energy of the superfluid state to the QCD equation of state is evaluated. At isospin chemical potential of a few GeV, where the lattice QCD and the perturbative QCD can be both applied, the effect of the condensation energy becomes dominant even compared to the next-to-leading order corrections to the pressure in the perturbation theory. It resolves the discrepancy between the recent lattice QCD results and the perturbative QCD result. Published by the American Physical Society 2024

Astronomy & Astrophysics↗
DOE OSTI2022

Investigation of the monopole magneto-chemical potential in spin ices using capacitive torque magnetometry

The single-ion anisotropy and magnetic interactions in spin-ice systems give rise to unusual non-collinear spin textures, such as Pauling states and magnetic monopoles. The effective spin correlation strength (J eff ) determines the relative energies of the different spin-ice states. With this work, we display the capability of capacitive torque magnetometry in characterizing the magneto-chemical potential associated with monopole formation. We build a magnetic phase diagram of Ho 2 Ti 2 O 7 , and show that the magneto-chemical potential depends on the spin sublattice (α or β), i.e., the Pauling state, involved in the transition. Monte Carlo simulations using the dipolar-spin-ice Hamiltonian support our findings of a sublattice-dependent magneto-chemical potential, but the model underestimates the J eff for the β-sublattice. Additional simulations, including next-nearest neighbor interactions (J 2 ), show that long-range exchange terms in the Hamiltonian are needed to describe the measurements. This demonstrates that torque magnetometry provides a sensitive test for J eff and the spin-spin interactions that contribute to it.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The scalar chemical potential in cosmological collider physics

Non-analyticity in co-moving momenta within the non-Gaussian bispectrum is a distinctive sign of on-shell particle production during inflation, presenting a unique opportunity for the “direct detection” of particles with masses as large as the inflationary Hubble scale ( H ). However, the strength of such non-analyticity ordinarily drops exponentially by a Boltzmann-like factor as masses exceed H . In this paper, we study an exception provided by a dimension-5 derivative coupling of the inflaton to heavy-particle currents, applying it specifically to the case of two real scalars. The operator has a “chemical potential” form, which harnesses the large kinetic energy scale of the inflaton, \( {\overset{\cdot }{\phi}}_0^{1/2}\approx 60H \) , to act as an efficient source of scalar particle production. Derivative couplings of inflaton ensure radiative stability of the slow-roll potential, which in turn maintains (approximate) scale-invariance of the inflationary correlations. We show that a signal not suffering Boltzmann suppression can be obtained in the bispectrum with strength f NL ~ \( \mathcal{O} \) (0 . 01–10) for an extended range of scalar masses \( \lesssim {\overset{\cdot }{\phi}}_0^{1/2} \) , potentially as high as 10 15 GeV, within the sensitivity of upcoming LSS and more futuristic 21-cm experiments. The mechanism does not invoke any particular fine-tuning of parameters or breakdown of perturbation-theoretic control. The leading contribution appears at tree-level , which makes the calculation analytically tractable and removes the loop-suppression as compared to earlier chemical potential studies of non-zero spins. The steady particle production allows us to infer the effective mass of the heavy particles and the chemical potential from the variation in bispectrum oscillations as a function of co-moving momenta. Our analysis sets the stage for generalization to heavy bosons with non-zero spin.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗