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Results for “free-energy calculation”

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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69 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

The equation of state for stellar envelopes. IV - Thermodynamic quantities and selected ionization fractions for six elemental mixes

The free-energy minimization technique in the form developed in the preceding papers in this series is employed to evaluate thermodynamic quantities and ionization fractions on a fine temperature and density grid for six astrophysical mixtures of 15 elements. The mixtures range from that appropriate to super-metal-rich stars, through solar abundance, to that for extreme Population II objects. In this paper, the results for solar abundances are summarized in a form that is illustrative and which facilitates comparison with the results from other equation of state calculations.

Mihalas, Dimitri↗
NASA NTRS2002

Phase-Field Methods for Structure Evolution in Sheared Multiphase Systems

A homogeneous disordered phase separates into ordered structures when quenched into a broken-symmetry phase. The competition of broken-symmetry phases to select an equilibrium state may be studied in terms of coarse-grained order parameters described by a suitable Landau free-energy function. A network of equilibrium-phase domains develops on quenching and coarsens with time with a topology that may be controlled by shear. We use three-dimensional simulations, in which time-dependent models for conserved-order parameters coupled to Navier-Stokes fluid models are solved, to investigate the evolution of such domains, e.g. spinodal decompositions of polymeric materials under shear. The numerical problems are formidable because of the strong nonlinearities inherent in the coupled model, and these are amongst the first 3D calculations undertaken. In linear shear fields we find stable nanostrings, also recently seen in experiments. The affinity of the ordered phases to boundaries plays a role in the form of the structures that develop, with stacked plate-like phase distributions emerging under certain conditions. Such methods appear quite promising for design and analysis of multiphase and complex fluid formulations. The behavior of foams in such conditions is of particular interest in microgravity environments. Additional information can be found in the original extended abstract.

Badalassi, Vittorio↗
DOE OSTI2025

Fully thermal meta-GGA exchange correlation free-energy density functional

The application of density functional theory to materials in the warm dense matter regime has motivated the development of exchange-correlation functionals which incorporate proper, explicit temperature dependence. Previous work has yielded fully-thermal exchange-correlation free energy functionals at the local density approximation (LDA) and generalized gradient approximation (GGA) levels of refinement. Recently an additive thermal correction scheme was utilized to construct a meta-GGA exchange-correlation (XC) functional in which thermal effects are treated at the GGA level. Here, the f TSCAN free-energy XC functional presented here includes thermal effects through the meta-GGA level in the context of the SCAN (strongly constrained and appropriately normed) ground-state functional. The f TSCAN functional provides generality while achieving similar performance to a thermal GGA functional at high temperatures, e.g. pressures within 1% of path integral Monte Carlo simulations of warm dense hydrogen, and a significant improvement over ground-state functionals. At low temperatures, f TSCAN demonstrates improvements in accuracy relative to lower-level and deorbitalized functionals, indicating that calculations using f TSCAN may be expected to perform well across experimentally relevant densities and pressures.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Tuning of altermagnetism by strain

For all collinear altermagnets, we sort out piezomagnetic free-energy invariants allowed in the nonrelativistic limit and relativistic piezomagnetic invariants bilinear in the Néel vector $\mathbf{L}$ and magnetization $\mathbf{M}$, which include strain-induced Dzyaloshinskii-Moriya interaction. The symmetry-allowed responses are fully determined by the nonrelativistic spin Laue group. In the nonrelativistic limit, two distinct mechanisms are discussed: the band-filling mechanism, which exists in metals and is illustrated using the simple two-dimensional Lieb lattice model, and the temperature-dependent exchange-driven mechanism, which is illustrated using first-principles calculations for transition-metal fluorides. The leading second-order nonrelativistic term in the strain-induced magnetization is also obtained for CrSb. Piezomagnetism due to the strain-induced Dzyaloshinskii-Moriya interaction is calculated from first principles for transition-metal fluorides, MnTe, and CrSb. Finally, we discuss triplet superconducting correlations supported by altermagnets and protected by inversion rather than time-reversal symmetry. We apply the nonrelativistic classification of Cooper pairs to describe the interplay between strain and superconductivity in the two-dimensional Lieb lattice and in bulk rutile structures. Here, we show that triplet superconductivity is, on average, unitary in an unstrained altermagnet, but becomes non-unitary under piezomagnetically active strain.

FOS: Physical sciences↗
DOE OSTI2026

Computational discovery of a tetragonal MBene phase: diamond-shaped boron lattices, viable MAB precursors, and selective CO 2 reduction

MBenes are a class of two-dimensional transition-metal borides derived from layered MAB phases. Here, we use first-principles calculations to predict a new tetragonal MB (1 : 1) MBene phase featuring a diamond-shaped B–B lattice and systematically assess its phase stability, synthetic accessibility, and catalytic performance towards the CO 2 reduction reaction (CO 2 RR). Four tetragonal configurations are benchmarked against known hexagonal and orthorhombic phases, and a multi-tier screening identifies six robust members (CrB, FeB, MoB, WB, IrB, and PtB). Exploration of the I4/mmm MAB space reveals 11 viable precursors, including the experimentally synthesized Ir 2 ZnB 2 , which validates our screening approach. CO 2 RR free-energy diagrams show that CrB favors CH 3 OH while FeB, MoB, WB, IrB, and PtB preferentially yield HCOOH. The corresponding limiting potentials are competitive with, and in some cases superior to, those reported for state-of-the-art orthorhombic and hexagonal MBenes. These findings expand the MBene landscape by establishing a tetragonal phase with structural, synthetic, and catalytic promise.

Lu, Linguo [University of Puerto Rico, San Juan, P↗
NASA NTRS1980

User's guide for the computer code COLTS for calculating the coupled laminar and turbulent flow over a Jovian entry probe

A user's guide for a computer code 'COLTS' (Coupled Laminar and Turbulent Solutions) is provided which calculates the laminar and turbulent hypersonic flows with radiation and coupled ablation injection past a Jovian entry probe. Time-dependent viscous-shock-layer equations are used to describe the flow field. These equations are solved by an explicit, two-step, time-asymptotic finite-difference method. Eddy viscosity in the turbulent flow is approximated by a two-layer model. In all, 19 chemical species are used to describe the injection of carbon-phenolic ablator in the hydrogen-helium gas mixture. The equilibrium composition of the mixture is determined by a free-energy minimization technique. A detailed frequency dependence of the absorption coefficient for various species is considered to obtain the radiative flux. The code is written for a CDC-CYBER-203 computer and is capable of providing solutions for ablated probe shapes also.

Kumar, A.↗
DOE OSTI2022

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

The kinetics of hydride transfer from Re( R bpy)(CO) 3 H (bpy = 4,4'-R-2,2'-bipyridine; R = OMe, t Bu, Me, H, Br, COOMe, CF 3 ) to CO 2 and seven different cationic N-heterocycles were determined. Additionally, the thermodynamic hydricities of complexes of the type Re( R bpy)(CO) 3 H were established primarily using computational methods. Linear free-energy relationships (LFERs) derived by correlating thermodynamic and kinetic hydricities indicate that, in general, the rate of hydride transfer increases as the thermodynamic driving force for the reaction increases. Kinetic isotope effects range from inverse for hydride transfer reactions with a small driving force to normal for reactions with a large driving force. Hammett analysis indicates that hydride transfer reactions with greater thermodynamic driving force are less sensitive to changes in the electronic properties of the metal hydride, presumably because there is less buildup of charge in the increasingly early transition state. Bronsted α values were obtained for a range of hydride transfer reactions and along with DFT calculations suggest the reactions are concerted, which enables the use of Marcus theory to analyze hydride transfer reactions involving transition metal hydrides. It is notable, however, that even slight perturbations in the steric properties of the Re hydride or the hydride acceptor result in large deviations in the predicted rate of hydride transfer based on thermodynamic driving forces. This indicates that thermodynamic considerations alone cannot be used to predict the rate of hydride transfer, which has implications for catalyst design.

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

Mechanical and Thermal Properties for Uranium and U–6Nb Alloy from First-Principles Theory

Elasticity, lattice dynamics, and thermal expansion for uranium and U–6Nb alloy (elastic moduli) are calculated from density functional theory that is extended to include orbital polarization (DFT+OP). Introducing 12.5 at.% of niobium, substitutionally, in uranium softens all the cii elastic moduli, resulting in a significantly softer shear modulus (G). Combined with a nearly invariant bulk modulus (B), the quotient B/G increases dramatically for U–6Nb, suggesting a more ductile material. Lattice dynamics from a harmonic model coupled with a DFT+OP electronic structure is applied for α uranium, and the obtained phonon density of states compares well with inelastic neutron-scattering measurements. The Debye temperature associated with the lattice dynamics falls within the range of experimentally observed Debye temperatures and it also validates our quasi-harmonic (QH) phonon model. The QH Debye–Grüneisen phonon method is combined with a DFT+OP electronic structure and used to explore the anisotropic thermal expansion in α uranium. The anomalous negative thermal expansion (contraction) of the b lattice parameter of the α-phase orthorhombic cell is relatively well reproduced from a free-energy model consisting of QH-phonon and DFT+OP electronic structure contributions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Interplay Between Metastability and Mechanically Induced Structural Instability in CsPbBr 3 Photovoltaic Perovskite

An atomic-level understanding of the underlying structural metastability is still absent in halide perovskite photovoltaic systems. Focusing on the model material CsPbBr 3 , the impact of mechanically induced atomic structure alteration is elucidated through structural modeling and X-ray diffraction measurements. Sudden Cs–Br bond breaking drives the system metastability, where the first-order transition arises from cation-halide bond strain relief by severing the corner connectivity of the PbBr 6 units. The pressure–volume and entropy terms govern the Gibbs free-energy landscape in halide perovskites. In conclusion, metastability is revealed as a critical factor limiting the performance of lead halide perovskites under extreme but natural environments.

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

Theory of the charge density wave in A V 3 Sb 5 kagome metals

The family of metallic kagome compounds AV 3 Sb 5 (A = K, Rb, Cs) was recently discovered to exhibit both superconductivity and charge order. The nature of the charge density wave (CDW) phase is presently unsettled, which complicates the interpretation of the superconducting ground state. In this paper, we use group theory and density functional theory (DFT) to derive and solve a phenomenological Landau model for this CDW state. The DFT results reveal three unstable phonon modes with the same in-plane momentum but different out-of-plane momenta, whose frequencies depend strongly on the electronic temperature. This is indicative of an electronically driven CDW, stabilized by features of the in-plane electronic dispersion. Motivated by the DFT analysis, we construct a Landau free-energy expansion for coupled CDW order parameters with wave vectors at the M and L points of the hexagonal Brillouin zone. We find an unusual trilinear term coupling these different order parameters, which can promote the simultaneous condensation of both CDWs even if the two modes are not nearly degenerate. We classify the different types of coupled multi-Q CDW orders, focusing on those that break the sixfold rotational symmetry and lead to a unit-cell doubling along all three crystallographic directions, as suggested by experiments. Here, we determine a region in parameter space, characterized by large nonlinear Landau coefficients, where these phases—dubbed staggered trihexagonal and staggered Star of David—are the leading instabilities of the system. Finally, we discuss the implications of our results for the kagome metals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Molecular simulation of the separation of toluene and p-xylene with the thermally-robust ionic liquid triphenyl-p-phenyl sulfonyl phenyl phosphonium

In this work, we use molecular dynamics simulations to evaluate the behavior of toluene (TOL) and p-xylene (XYL) within three different solvents: n -hexane (HEX), n -heptane (HEP), and a thermally-robust ionic liquid (triphenyl-p-phenyl sulfonyl phenyl phosphonium + bis(trifluoromethylsulfonyl)imide (TPSP + Tf 2 N)). Several different temperatures are explored, while the solvation structures, energetics, and dynamics of TOL and XYL are evaluated. The solvation free energy (ΔG solv ) and transfer free energy (ΔG transfer ) of TOL and XYL are calculated using thermodynamic integration (TI). The transfer free energy of XYL from HEP/HEX to TPSP + Tf 2 N is more favorable than that of TOL over the entire temperature range, while the transfer of both TOL and XYL becomes less favorable as the temperature increases. The diffusion rates of TOL and XYL are lower in the ionic liquid when compared to HEP and HEX, but the thermal stability of TPSP + Tf 2 N may allow for higher operating temperatures and accelerated mass transport rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Binding Affinity Prediction by Pairwise Function Based on Neural Network

In this paper, we present a new approach to estimate the binding affinity from given three-dimensional poses of protein–ligand complexes. In this scheme, every protein–ligand atom pair makes an additive free-energy contribution. The sum of these pairwise contributions then gives the total binding free energy or the logarithm of the dissociation constant. The pairwise contribution is calculated by a function implemented via a neural network that takes the properties of the two atoms and their distance as input. The pairwise function is trained using a portion of the PDBbind 2018 data set. The model achieves good accuracy for affinity predictions when evaluated with PDBbind 2018 and with the CASF-2016 benchmark, comparing favorably to many scoring functions such as that of AutoDock Vina. The framework here may be extended to incorporate other factors to further improve its accuracy and power.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Towards accurate orbital-free simulations: A generalized gradient approximation for the noninteracting free energy density functional

For orbital-free ab initio molecular dynamics, especially on systems in extreme thermodynamic conditions, we provide the first pseudo-potential-adapted generalized gradient approximation (GGA) functional for the non-interacting free energy. This is achieved by systematic finite-temperature extension of our recent LKT ground state non-interacting kinetic energy GGA functional (Phys. Rev. B 98, 041111(R) (2018)). We test the performance of the new functional first via static lattice calculations on crystalline aluminum and silicon. Then we compare deuterium equation of state results against both path-integral Monte Carlo and conventional (orbital-dependent) Kohn-Sham results. The new functional, denoted LKTF, outperforms the previous best semi-local free energy functional, VT84F (Phys. Rev. B 88, 161108(R) (2013)), and provides modestly faster simulations. Finally, we discuss subtleties of identification of kinetic and entropic contributions to non-interacting free-energy functionals obtained by extension from ground state orbital-free kinetic energy functionals.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Spectral-partitioned Kohn-Sham density functional theory

Here we introduce a general, variational scheme for systematic approximation of a given Kohn-Sham free-energy functional by partitioning the density matrix into distinct spectral domains, each of which may be spanned by an independent diagonal representation without requirement of mutual orthogonality. It is shown that by generalizing the entropic contribution to the free energy to allow for independent representations in each spectral domain, the free energy becomes an upper bound to the exact (unpartitioned) Kohn-Sham free energy, attaining this limit as the representations approach Kohn-Sham eigenfunctions. A numerical procedure is devised for calculation of the generalized entropy associated with spectral partitioning of the density matrix. The result is a powerful framework for Kohn-Sham calculations of systems whose occupied subspaces span multiple energy regimes. As a case in point, we apply the proposed framework to warm- and hot-dense matter described by finite-temperature density functional theory, where at high energies the density matrix is represented by that of the free-electron gas, while at low energies it is variationally optimized. We derive expressions for the spectral-partitioned Kohn-Sham Hamiltonian, atomic forces, and macroscopic stresses within the projector-augmented wave (PAW) and the norm-conserving pseudopotential methods. It is demonstrated that at high temperatures, spectral partitioning facilitates accurate calculations at dramatically reduced computational cost. Moreover, as temperature is increased, fewer exact Kohn-Sham states are required for a given accuracy, leading to further reductions in computational cost. Finally, it is shown that standard multiprojector expansions of electronic orbitals within atomic spheres in the PAW method lack sufficient completeness at high temperatures. Spectral partitioning provides a systematic solution for this fundamental problem.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Orbital-Free Quantum Simulation Methods for Application to Warm Dense Matter (Final Technical Report)

Predictive simulations for prediction of condensed system behavior in state conditions far from ambient is increasingly crucial to DOE priorities. Warm dense matter (WDM) is the paradigm: temperature T > 1-15 eV, pressures P to 1 Mbar or greater. Experiments under such state conditions are difficult and costly. We summarize work driven by the need and opportunity to make free-energy density functional theory (DFT) as powerful a tool for ab initio simulation of matter under such extreme conditions as ground state DFT is for ordinary matter Advancing orbital-free DFT (OF-DFT) to eliminate the Kohn-Sham (KS) scaling bottleneck in such simulations is the other priority. The concurrent challenge for both goals is the intrinsic complexity of WDM. We summarize 15 years of successes and major progress on (1) free energy exchange-correlation functionals; (2) non-interacting free energy functionals (counterpart to T=0 Kohn-Sham kinetic energy density functionals); (3) rigorous results and constraints for free-energy DFT; (4) software for free energy DFT calculations in both conventional Kohn-Sham and OF-DFT form; (5) de-orbitalization of advanced orbital-dependent ground state functionals for use in OF-DFT; (6) demonstration calculations; (7) ancillary achievements (e.g. major review articles, secondary explorations motivated by primary goals).

36 MATERIALS SCIENCE↗