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Results for “Enthalpy of formation”

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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Primary solidification of ternary compounds in Al-rich Al–Ce–Mn alloys

Primary solidification of ternary compounds Al 20 Mn 2 Ce and Al 10 Mn 2 Ce were analyzed through the coupling of the thermodynamic modeling and classic nucleation theory. Thermodynamic models of Al 20 Mn 2 Ce and Al 10 Mn 2 Ce were developed using the CALPHAD approach based on first-principles calculated enthalpy of formation and experimental data obtained from this work and the literature. The analysis suggested that despite the larger thermodynamic driving force for nucleation of Al 10 Mn 2 Ce, nucleation is preferred for the Al 20 Mn 2 Ce phase in the highly undercooled liquid due to its smaller interfacial energy. Therefore, manufacturing methods with rapid cooling rates will favor primary solidification of Al 20 Mn 2 Ce for Al-rich Al–Ce–Mn alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Ab initio modeling and thermodynamics of hydrated plutonium oxalates

An ab initio study on the plutonium oxalate hydrates: Pu 2 (C 2 O 4 ) 3 ·10H 2 O and Pu(C 2 O 4 ) 2 ·6H 2 O, using PBE exchange-correlation with D3 dispersion correction and Hubbard correction for the plutonium atoms, was performed and compared to experimental vibrational spectral and thermodynamic property values. Here we demonstrated that this technique can accurately predict the experimental infrared spectra Pu(III) oxalate hydrate, as well as the Raman peak of PuO 2 (used to calculate the thermodynamic properties of the oxalates). For Pu(IV) oxalate hydrate we found that our predicted structure agreed qualitatively with PXRD measurements, the only available experimental determination of the structure. Using this method at standard temperature and pressure, we predicted standard enthalpies of formation of -6,755 kJ mol -1 and -3,923 kJ mol -1 and standard Gibbs free energy of formation of -5,899 kJ mol -1 and -3,386 kJ mol -1 for Pu 2 (C 2 O 4 ) 3 ·10H 2 O and Pu(C 2 O 4 ) 2 ·6H 2 O, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2022

IMPROVING THE ACCURACY OF COMPOSITE METHODS: A G4MP2 METHOD WITH G4-LIKE ACCURACY AND IMPLICATIONS FOR MACHINE LEARNING

G4MP2 theory has proven to be a reliable and accurate quantum chemical composite method for the calculation of molecular energies using an approximation based on second-order perturbation theory to lower computational costs compared to G4 theory. However, it has been found to have significantly increased errors when applied to larger organic molecules with 10 or more nonhydrogen atoms. We report here on an investigation of the cause of the failure of G4MP2 theory for such larger molecules. One source of error is found to be the "higher-level correction (HLC)", which is meant to correct for deficiencies in correlation contributions to the calculated energies. This is because the HLC assumes that the contribution is independent of the element and the type of bonding involved, both of which become more important with larger molecules. We address this problem by adding an atom-specific correction, dependent on atom type but not bond type, to the higher-level correction. We find that a G4MP2 method that incorporates this modification of the higher-level correction, referred to as G4MP2A, becomes as accurate as G4 theory (for computing enthalpies of formation) for a test set of molecules with less than 10 nonhydrogen atoms as well as a set with 10-14 such atoms, the set of molecules considered here, with a much lower computational cost. The G4MP2A method is also found to significantly improve ionization potentials and electron affinities. Finally, we implemented the G4MP2A energies in a machine learning method to predict molecular energies.

Dandu, Naveen↗
DOE OSTI2026

Thorium Monosilicide, ThSi: An Experimental and Theoretical Study

The present theoretical and experimental combination study investigates the ThSi molecule in detail. Computationally, we utilized high-level multireference and coupled-cluster levels of theory conjoined with large correlation consistent basis sets to study a series of electronic and spin–orbit states of ThSi. Here, we report potential energy curves (PECs), electron configurations at equilibrium distances, spectroscopic constants, energetics, and spin–orbit coupling effects for 16 electronic states of ThSi. The studied 16 electronic states are arranged tightly within 0.9 eV, highlighting the complexity of the electronic spectrum of ThSi. The ground electronic state of ThSi is a single-reference 1 1 Σ + state that derives from the 1σ 2 2σ 2 1π 4 electronic configuration. The Ω = 0 + spin–orbit ground state of ThSi is composed of 1 1 Σ + (47%) and 13Π (44%) electronic states. Our measured bond energy (D0) of ThSi, obtained using resonant two-photon ionization (R2PI) spectroscopy is 3.146(4) eV, where the assigned error limit is given in parentheses in units of the last quoted digits. The computed D0 of ThSi (Ω = 0 + ) at the CBS-C-CCSD(T)-δT(Q)-δDK-δSO level (3.181 eV) is in good agreement with the experimental value. Our derived enthalpy of formation for ThSi, Δ f H 0K o (ThSi(g)), is 971.8(6.0) kJ/mol. Finally, we have performed density functional theory (DFT) calculations for ThSi(1 1 Σ + ) using 16 exchange correlation functionals that span multiple rungs of “Jacob’s ladder” of density functional approximation (DFA) to assess the DFT errors on D 0 , r e , and ω e of ThSi with respect to experimental and ab initio coupled-cluster values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Procedures for Assessing the Stability of Proposed Topological Materials

Here, we investigate the stability of MnPb 2 Bi 2 Te 6 (MPBT), which is predicted to be a magnetic topological insulator (TI), using density functional theory calculations. Our analysis includes various measures such as enthalpies of formation, Helmholtz free energies, defect formation energies, and dynamical stability. Our thermodynamic analysis shows that the phonon contribution to the energy gain from finite temperature is estimated to be less than 10 meV/atom, which may not be sufficient to stabilize MPBT at high temperatures, even with the most favorable reactions starting from binaries. While MPBT is generally robust against the formation of various defects, we find that the anti-site defect formation of MnPb is the most likely to occur, with a corresponding energy less than 60 meV. This can be attributed to the significant energy cost from compressive strain at the PbTe layer. Our findings suggest that MPBT is on the brink of stability in terms of thermodynamics and defect formation, underscoring the importance of conducting systematic analyses of the stability of proposed TIs, including MPBT, for their practical utilization. This study offers valuable insights into the design and synthesis of desirable magnetic TI materials with robust stabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Effect of Anions on the Delithiation of [Li–Al] Layered Double Hydroxides: Thermodynamic Insights

The utilization of lithium aluminum [Li–Al] layered double hydroxides (LDHs) is explored for direct lithium extraction (DLE) from geothermal brines and minerals. Following extraction, the Li + ions need to be removed from the LDH structure and converted into LiOH or Li 2 CO 3 products, making them suitable for battery applications. The research investigates the delithiation of [Li–Al-X] LDHs (where X = Cl – , OH – , and SO 4 2– ), which were synthesized and dried under different conditions. Herein the study aims to understand how the choice of anions and drying conditions affects the delithiation process. To determine the stability of these [Li–Al] LDHs, high-temperature oxide melt solution calorimetry is employed. The results reveal that the stability of LDHs varies significantly based on postdrying conditions, anion choice, and the water content in the interlayer. The order of stability, as indicated by the enthalpy of formation values, is found to be OH-LDH-O > OH-LDH-A > SO 4 -LDH-O > SO4-LDH-A > Cl-LDH-O > Cl-LDH-A. This trend is attributed to the interactions among the interlayer species and the metal hydroxide layers.

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

Stress-Dependent Chemo-Mechanical Performance of Amorphous Si Anodes for Li-Ion Batteries upon Lithiation

Alloying-type anodes are significantly governed by their chemo-mechanical performance during the electrochemical cycling. The reaction-induced huge volumetric change of these anodes may cause material degradation and failure under mechanical constraints. Here, we investigate the stress-dependent lithiation behavior of amorphous Si (a-Si) anodes using molecular dynamics simulations. It is indicated that a-Si anodes can sustain higher hydrostatic stress than biaxial/uniaxial ones without the occurrence of mechanical failure. Thermodynamic and electrochemical calculations demonstrate that although the lithiation procedure also affects the thermodynamic stability of a-Si anodes, it is mainly dominated by the external mean stresses. Compressive stress is confirmed to destabilize a-Si anodes and further trigger their capacity fading. Compared with our atomistic simulations, previous continuum models underestimate the open-cell potentials of a-Si anodes, due to their ignored large volumetric deformation at higher stresses and Li concentrations. Finally, this computational study provides the intensive atomic-level understanding of the stress-dependent lithiation behavior of a-Si anodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Ga + -Chabazite Zeolite: A Highly Selective Catalyst for Nonoxidative Propane Dehydrogenation

Ga-chabazite zeolites (Ga-CHA) have been found to efficiently catalyze propane dehydrogenation with high propylene selectivity (96%). In situ FTIR spectroscopy and pulse titrations are employed to determine that upon reduction, surface Ga 2 O 3 is reduced and diffuses into the zeolite pores, displacing the Brønsted acid sites (BAS) and forming extra-framework Ga + sites. This isolated Ga + site reacts reversibly with H 2 to form GaHx (2034 cm -1 ) with an enthalpy of formation of ~ -51.2 kJ·mol -1 , a result supported by Density functional theory (DFT) calculations. The initial C 3 H 6 dehydrogenation rates decrease rapidly (40%) during the first 100 min and then decline slowly afterward, while the C 3 H 6 selectivity is stable at ~ 96%. The reduction in the reaction rate is correlated with the formation of polycyclic aromatics inside the zeolite (using UV-vis spectroscopy) indicating that the accumulation of polycyclic aromatics is the main cause of the deactivation. The carbon species formed can be easily oxidized at 600 °C with complete recovery of the PDH catalytic properties. The correlations between GaH x vs. Ga/Al ratio, and PDH rates vs. Ga/Al ratio show that extra-framework Ga + is the active center catalyzing propane dehydrogenation. The higher reaction rate on Ga + than In + in CHA zeolites, by a factor of 43, is the result of differences in the stabilization of the transition state due to the higher stability of Ga 3+ vs. In 3+ . The uniformity of the Ga + sites in this material makes it an excellent model for the molecular understanding of metal cation exchanged hydrocarbon interactions in zeolites.

10 SYNTHETIC FUELS↗
DOE OSTI2023

A map of single-phase high-entropy alloys

High-entropy alloys have exhibited unusual materials properties. The stability of equimolar single-phase solid solution of five or more elements is supposedly rare and identifying the existence of such alloys has been challenging because of the vast chemical space of possible combinations. Herein, based on high-throughput density-functional theory calculations, we construct a chemical map of single-phase equimolar high-entropy alloys by investigating over 658,000 equimolar quinary alloys through a binary regular solid-solution model. We identify 30,201 potential single-phase equimolar alloys (5% of the possible combinations) forming mainly in body-centered cubic structures. We unveil the chemistries that are likely to form high-entropy alloys, and identify the complex interplay among mixing enthalpy, intermetallics formation, and melting point that drives the formation of these solid solutions. We demonstrate the power of our method by predicting the existence of two new high-entropy alloys, i.e. the body-centered cubic AlCoMnNiV and the face-centered cubic CoFeMnNiZn, which are successfully synthesized.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Regularized machine learning on molecular graph model explains systematic error in DFT enthalpies

Abstract A major goal of materials research is the discovery of novel and efficient heterogeneous catalysts for various chemical processes. In such studies, the candidate catalyst material is modeled using tens to thousands of chemical species and elementary reactions. Density Functional Theory (DFT) is widely used to calculate the thermochemistry of these species which might be surface species or gas-phase molecules. The use of an approximate exchange correlation functional in the DFT framework introduces an important source of error in such models. This is especially true in the calculation of gas phase molecules whose thermochemistry is calculated using the same planewave basis set as the rest of the surface mechanism. Unfortunately, the nature and magnitude of these errors is unknown for most practical molecules. Here, we investigate the error in the enthalpy of formation for 1676 gaseous species using two different DFT levels of theory and the ‘ground truth values’ obtained from the NIST database. We featurize molecules using graph theory. We use a regularized algorithm to discover a sparse model of the error and identify important molecular fragments that drive this error. The model is robust to rigorous statistical tests and is used to correct DFT thermochemistry, achieving more than an order of magnitude improvement.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A framework for quantifying uncertainty in DFT energy corrections

In this work, we demonstrate a method to quantify uncertainty in corrections to density functional theory (DFT) energies based on empirical results. Such corrections are commonly used to improve the accuracy of computational enthalpies of formation, phase stability predictions, and other energy-derived properties, for example. We incorporate this method into a new DFT energy correction scheme comprising a mixture of oxidation-state and composition-dependent corrections and show that many chemical systems contain unstable polymorphs that may actually be predicted stable when uncertainty is taken into account. We then illustrate how these uncertainties can be used to estimate the probability that a compound is stable on a compositional phase diagram, thus enabling better-informed assessments of compound stability.

42 ENGINEERING↗
DOE OSTI2023

Refining the thermochemical properties of CF, SiF, and their cations by combining photoelectron spectroscopy, quantum chemical calculations, and the Active Thermochemical Tables approach

Fluorinated species have a pivotal role in semiconductor material chemistry and some of them have been detected beyond the Earth's atmosphere. Achieving good energy accuracy on fluorinated species using quantum chemical calculations has long been a challenge. In addition, obtaining direct experimental thermochemical quantities has also proved difficult. Here, we report the threshold photoelectron and photoion yield spectra of SiF and CF radicals generated with a fluorine reactor. The spectra were analysed with the support of ab initio calculations, resulting in new experimental values for the adiabatic ionisation energies of both CF (9.128 ± 0.006 eV) and SiF (7.379 ± 0.009 eV). Using these values, the underlying thermochemical network of Active Thermochemical Tables was updated, providing further refined enthalpies of formation and dissociation energies of CF, SiF, and their cationic counterparts.

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

Accurate and reliable thermochemistry by data analysis of complex thermochemical networks using Active Thermochemical Tables: the case of glycine thermochemistry

Active Thermochemical Tables (ATcT) were successfully used to resolve the existing inconsistencies related to the thermochemistry of glycine, based on statistically analyzing and solving a thermochemical network that includes >3350 chemical species interconnected by nearly 35 000 thermochemically-relevant determinations from experiment and high-level theory. Here, the current ATcT results for the 298.15 K enthalpies of formation are −394.70 ± 0.55 kJ mol −1 for gas phase glycine, −528.37 ± 0.20 kJ mol −1 for solid α-glycine, −528.05 ± 0.22 kJ mol −1 for β-glycine, −528.64 ± 0.23 kJ mol −1 for γ-glycine, −514.22 ± 0.20 kJ mol −1 for aqueous undissociated glycine, and −470.09 ± 0.20 kJ mol −1 for fully dissociated aqueous glycine at infinite dilution. In addition, a new set of thermophysical properties of gas phase glycine was obtained from a fully corrected nonrigid rotor anharmonic oscillator (NRRAO) partition function, which includes all conformers. Corresponding sets of thermophysical properties of α-, β-, and γ-glycine are also presented.

Active Thermochemical Tables↗
DOE OSTI2025

Electronic properties of ThC − and ThC

The present study investigates the properties of low-lying states of ThC − and ThC using correlated wave function theories. To this end, we employed multireference calculations and various coupled-cluster approaches in combination with large correlation-consistent basis sets. These methods were applied to examine potential energy curves (PECs), electron configurations, energetics, spectroscopic constants, and spin–orbit coupling effects for 9 states of ThC − and 18 states of ThC. The ground states of ThC − and ThC were identified as single-reference 2 Σ + 1/2 (I) and $^3Σ^+_{0^-} (\textrm{I})$, respectively. Electron detachment from the 7s orbital of the Th center in ThC − [ 2 Σ + (I); 1σ 2 2σ1 3 σ2 1 π 4 ] yields ThC [ 3 Σ + (I); 1σ 2 2σ 1 3σ 1 1π 4 ]. The calculated adiabatic detachment energy (ADE) and vertical detachment energy (VDE) for this process are 1.591 and 1.604 eV, respectively. Furthermore, the dissociation energy (D 0 ) of ThC [$^3Σ^+_{0^-} (\textrm{I})$] is predicted to be 5.099 eV. The standard enthalpy of formation, $ΔH^{°}_{\textrm{f}}$ (298 K), of ThC is estimated to be 822.52 ± 6 kJ mol −1 .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

First-principles study and experimental characterization of metal incorporation in germanium telluride

Germanium telluride is a well-known phase change material (PCM) used in non-volatile memory cells and radio frequency switches. Controlling the properties of GeTe for improved PCM device performance has sometimes been achieved by doping and/or alloying with metals, often at concentrations greater than 10 at. % and using non-equilibrium methods. Here, since switching PCMs between the low-resistance crystalline and high-resistance amorphous states requires a heating cycle, the stability of metal-incorporated GeTe (Ge 0.5–x M x Te 0.5 ) films is also critical to practical implementation of these materials in electronic and optoelectronic devices. In this work, we use both density-functional theory and experimental characterization methods to probe the solubility and critical properties of Ge 0.5–x M x Te 0.5 films. Using first-principles calculations, we determine the enthalpy of formation for GeTe with 2.08, 4.17, and 6.25 at. % of Cu, Fe, Mn, Mo, and Ti and show trends between the stability of the Ge 0.5–x M x Te 0.5 systems and the atomic position, composition, and distribution of the metal atoms in the GeTe matrix.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Thermodynamics of gallium-stabilized delta-plutonium: A high-temperature drop calorimetry study

Throughout the Cold War (1947–1991), both the United States and the former Soviet Union independently derived a phase diagram for the Pu-Ga system that has different implications on Pu phase stability. In the phase diagram produced by the United States, the Pu δ-phase is thermodynamically stable at room temperatures when Ga content is between 2 and 9 at. %. The diagram produced by the Soviet Union shows the δ-phase undergoing an eutectoid decomposition into the α-Pu + α-Pu 3 Ga at 7.9 at. % Ga and 370 K. This would suggest that Ga-stabilized δ-Pu is metastable with respect to α-Pu + α-Pu 3 Ga at 298 K. To investigate this, and the thermodynamic behavior of Ga in the FCC lattice of δ-Pu, we have utilized high-temperature drop calorimetry to study the enthalpy of formation of two δ-Pu 1−x Ga x compositions. In doing so, mixing models (regular and subregular) were developed to understand the thermodynamic behavior of Ga in the FCC lattice of δ-Pu and found a strong departure from ideal conditions, which suggests Ga ordering in the FCC lattice of δ-Pu. Overall, it was found that δ-Pu 1−x Ga x is enthalpically metastable with respect to α-Pu + Pu 3 Ga at 298 K.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Thermodynamic characterization of synthetic lead-arsenate apatites with different halogen substitutions

Abstract Thermodynamic parameters have been measured for synthetic analogs of the mimetite-group minerals Pb5(AsO4)3X (X = OH, Cl, Br, I) belonging to the apatite supergroup. Phases precipitated from aqueous solutions under ambient conditions with well characterized structures and compositions were studied. For each phase, dissolution enthalpy was experimentally determined by oxide melt drop solution calorimetry in a molten solvent of sodium molybdate (3Na2O·4MoO3) at 976 K. The enthalpy of formation from the elements ΔHf,elo was calculated using thermochemical cycles and was −3030.6 ± 11.5, −3026.6 ± 15.8, −2967.6 ± 25.0, and −2993.1 ± 12.2 kJ/mol for Pb5.00(AsO4)3.00OH0.86(CO3)0.07, Pb5.00(AsO4)3.00Cl0.80(CO3)0.10, Pb5.00(AsO4)3.00Br0.80(CO3)0.10, and Pb5.00(AsO4)3.00I0.45OH0.35(CO3)0.10, respectively. These ΔHf,elo values exhibit typical trends for apatites: they increased (were less negative) with the increasing molar mass and ionic radius of X and decreased with the electronegativity and ionization energy of X. The compilation and comparison of data for Ca-, Pb-, P-, and As-apatites revealed correlations indicating that thermodynamic enthalpic stability is largely influenced by chemical factors (e.g., differences in electronegativities of the elements, ionization energy, or ionic characteristics of the bonds) and to a lesser extent by physical and geometric parameters in the crystal structure related to the mass and size of the X anion. Using the correlations, it was possible to estimate the value of hitherto unknown ΔHf,elo for Pb5(AsO4)3F, −3144.3 ± 66.5 kJ/mol. The observed relationships apply to the entire apatite supergroup and can be used to predict the values of ΔHf,elo for phases that have not been studied experimentally. The new data on environmentally significant phases will contribute to the modeling of mineral-water interactions, particularly for potential use in the remediation of soils and wastes contaminated with Pb and As and in the immobilization of radioactive waste containing I-129.

Geochemistry & Geophysics↗