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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Understanding the origin of structure sensitivity in hydrodechlorination of trichloroethylene on a palladium catalyst

Periodic density functional theory (DFT) calculations are employed to understand the origin of structure sensitivity in hydrodechlorination (HDC) of trichloroethylene (TCE) over different facets of a palladium catalyst. The HDC reaction is simulated on the terrace (Pd (111) and Pd (100)) and undercoordinated (Pd (211) and Pd (110)) sites of the Pd catalyst. The most stable binding configuration of TCE on the Pd surfaces is observed to be through the di-σ mode of binding, wherein each carbon atom of the TCE molecule is adsorbed atop of the Pd atom. On comparing TCE adsorption over different facets of Pd, a maximum binding energy of –178 kJ mol –1 is calculated over the Pd (110) surface. TCE, upon adsorption on Pd catalyst, undergoes dechlorination followed by hydrogenation of the hydrocarbon intermediates. The activation energies for C–Cl bond dissociation steps are significantly low when compared to the hydrogenation steps. The chlorine released from dechlorination tends to block the active sites, thereby poisoning the surface with high binding energies (B.E > –160 kJ mol –1 ) on all the surfaces. The trend in chlorine binding energies on Pd facets follows: Pd (110) > Pd (211) > Pd (100) > Pd (111). The removal of surface chlorine is facilitated by its reaction with surface hydrogen to form hydrogen chloride. The activation energy for hydrogen chloride formation is calculated to be 90 kJ mol –1 and 88 kJ mol –1 on Pd (111) and Pd (100) terrace sites, respectively and 109 kJ mol –1 and 118 kJ mol –1 on the step Pd (211) and corrugated Pd (110) facets, respectively. This suggests the ease of removal of Cl as HCl from the terrace sites as compared to the step and corrugated sites. The structure sensitivity in the TCE HDC reaction could possibly arise due to the differences in the energetics of Cl removal on different Pd facets. As a result, this mechanistic understanding could provide a rationale for designing suitable catalysts for the HDC of TCE.

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

The electronic structure of diatomic nickel oxide

High level calculations at the MRCI+Q and CCSD(T) levels were used to predict the spectroscopic properties and bond dissociation energy of NiO. A range of DFT functionals were tested and most did not provide good agreement.

Chemistry↗
DOE OSTI2026

Effects of heteroatom doping on hydrogen uptake in tungsten oxide

Redox-active transition metal oxides (TMOs) that can undergo proton-insertion coupled electron transfer (PICET) are promising candidates for catalyzing molecular conversion reactions which require the transfer of hydrogen atoms (or the thermochemical equivalent, H + , e − ). Herein, we studied the effects of isovalent (Mo 6+ ) and aliovalent (V 5+ and Nb 5+ ) heteroatom doping on the electrochemical PICET behavior of monoclinic tungsten oxide (WO 3 ). Cyclic voltammetry in aqueous acidic electrolytes shows that the addition of redox-active heteroatoms (Mo 6+ and V 5+ ) leads to systematic shifts in redox couple half-wave potentials (E 1/2 ), broadening, and an overall decrease in the current response. Conversely, the non-redox active heteroatom (Nb 5+ ) only reduces the current response with no observable peak-current broadening. This broadening is attributed to changes in the proton binding affinities of oxygen in different chemical environments, i.e., bridging different pairs of redox-active transition metal cations. We determined the hydrogen bond dissociation free energy (H BDFE) values to elucidate the thermodynamic effect of heteroatom substitution. Density functional theory calculations reveal a differentiation in the hydrogen binding and oxygen vacancy formation energies between heteroatom doped structures. The PICET-induced structural phase transitions of the pristine and doped samples were further probed with operando electrochemical X-ray diffraction (EC-XRD) and with ex situ chemical reduction. The broadening of the potential-dependent current response with increased heteroatom doping manifests in the operando EC-XRD results as prolonged structural regions where multiple hydrogen bronze phases exist and the appearance of cubic bronze phases at lower degrees of reduction compared to pristine WO 3 .

Holzapfel, Noah P. [North Carolina State Universit↗
DOE OSTI2026

An–imidophosphorane (An = U–Pu) bond covalency and proton-coupled electron transfer thermodynamics driven by orbital energy matching

A series of mid-actinide (An = U–Pu) tetrahomoleptic complexes supported by highly electron-donating imidophosphorane ligands, NPC ([NP t Bu(pyrr) 2 ] − , where t Bu = C(CH 3 ) 3 ; pyrr = pyrrolidinyl = N(C 4 H 8 )), are systematically investigated computationally and experimentally to elucidate the nature of actinide–ligand (An–L) covalency across the An 3+/4+/5+ oxidation states. Trends in An–L bonding and redox properties for these complexes, together with their protonated counterparts, are examined using orbital-, electron density-, and energy-decomposition-based methods. This integrated approach reveals progressively improved energy matching between α-spin An 5f and N im 2p orbitals with increasing atomic number and oxidation state, becoming particularly pronounced in the ligand-dominant π-bonding orbitals of An 4+ and An 5+ . In contrast to the An 3+ species, the enhanced An 5f π contributions in the higher-valent counterparts drive the increase in An–N im covalency for later An, thereby inverting the covalency trend to U < Np < Pu. Redistribution of electron density towards the An and N im atomic basins due to the growing energy-matching assisted covalency correlates with higher pKa values and increased N im –H bond dissociation free energies in protonated An 4+ complexes. Electron density at Nim in An 4+ shows a linear correlation with the p K a values calculated via the Bordwell equation. Calculations predict a cathodic shift of 0.84–1.00 V in the redox couples upon protonation, a trend validated when experimentally accessible. These findings demonstrate an increasing role of covalency driven by orbital energy matching from U to Pu in tuning the thermodynamic driving force for proton-coupled electron transfer in the An 5+ species.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

Non-ideal stoichiometry and thermochemistry of aqueous iridium oxide nanoparticles in proton-coupled electron transfer and oxygen-atom transfer

Reported here are reactions of aqueous colloidal IrO x nanoparticles (NPs) with proton-coupled electron transfer (PCET) and oxygen-atom transfer (OAT) organic reagents, determining the reaction stoichiometries and thermochemistry. IrO x NPs have attracted much attention for their high electrocatalytic activity, but understanding of their fundamental reaction chemistry is limited. This IrO x NP model system is simple, with UV-vis titrations demonstrating reversible interconversion between predominantly Ir IV and predominantly Ir III NPs. This simplicity allows studies that reveal their complex non-idealities. The NP redox chemistry has a “super-Nernstian” stoichiometry of ∼1.3H + per 1e − transferred during both PCET and OAT reactions, as measured with electrochemistry and chemical methods. Spectroelectrochemistry revealed a broad distribution of surface IrO x –H bond dissociation free energies (BDFEs), becoming weaker as more H is added. Such variation in binding strengths—a non-ideal binding isotherm—is common for surface adsorbates. For IrO x , the variation of BDFE(IrO–H)s is fit well to a Frumkin isotherm with a width of 6.5 kcal mol −1 . For OAT from the reactive oxygen atoms of IrO x NPs, bracketing experiments gave 93 ± 24 kcal mol −1 for the average BDFE(O x Ir–O), with a predicted spread much larger than that for the BDFE(IrO–H). Taken together, the results show the importance of non-ideal stoichiometry and thermochemistry for IrO x NPs, and they open a path to more complete models to understand catalytic redox reactions at such surfaces.

Iridium Oxide Nanoparticles (NPs)↗
DOE OSTI2022

Molecular-orbital-based machine learning for open-shell and multi-reference systems with kernel addition Gaussian process regression

We introduce a novel machine learning strategy, kernel addition Gaussian process regression (KA-GPR), in molecular-orbital-based machine learning (MOB-ML) to learn the total correlation energies of general electronic structure theories for closed- and open-shell systems by introducing a machine learning strategy. The learning efficiency of MOB-ML(KA-GPR) is the same as the original MOB-ML method for the smallest criegee molecule, which is a closed-shell molecule with multi-reference characters. In addition, the prediction accuracies of different small free radicals could reach the chemical accuracy of 1 kcal/mol by training on one example structure. Accurate potential energy surfaces for the H10 chain (closed-shell) and water OH bond dissociation (open-shell) could also be generated by MOB-ML(KA-GPR). To explore the breadth of chemical systems that KA-GPR can describe, we further apply MOB-ML to accurately predict the large benchmark datasets for closed- (QM9, QM7b-T, and GDB-13-T) and open-shell (QMSpin) molecules.

Chemistry↗
DOE OSTI2025

Taming the virtual space for incremental full configuration interaction

Incremental full configuration interaction (iFCI) closely approximates the FCI limit with polynomial cost through a many-body expansion of the correlation energy, providing highly accurate total energies within a given basis set. To extend iFCI beyond previous basis set limitations, this work introduces a novel natural orbital (NO) screening approach, incremental NO full configuration interaction (iNO-FCI). By consideration of the importance of virtual orbital selection in the convergence of iFCI, iNO-FCI maximizes the consistency between orbitals selected for each correlated body. iNO-FCI employs a principle of cancellation of errors and ensures that the same set of virtual NOs is used for interdependent terms. Here, this strategy significantly reduces computational cost without compromising precision. Computational savings of up to 95% are demonstrated, allowing access to larger basis sets that were previously computationally prohibitive. iNO-FCI is herein introduced and benchmarked for several difficult test cases involving double-bond dissociation, biradical systems, conjugated π systems, and the spin gap of a Cu-based transition metal complex.

Correlation energy↗
DOE OSTI2026

Consistent inclusion of triple substitutions within a coupled cluster based static quantum embedding theory

We have previously proposed the MPCC static embedding framework for quantum chemistry that self-consistently couples a high-level coupled cluster (CC) treatment of the fragment (active region) with a lower level, Møller–Plesset perturbation treatment of the environment. Our initial implementation was limited to single and double (SD) substitutions, with CCSD for the fragment and first-order perturbative SD amplitudes for the environment. Here, we extend the MPCC embedding treatment to triple substitutions, which is essential for achieving chemical accuracy in energy differences. To this end, we employ a CCSDT solver for the fragment subsystem. For the environment subsystem, we construct a perturbative estimate of the triples amplitudes, explicitly accounting for feedback from all fragment amplitudes. The resulting approach is denoted MPCCSDT(pt). We further introduce a more complete formulation in which feedback from the environment amplitudes to the fragment amplitudes is also included. This scheme involves an iterative treatment of the environment triples amplitudes and is denoted MPCCSDT(it). In addition, we assess the accuracy of the previously proposed low-level method by introducing a modified low-level approach that incorporates a lowest-order treatment of selected long-range effects, including spin fluctuations and charge polarization. All resulting approaches may be viewed as post-CCSD(T) methods. We therefore consider test cases for which CCSD(T) exhibits substantial deviations from CCSDT. These include (i) single- and triple-bond stretching in F 2 and N 2 , (ii) bond dissociation energies of selected molecules from the W4-11 dataset, and (iii) total atomization energies of transition metal hydrides. Our results demonstrate that inclusion of triples amplitudes at the fragment level alone is insufficient; a perturbative treatment of the environment triples amplitudes is required. For many energy-difference applications, feedback from the environment triples amplitudes to the fragment amplitudes is not essential, but it does play a role in the very challenging CoH and FeH molecules. A very interesting finding from our study is that in some challenging cases, we need an improved (second-order) perturbative method for the SD amplitudes, going beyond the first-order one used in our earlier work. In conclusion, considering both cost and accuracy, the MP2CCSDT(pt) model is the most promising for future applications among the candidates considered here.

Shee, Avijit [University of California, Berkeley, ↗
DOE OSTI2021

Active Thermochemical Tables: the thermophysical and thermochemical properties of methyl, CH 3 , and methylene, CH 2 , corrected for nonrigid rotor and anharmonic oscillator effects

The thermophysical properties (isobaric heat capacity, entropy, enthalpy increment) of two prominent radicals, methyl, CH 3 , and methylene, CH 2 , were computed using the Nonrigid Rotor Anharmonic Oscillator (NRRAO) approach and compared to their RRHO counterparts, demonstrating significant differences between the results from the two approaches. Methylene presents a typical case in which the NRRAO thermophysical properties have significantly higher values than their RRHO counterparts at higher temperatures. In the case of methyl, the positive anharmonicity of the umbrella motion causes an opposite effect, and the NRRAO corrected thermophysical properties have lower values than their RRHO counterparts. The NRRAO corrected thermophysical properties, in turn, affect the resulting thermochemical properties. Here, two reactions important in combustion modelling were tested: the recombination of methyl radical with hydrogen atoms to form methane, and the recombination of two methyl radicals to form ethane. The related NRRAO equilibrium constants differ significantly from their RRHO analogs, and the consequences for chemical modelling are discussed. Also reported are the most current ATcT enthalpies of formation for CH n (n = 4-0) species and for C 2 H 6 , together with the tightly related sequential bond dissociation enthalpies along with the CHn series.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Spinor-based coupled cluster thermochemistry: RgF and CnF 0/+ as compared to AuF and HgF 0/+

A relativistic coupled cluster approach that includes spin-orbit variationally in the eXact 2-component (X2C) approximation with the inclusion of the Gaunt interaction (X2Cg) was used to probe the thermochemistry and ground state spectroscopic constants of RgF, CnF, and CnF + . Utilizing large sequences of correlation consistent basis sets at the X2Cg-CCSD(T) level of theory, this work reports 0 K bond dissociation energies (BDEs) of AuF, RgF, HgF 0/+ , and CnF 0/+ , as well as ionization energies of Au, Rg, Hg, Cn, HgF, and CnF.

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

Electronic spectroscopy and ionization potentials for YbOH and YbOCH 3

The polyatomic molecules YbOH and YbOCH 3 have been recognized as being of potential value for spectroscopic experiments that explore charge-parity and time reversal symmetry violation effects. These measurements require very high precision, which, in turn, will necessitate that the molecules be manipulated at ultra-cold temperatures. Both YbOH and YbOCH 3 have electronic transitions that appear suitable for laser cooling ($\tilde{A}$ 2 Π 1/2 -$\tilde{X}$ 2 Σ + and $\tilde{A}$2E 1/2 -$\tilde{X}$ 2 A 1 , respectively) but the currently available spectroscopic data is not sufficient to determine the extent to which population leaks may compromise the optical cooling processes. A further complication is that the quantum states of interest for these measurements will need to be selectively populated. The $\tilde{A}$-$\tilde{X}$ band systems of both YbOH and YbOCH 3 show evidence of vibronic perturbations, such that there are unassigned vibronic features at energies that are just above the origin bands. Here, in the present study we have recorded spectra for the $\tilde{A}$ 2 Π 1/2 -$\tilde{X}$ 2 Σ + transition of jet-cooled YbOD to facilitate the vibronic assignments. In addition, spectra for the $\tilde{B}$ 2 Σ + - $\tilde{X}$ 2 Σ + transition of YbOH were recorded, establishing the origin band at 20473.8 cm -1 . Previously, the reaction of Yb with CH 3 OH has been used to generate gas-phase YbOCH 3 . As this reaction also yields YbOH, there have been complications in spectroscopic studies of YbOCH 3 due to overlap of the $\tilde{A} -\tilde{X}$ band systems. To identify specific regions of overlap, resonantly enhanced two-photon ionization spectra were recorded using mass-resolved detection of the YbOH + and YbOCH 3 + ions. These data confirmed the overlap of vibronic bands near 17640 and 17680 cm -1 . Two-photon ionization spectroscopy also provided accurate ionization energies of IE(YbOH)=45788(10) and IE(YbOCH 3 )=45283(10) cm -1 . The IE for YbOH is relevant to problems encountered in previous attempts to determine the bond dissociation energy of YbOH + .

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

Atomistic simulations for investigation of substrate and salt effects on lipid in-source fragmentation in secondary ion mass spectrometry: A follow-up study

In-source fragmentation (ISF) poses a significant challenge in secondary ion mass spectrometry (SIMS). These fragment ions increase the spectral complexity and can lead to incorrect annotation of fragments as intact species. The presence of salt that is ubiquitous in biological samples can influence the fragmentation and ionization of analytes in a significant manner, but their influences on SIMS have not been well characterized. To elucidate the effect of substrates and salt on ISF in SIMS, we have employed experimental SIMS in combination with atomistic simulations of a sphingolipid on a gold surface with various NaCl concentrations as a model system. Our results revealed that a combination of bond dissociation energy and binding energy between N-palmitoyl-sphingomyelin and a gold surface is a good predictor of fragment ion intensities in the absence of salt. However, ion-fragment interactions play a significant role in determining fragment yields in the presence of salt. Additionally, the charge distribution on fragment species may be a major contributor to the varying effects of salt on fragmentation. This study demonstrates that atomistic modeling can help predict ionization potential when salts are present, providing insights for more accurate interpretations of complex biological spectra.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Feasibility of a Novel Density Functional Method Outside the Kohn-Sham Framework for Modeling Global Potential Energy Surfaces of Molecular Chemical Reactions (Final Technical Report)

The project aimed towards the construction of computational methods capable of modeling the global potential energy surface (PES) of small molecules, molecular ions, and radicals — including the parts of the PES which correspond to chemical reactions, and the reaction paths connecting reactants, intermediates, and reaction products. This goal may seem humble at first glance, but for chemical systems with more than about six atoms in total, at the time the project was proposed, there were no established theoretical methods capable of simulating such systems reliably, not even for small molecules in the gas phase which are electronically benign. This restriction severely hampers our ability to model and control chemical processes under harsh conditions. With the goal of constructing a method capable of modeling such chemical systems, we proposed to pursue a novel approach towards a Multi-Configuration (MC) DFT outside the traditional frameworks of Kohn-Sham theory and other methods of coupling wave function theory with DFT. Rather than being a complete active space (CAS) method, the proposed DOCI-DFT would employ a special restricted form of the active space wave function, called Doubly-Occupied CI (DOCI)—this wave function form is sufficient to describe not only heterolytic, but also homolytic bond dissociation processes at the zeroth order (i.e., as active space wave function). There are no other standard mean field methods which can do so. In the original proposal, we also outlined strong formal and practical arguments speaking for this method. The project proposal was accepted by the Department of Energy and provided two years of seed funding for one graduate student, as well as two years of two weeks PI summer-salary for the PI. However, ultimately the project could not be effectively pursued due to severe interferences outside the context scientific problems and was cancelled. Apart from two weeks of PI salary (and associated fringe & overhead costs issues by the performing institution), no costs were charged against the award, with the entire rest of funding returned to the Department of Energy. This report reiterates the primary background information regarding the project, its original goals, and outlines the preliminary work performed during the two weeks of DOE funding charged.

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

DOE STTR Phase I Final Report Report: Machine-learning Based Prediction of Thermal Limits for Conjugated Organic Materials

The SCANN-DT Phase I STTR project led by NLM Photonics and partnering with the National Renewable Energy Laboratory (NREL) sought to apply machine learning techniques based on graph neural networks (GNNs) towards the prediction of decomposition temperatures (Td) of organic semiconductors, based on prior work on bond dissociation energy (BDE) prediction as implemented in NREL’s ALFABET prediction tool. Using a curated set of experimental decomposition energies, the project examined GNN-based, classical quantitative structure-property relationship (QSPR) based on DFT calculations, and combinations of both methods to predict Td. While the best MAEs in Td achieved were near 40°C, below project targets, the project led to improvements in the ALFABET model, improvements in cloud-based implementations of NWChem software, and a substantial dataset of calculations on medium-sized conjugated organic molecules.

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

Variational Quantum Chemistry Programs in JaqalPaq

We present example quantum chemistry programs written with JaqalPaq, a python meta-programming language used to code in Jaqal (Just Another Quantum Assembly Language). These JaqalPaq algorithms are intended to be run on the Quantum Scientific Computing Open User Testbed (QSCOUT) platform at Sandia National Laboratories. Our exemplars use the variational quantum eigensolver (VQE) quantum algorithm to compute the ground state energies of the H2, HeH+, and LiH molecules. Since the exemplars focus on how to program in JaqalPaq, the calculations of the second-quantized Hamiltonians are performed with the PySCF python package, and the mappings of the fermions to qubits are obtained from the OpenFermion python package. Using the emulator functionality of JaqalPaq, we emulate how these exemplars would be executed on an error-free QSCOUT platform and compare the emulated computation of the bond-dissociation curves for these molecules with their exact forms within the relevant basis.

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

Experimental and theoretical study of the soot-forming tendencies of furans as potential biofuels

Sustainably-produced biofuels, including furans derived from lignocellulosic biomass, are being studied as potential next-generation fuels. Biofuels have unique structures that are absent in conventional fuels and they potentially emit fewer particulates than conventional fuels because of the presence of oxygen atoms. In this work, we focus on quantification and measurement of sooting tendency. A set of furans was selected and their sooting tendencies were characterized by Yield Sooting Index (YSI), which was obtained by measuring the line-of-sight spectral radiance (LSSR) of a coflow laminar diffusion flame doped with 1000 ppm of each test fuel. The measured YSIs are lower than traditional gasoline fuels and benzenoid aromatics (e.g., YSIbenzene = 100). We also performed numerical simulations with a detailed chemical kinetic mechanism to analyze the flame chemistry of 2-methylfuran (2MF). 4→5 H-atom migration in the furan ring causes 31.0% of the total decomposition and is the dominant fuel consumption pathway leading to soot. DFT calculations via the G4 composite method were carried out to obtain activation energies (Ea) and bond dissociation energies (BDE). The results showed that the 4→5 H-atom migration in the furan ring has the second lowest Ea and subsequently forms a 1,2-diene-substituted ketone derivative as a stable species. The ring-opening products of the 4→5 H-atom migration are propyne + a linear ketene for 2-n-alkylfurans, and 1-butyne + a methyl-substituted ketene for 2-t-butylfuran. These results can explain the trends of the measured YSIs of 2-alkylfurans.

09 BIOMASS FUELS↗
DOE OSTI2020

Disruption of a key ligand-H-bond network drives dissociative properties in vamorolone for Duchenne muscular dystrophy treatment

Duchenne muscular dystrophy is a genetic disorder that shows chronic and progressive damage to skeletal and cardiac muscle leading to premature death. Antiinflammatory corticosteroids targeting the glucocorticoid receptor (GR) are the current standard of care but drive adverse side effects such as deleterious bone loss. Through subtle modification to a steroidal backbone, a recently developed drug, vamorolone, appears to preserve beneficial efficacy but with significantly reduced side effects. We use combined structural, biophysical, and biochemical approaches to show that loss of a receptor-ligand hydrogen bond drives these remarkable therapeutic effects. Moreover, vamorolone uniformly weakens coactivator associations but not corepressor associations, implicating partial agonism as the main driver of its dissociative properties. Additionally, we identify a critical and evolutionarily conserved intramolecular network connecting the ligand to the coregulator binding surface. Interruption of this allosteric network by vamorolone selectively reduces GR-driven transactivation while leaving transrepression intact. Our results establish a mechanistic understanding of how vamorolone reduces side effects, guiding the future design of partial agonists as selective GR modulators with an improved therapeutic index.

59 BASIC BIOLOGICAL SCIENCES↗