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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Measurement of $\mathrm{t\bar t}$ normalised multi-differential cross sections in pp collisions at $\sqrt s=13$ TeV, and simultaneous determination of the strong coupling strength, top quark pole mass, and parton distribution functions

Normalised multi-differential cross sections for top quark pair ($\mathrm{t\overline{t}}$) production are measured in proton-proton collisions at a centre-of-mass energy of 13 TeV using events containing two oppositely charged leptons. The analysed data were recorded with the CMS detector in 2016 and correspond to an integrated luminosity of 35.9 fb$^{-1}$. The double-differential $\mathrm{t\overline{t}}$ cross section is measured as a function of the kinematic properties of the top quark and of the $\mathrm{t\overline{t}}$ system at parton level in the full phase space. A triple-differential measurement is performed as a function of the invariant mass and rapidity of the $\mathrm{t\overline{t}}$ system and the multiplicity of additional jets at particle level. The data are compared to predictions of Monte Carlo event generators that complement next-to-leading-order (NLO) quantum chromodynamics (QCD) calculations with parton showers. Together with a fixed-order NLO QCD calculation, the triple-differential measurement is used to extract values of the strong coupling strength $\alpha_S$ and the top quark pole mass ($m_\mathrm{T}^\text{pole}$) using several sets of parton distribution functions (PDFs). Furthermore, a simultaneous fit of the PDFs, $\alpha_S$, and $m_\mathrm{T}^\text{pole}$ is performed at NLO, demonstrating that the new data have significant impact on the gluon PDF, and at the same time allow an accurate determination of $\alpha_S$ and $m_\mathrm{T}^\text{pole}$.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1995

The Sensitivity of B3LYP Atomization Energies to the Basis Set and a Comparison of the Basis Set Requirements for CCSD(T) and B3LYP

The atomization energies of the 55 G2 molecules are computed using the B3LYP approach with a variety of basis sets. The 6-311 + G(3df) basis set is found to yield superior results to those obtained using the augmented - correlation - consistent valence-polarized triple-zeta set. The atomization energy of SO2 is found to be the most sensitive to basis set and is studied in detail. Including tight d functions is found to be important for obtaining good atomization energies. The results for SO2 are compared with those obtained using the coupled-cluster singles and doubles approach including a perturbational estimate of the triple excitations.

Bauschlicher, Charles W., Jr.↗
DOE OSTI2025

Microstructure-based modeling of inner oxygen pressure in solid oxide electrolysis cells: Analysis of electrode delamination and mitigation

One major degradation mechanism during long-term operation of solid oxide electrolysis cells (SOECs) is delamination of oxygen electrodes (OEs). The driving force for the electrode delamination could be the generated high inner oxygen pressure near the electrode-electrolyte interface during operation. However, the effects of transport properties and electrode thickness on the inner oxygen partial pressure are not well understood. Here a microstructure-based electrochemical model, which includes the conduction of electrons and oxygen ions coupled with Butler-Volmer-type chemical reactions at triple-phase-boundaries (TPBs), is employed to investigate the oxygen pressure in lanthanum strontium manganate (LSM)-based SOECs. The model is applied to both two-dimensional (2D) prototype microstructures and three-dimensional (3D) realistic microstructures, and the oxygen pressure is analyzed as a function of transport properties and electrode thickness under both potentiostatic and galvanostatic operations. The simulation results suggest strategies to suppress electrode delamination. The simulation results are compared to an analytical solution, and the discrepancies are attributed to the Butler-Volmer-type kinetics included in the microstructure-based model.

25 ENERGY STORAGE↗
DOE OSTI2022

Diffusion Monte Carlo evaluation of disiloxane linearisation barrier

The disiloxane molecule is a prime example of silicate compounds containing the Si-O-Si bridge. The molecule is of significant interest within the field of quantum chemistry, owing to the difficulty in theoretically predicting its properties. Herein, the linearisation barrier of disiloxane is investigated using a fixed-node diffusion Monte Carlo (FNDMC) approach, which is one of the most reliable ab initio methods in accounting for the electronic correlation. Calculations utilizing the density functional theory (DFT) and the coupled cluster method with single and double substitutions, including noniterative triples (CCSD(T)) are carried out alongside FNDMC for comparison. It is concluded that FNDMC successfully predicts the disiloxane linearisation barrier and does not depend on the completeness of the basis-set as much as DFT or CCSD(T), thus establishing its suitability.

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

Pitfalls in the n -mode representation of vibrational potentials

Simulations of anharmonic vibrational motion rely on computationally expedient representations of the governing potential energy surface. The n-mode representation (n-MR)—effectively a many-body expansion in the space of molecular vibrations—is a general and efficient approach that is often used for this purpose in vibrational self-consistent field (VSCF) calculations and correlated analogues thereof. In the present analysis, a lack of convergence in many VSCF calculations is shown to originate from negative and unbound potentials at truncated orders of the n-MR expansion. For cases of strong anharmonic coupling between modes, the n-MR can both dip below the true global minimum of the potential surface and lead to effective single-mode potentials in VSCF that do not correspond to bound vibrational problems, even for bound total potentials. The present analysis serves mainly as a pathology report of this issue. Furthermore, this insight into the origin of VSCF non-convergence provides a simple, albeit ad hoc, route to correct the problem by “painting in” the full representation of groups of modes that exhibit these negative potentials at little additional computational cost. Somewhat surprisingly, this approach also reasonably approximates the results of the next-higher n-MR order and identifies groups of modes with particularly strong coupling. The method is shown to identify and correct problematic triples of modes—and restore SCF convergence—in two-mode representations of challenging test systems, including the water dimer and trimer, as well as protonated tropine.

Chemistry↗
DOE OSTI2024

Microstructure-Based Modeling of Inner Oxygen Pressure in Solid Oxide Electrolysis Cells

One major degradation mechanism during long-term operation of solid oxide electrolysis cells (SOECs) is delamination of oxygen electrodes (OEs). The driving force for the electrode delamination could be the generated high inner oxygen pressure near the electrode-electrolyte interface during operation. However, the effects of transport properties and electrode thickness on the inner oxygen partial pressure are not well understood. Here, a microstructure-based electrochemical model which includes the conduction of electrons and oxygen ions coupled with Butler-Volmer-type chemical reactions at triple-phase-boundaries (TPBs), is employed to investigate the oxygen pressure in lanthanum strontium manganate (LSM)-based SOECs. The model is applied to both two-dimensional (2D) prototype microstructures and three-dimensional (3D) realistic microstructures, and the oxygen pressure is analyzed as a function of transport properties and electrode thickness under both potentiostatic and galvanostatic operations. The simulation results suggest strategies to suppress electrode delamination. The simulation results are compared to an analytical solution, and the discrepancies are attributed to the Butler-Volmer-type kinetics included in the microstructure-based model.

Xue, Fei↗
NASA NTRS1995

Characterization of the Minimum Energy Paths and Energetics for the Reaction of Vinylidene with Acetylene

The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinyl-acetylene and for a number of isomers of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinyl-acetylene.

Walch, Stephen P.↗
NASA NTRS1995

Characterization of the Minimum Energy Paths and Energetics for the reaction of Vinylidene with Acetylene

The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinylacetylene and for a number of isomers Of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinylacetylene.

Walch, Stephen P.↗
NASA NTRS2011

Highly Accurate Quartic Force Fields, Vibrational Frequencies, and Spectroscopic Constants for Cyclic and Linear C3H3(+)

High levels of theory have been used to compute quartic force fields (QFFs) for the cyclic and linear forms of the C H + molecular cation, referred to as c-C H + and I-C H +. Specifically the 33 3333 singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, CCSD(T), has been used in conjunction with extrapolation to the one-particle basis set limit and corrections for scalar relativity and core correlation have been included. The QFFs have been used to compute highly accurate fundamental vibrational frequencies and other spectroscopic constants using both vibrational 2nd-order perturbation theory and variational methods to solve the nuclear Schroedinger equation. Agreement between our best computed fundamental vibrational frequencies and recent infrared photodissociation experiments is reasonable for most bands, but there are a few exceptions. Possible sources for the discrepancies are discussed. We determine the energy difference between the cyclic and linear forms of C H +, 33 obtaining 27.9 kcal/mol at 0 K, which should be the most reliable available. It is expected that the fundamental vibrational frequencies and spectroscopic constants presented here for c-C H + 33 and I-C H + are the most reliable available for the free gas-phase species and it is hoped that 33 these will be useful in the assignment of future high-resolution laboratory experiments or astronomical observations.

Huang, Xinchuan↗
NASA NTRS2019

Highly Accurate Quartic Force Field and Rovibrational Spectroscopic Constants for the Azirinyl Cation (c-C2NH2+) and Its Isomers

Azirinyl cation is an aromatic cyclic molecule that is isoelectronic with cyclopropenylidene, c-C3H2, and c-C3H3+. Cyclopropenylidene has been shown to be ubiquitous, existing in many different astrophysical environments. Given the similar chemistry between C and N, and the relative abundances between C and N in astrophysical environments, it is expected that there should be aromatic ringed molecules that incorporate N in the ring, but as yet, no such molecule has been identified. To address this issue, the present study uses high levels of electronic structure theory to compute a highly accurate quartic force field (QFF) for azirinyl cation and its two lowest lying isomers, the cyanomethyl and isocyanomethyl cations. The theoretical approach uses the singles and doubles coupled-cluster method that includes a perturbative correction for connected triple excitations, CCSD(T), together with extrapolation to the one-particle basis set limit and corrections for scalar relativity and core-correlation. The QFF is then used in a second order vibrational perturbation theory analysis (VPT2) to compute the fundamental vibrational frequencies and rovibrational spectroscopic constants for all three C2NH2+ isomers. The reliability of the VPT2 vibrational frequencies is tested by comparison to vibrational configuration interaction (VCI) calculations and excellent agreement is found between the two approaches. Fundamental vibrational frequencies and rovibrational spectroscopic constants for all singly substituted 13C, 15N, and D isotopologues are also reported. It is expected that the highly accurate spectroscopic data reported herein will be useful in the identification of these cations in high resolution experimental or astronomical observations.

Partha P Bera↗
DOE OSTI2023

Stabilization of collinear ferromagnetic order in Ir-doped triple-layer ruthenate Sr 4 Ru 3 O 10

The triple-layer Sr 4 Ru 3 O 10 is a spin-orbit-coupled metal featuring an intriguing combination of ferromagnetic and metamagnetic states. Here we report a comprehensive study of single-crystal neutron and x-ray diffraction on Sr 4 Ru 3 O 10 with 4% iridium doping. The system crystallizes in an orthorhombic Bbem structure in which two triple layers are related by a base centering symmetry operation within one unit cell. The 4% Ir doping at the Ru site sensitively alters the structural balance between the RuO 6 layers, as such the two outer-layer octahedra rotate 6.7° about the c axis, while the central-layer one rotates in the opposite direction by 11.0°. The increased lattice distortion stabilizes a collinear ferromagnetic state with magnetic moments fully aligned along the c axis. The emerging perpendicular magnetic anisotropy naturally increases the critical field for the inplane metamagnetic transition to 4.5 Tesla. All results highlight the critical linkage between the magnetic properties and underlying lattice through orbital degrees of freedom, as well as the enhanced spin orbit coupling due to heavier 5d ions. Our observation provides a viable route for an efficient manipulation of the magnetic states with functionalities.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Approaching hydro-equivalent ignition in laser direct-drive via target design optimization using novel statistical modeling

Laser direct-drive offers significant advantages in terms of target simplicity, improved energy coupling, and large fuel masses over indirect drive. However, performance degradations from hydrodynamic and laser-plasma instabilities seeded and driven by the direct illumination pose limitations on the parameter space available for achieving ignition. In this paper, new design improvements are identified to forge a path forward for a hydro-equivalent ignition demonstration. The first is related to a new formulation of the statistical model (SM) used to accurately predict target performance directly from input parameters such as laser pulse shape and target specifications. This new SM formulation provides direct guidance on target dimensions and laser beam-to-target radius to achieve the highest fusion yield on the OMEGA laser. The second improvement comes from cooling the deuterium–tritium (DT) ice layer below the triple point right before shot time leading to lower DT vapor densities and higher convergence. Guided by these design improvements, a Bayesian optimization algorithm was used to design an implosion that is predicted to closely approach a Lawson triple product that hydrodynamically scales to ignition if equivalent laser–target coupling is achieved at laser energies typical of the National Ignition Facility.

Deuterium↗
NASA NTRS2024

Deducing Land-Atmosphere Coupling Regimes from SMAP Soil Moisture

In recent years, there has been a growing recognition of the significance of Land-Atmosphere (L-A) interactions and feedback mechanisms in understanding and predicting Earth’s water and energy cycles. Soil moisture plays a critical role in mediating the strength of L-A interactions and is important for understanding the complex and governing processes across this interface. This study aims to identify the significance of soil moisture in identifying L-A coupling strength within the Convective Triggering Potential (CTP) and Humidity Index (HI) framework. To address this, a consistent and reliable dataset of atmospheric profiles is created by merging CTP and HI using Triple Collocation (TC) with three reanalysis datasets. The merged CTP and HI product demonstrates enhanced performance globally as compared to the individual datasets when validated with radiosonde and satellite observations. This merged product of CTP and HI is then used to compare the L-A coupling strength based on Soil Moisture Active Passive Level 3 (SMAPL3) and SMAP Level 4 (SMAPL4) over two decades (2003-2022) where L-A coupling strength is defined as the persistence probability within the dry and wet coupling regimes. Results indicate that the persistency-based coupling strength is related to the ability of soil moisture to predict future atmospheric humidity and dry vs. wet coupling state. The coupling strength in SMAPL4 is consistently stronger than in SMAPL3 and is likely due to its reliance on a land surface model and reduced susceptibility to random noise. The difference in coupling strength based on the same CTP-HI underscores the importance of soil moisture data in estimating coupling strength within the CTP-HI framework. These findings lay the groundwork for understanding the role of L-A interactions and drought evolution due to soil moisture variations, by providing insight into the quantification of coupling strength and its role in drought monitoring and forecast efforts.

Land-atmosphere coupling↗
NASA NTRS1991

Quantum mechanical calculations to chemical accuracy

The accuracy of current molecular-structure calculations is illustrated with examples of quantum mechanical solutions for chemical problems. Two approaches are considered: (1) the coupled-cluster singles and doubles (CCSD) with a perturbational estimate of the contribution of connected triple excitations, or CCDS(T); and (2) the multireference configuration-interaction (MRCI) approach to the correlation problem. The MRCI approach gains greater applicability by means of size-extensive modifications such as the averaged-coupled pair functional approach. The examples of solutions to chemical problems include those for C-H bond energies, the vibrational frequencies of O3, identifying the ground state of Al2 and Si2, and the Lewis-Rayleigh afterglow and the Hermann IR system of N2. Accurate molecular-wave functions can be derived from a combination of basis-set saturation studies and full configuration-interaction calculations.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1994

Theoretical Study of the First Transition Row Oxides and Sulfides

The first transition row oxides and sulfides are studied using several different levels of theory. The calculations show the bonding mechanism in the sulfides and oxides to be very similar. For the oxides, accurate experimental data allow the theoretical methods to be calibrated. The same level of theory is used to study the sulfides where there is far less experimental information. For ScO through MnO and CuO the coupled cluster singles and doubles technique including a perturbational estimate of the unliked triple excitations [CCSD(T)] yields spectroscopic constants ((tau)e, (omega)e, and D0) in good agreement with experiment. The triple excitations are found to be very important in achieving this accuracy. For FeO to NiO, the single determinant self-consistent-field (SCF) approach yields pi orbitals that are localized on the metal or oxygen. This appears to cause problems for the single reference techniques; this is discussed in detail for NiO. The complete-active-space SCF/internally contracted averaged coupled pair functional approach (CASSCF/ICACPF) works well for FeO to NiO. The calculation of accurate dipole moments is found to be very difficult.

Bauschlicher, Charles W., Jt.↗
DOE OSTI2025

Comparison of Ce( iv )/Th( iv )-alkynyl complexes and observation of a trans -influence ligand series for Ce( iv )

Organometallic cerium(iv) complexes have been challenging to isolate and characterize due to the strongly oxidizing nature of the cerium(iv) cation. Herein, we report two cerium(iv) alkynyl complexes, [Ce(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-CeTMS) and [Ce(TriNOx)(C[triple bond, length as m-dash]C-Ph)] (1-CePh) (TriNOx3- = tris(2-tert-butylhydroxylaminato)benzylamine), that include terminal alkyne moieties. The isostructural thorium analogue [Th(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-ThTMS) was also synthesized and compared with 1-CeTMS in bond distance, 13C-NMR spectra, vibrational spectra and electronic structure. The Ce-C bond distances were 2.501(3) Å for 1-CePh and 2.513(5) Å for 1-CeTMS on the shorter end of the few reported CeIV-C single bonds (2.478(3)-2.705(2) Å), possibly indicating significant Ce 5d- and 4f-orbital involvement. 13C-NMR spectroscopy was also consistent with Ce-C covalency, with significantly deshielded resonances ranging from 185-213 ppm. Such 13C-NMR shifts demonstrate a strong influence from spin-orbit coupling (SOC) effects, corroborated by computational studies. Raman analysis showed ν C[triple bond, length as m-dash]C stretching frequencies of 2000 cm-1 (1-CeTMS) and 2052 cm-1 (1-CePh), indicating the cerium(iv)-alkynyl interaction, compared to the parent HC[triple bond, length as m-dash]CPh (IR = 2105 cm-1 and Raman = 2104 cm-1). L3-edge X-ray absorption measurements revealed a predominant Ce(iv) electronic configuration, and magnetic measurements revealed temperature-independent paramagnetism. Electrochemical studies similarly revealed the electron donating ability of the alkynyl ligands, stronger than either fluoride or imido ligands for the Ce(iv)(TriNOx)-framework, with a cerium(iv/iii) reduction potential of E pc = -1.58 to -1.66 V vs. Fc/Fc+. Evidence for a trans-influence has been observed by evaluating a series including previously reported [CeIV(TriNOx)X]+/0 complexes with axial ligands X = THF, I-, Br-, Cl-, F-, -C[triple bond, length as m-dash]C-Ph, -C[triple bond, length as m-dash]C-SiMe3, -NH(3,5-(CF3)2-Ar), -OSiPh3, -N(M(L))(3,5-(CF3)2-Ar) [M(L) = Li(TMEDA), K(DME)2 or Cs(2,2,2-crypt)]. These data stand in contrast with previous reports of an inverse trans-influence at cerium(iv) and point to differences in involvement of cerium 4f- versus 5d-orbitals in the electronic structures of the complexes.

Yang, Qiaomu↗
DOE OSTI2025

Historical and Future Windstorms in the Northeastern United States

Large-scale windstorms represent an important atmospheric hazard in the Northeastern US (NE) and are associated with substantial socioeconomic losses. Regional simulations performed with the Weather Research and Forecasting (WRF) model using lateral boundary conditions from three Earth System Models (ESMs: Geophysical Fluid Dynamics Laboratory (GFDL), Hadley Centre Global Environment Model (HadGEM) and Max Planck Institute (MPI)) are used to quantify possible future changes in windstorm characteristics and/or changes in the parent cyclone types responsible for windstorms. WRF nested within MPI ESM best represents important aspects of historical windstorms and the cyclone types responsible for generating windstorms compared with a reference simulation performed with the ERA-Interim reanalysis for the historical climate. The spatial scale and frequency of the largest windstorms in each simulation defined using the greatest extent of exceedance of local 99.9th percentile wind speeds (U > U999) plus 50-year return period wind speeds (U50,RP) do not exhibit secular trends. Projections of extreme wind speeds and windstorm intensity/frequency/geolocation and dominant parent cyclone type associated with windstorms vary markedly across the simulations. Only the MPI nested simulations indicate statistically significant differences in windstorm spatial scale, frequency and intensity over the NE in the future and historical periods. This model chain, which also exhibits the highest fidelity in the historical climate, yields evidence of future increases in 99.9th percentile 10 m height wind speeds, the frequency of simultaneous U > U999 over a substantial fraction (5–25%) of the NE and the frequency of maximum wind speeds above 22.5 ms−1. These geophysical changes, coupled with a projected doubling of population, leads to a projected tripling of a socioeconomic loss index, and hence risk to human systems, from future windstorms.

Pryor, Sara C. (ORCID:0000000348473440)↗
NASA NTRS1992

The calculation of the vibrational frequencies of CuCO+, NiCO and CuCH3

The vibrational frequencies of CuCO+, NiCO, and CuCH3 are computed at both the self-consistent-field (SCF) and coupled-cluster singles and doubles, with a perturbational estimate of the triples (CCSD(T)), levels of theory. Overall the SCF frequencies are in qualitative agreement with the CCSD(T) results. The calculations show that the frequencies for the electrostatically bound CuCO+ are quite different from the datively bound NiCO. The CCSD(T) calculations support a previous suggestion that the C-H stretches in CuCH3 have been misassigned.

Sodupe, M.↗