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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Ab initio calculation of a global potential, vibrational energies, and wave functions for HCN/HNC, and a simulation of the (A-tilde)-(X-tilde) emission spectrum

A potential energy surface for the HCN/HNC system which is a fit to extensive, high-quality ab initio, coupled-cluster calculations is presented. All HCN and HNC states with energies below the energy of the first delocalized state are reported and characterized. Vibrational transition energies are compared with all available experimental data on HCN and HNC, including high CH-overtone states up to 23,063/cm. A simulation of the (A-tilde)-(X-tilde) stimulated emission pumping (SEP) spectrum is also reported, and the results are compared to experiment. Franck-Condon factors are reported for odd bending states of HCN, with one quantum of vibrational angular momentum, in order to compare with the recent assignment by Jonas et al. (1992), on the basis of axis-switching arguments of a number of previously unassigned states in the SEP spectrum.

Bowman, Joel M.↗
NASA NTRS1994

Symmetry breaking in O4(+): An application of the Brueckner coupled-cluster method

A recent calculation of the antisymmetric stretch frequency for the rectangular structure of quartet O4(+) using the singles and doubles quadratic configuration interaction method with a perturbational estimate of connected triple excitations (QCISD(T)) method gave a value of 3710 cm(exp -1). This anomalous frequency is shown to be a consequence of symmetry breaking effects, which occur even though the QCISD(T) solution derived from a delocalized SCF reference function lies energetically well below the two localized (symmetry-broken) solutions at the equilibrium geometry. The symmetry breaking is almost eliminated at the CCSD level of theory, but the small remaining symmetry breaking effects are magnified at the CCSD(T) level of theory so that the antisymmetric stretch frequency is still significantly in error. The use of the Brueckner coupled cluster method, however, leads to a symmetrical solution which is free of symmetry breaking effects, with an antisymmetric stretch frequency of 1322 cm(exp -1), in good agreement with our earlier calculations using the complete active space self consistent field/complete active space state interaction (CASSCF/CASSI) method.

Barnes, Leslie A.↗
NASA NTRS1992

Evaluation of a doubly-swept blade tip for rotorcraft noise reduction

A computational study was performed for a doubly-swept rotor blade tip to determine its benefit for high-speed impulsive (HSI) and blade-vortex interaction (BVI) noise. This design consists of aft and forward sweep. For the HSI-noise computations, unsteady Euler calculations were performed for several variations to a rotor blade geometry. A doubly-swept planform was predicted to increase the delocalizing Mach number to 0.94 (representative of a 200+ kt helicopter). For the BVI-noise problem, it had been hypothesized that the doubly-swept blade tip, by producing a leading-edge vortex, would reduce the tip-vortex effect on BVI noise. A procedure was used in which the tip vortex velocity profile computed by a Navier-Stokes solver was used to compute the inflow associated with BVI. This inflow was used by a Euler solver to compute the unsteady pressures for an acoustic analysis. The results of this study were inconclusive due to the difficulty in accurately predicting the viscous tip vortex downstream of the blade. Also, for the condition studied, no leading-edge vortex formed at the tip.

Wake, Brian E.↗
NASA NTRS1995

Proton affinity determinations and proton-bound dimer structure indications in C2 to C15, (alpha),(omega)-alkyldiamines

The 'kinetic method' was used to determine the proton affinity (PA) of a,coalkyldiamines from collision induced dissociation (CID) studies of protonated heterodimers. These PA values were consistently lower than those reported in the proton affinity scale. The apparent discrepancy was rationalized in terms of differences in the conformation of the protonated diamine monomers. The minimum energy species, formed by equilibrium proton transfer processes, have a cyclic conformation and the ion charge is shared by both amino-groups which are bridged by the proton. On the other hand, the species formed through dissociation of protonated dimers have a linear structure and the charge is localized on one of the amino-groups. Thus, the difference in the PA values obtained by both methods is a measure of the additional stability acquired by the protonated diamines through cyclization and charge delocalization. The major collision dissociation pathway of the protonated diamine monomers involved elimination of an ammonia moiety. Other reactions observed included loss of the second amino-group and several other bond cleavages. CID of the protonated dimers involved primarily formation of a protonated monomer through cleavage of the weaker hydrogen bond and subsequently loss of ammonia at higher collision energies. As observed from the CID studies, doubly charged ions were also formed from the diamines under conditions of the electrospray ionization.

Karpas, Z.↗
NASA NTRS1995

Boson localization and universality in YBa2Cu(3-x)M(x)O(7-delta)

We consider a two component mixture of charged fermions on neutralizing background with all sign combinations and arbitrarily small mass ratios. In the two impurity limit for the heavier component we show that the pair forms a bound state for all charge combinations. In the lowest order approximation we derive a closed form expression Veff(r) for the binding potential which has short-range repulsion followed by attraction. In the classical limit, when the mass of embedded particles is large m2 much greater than m, we can calculate from Veff(r) also the cohesive energy E and the bond length R of a metallic crystal such as lithium. The lowest order result is R = 3.1 A, E = -0.9 eV, not entirely different from the experimental result for lithium metal. The same interaction for two holes on a parabolic band with m2 greater than m gives the quantum mechanical bound state which one may interpret as a boson or local pair in the case of high-Te and heavy fermion superconductors. We also show that for compounds of the type YBa2Cu(3 - x)M(x)O(7 - delta) one can understand most of the experimental results for the superconducting and normal states with a single temperature dependent boson breaking function f(T) for each impurity content x governing the decay of bosons into pairing fermions. In the normal state f(T) turns out to be a linear, universal function, independent of the impurity content I and the oxygen content delta. We predict with universality a depression in Tc(x) with slight down bending in agreement with experiment. As a natural consequence of the model the bosons become localized slightly above Tc due to the Wigner crystallization, enhanced with lattice local field minima. The holes remain delocalized with a linearly increasing concentration in the normal state, thus explaining the rising Hall density. The boson localization temperature T(sub BL) shows up as a minimum in the Hall density R(sub ab)(exp -1). We also give explanation for very recently observed scaling of temperature dependent Hall effect in La(2 - x)Sr(x)CuO4.

Kallio, A.↗
NASA NTRS1996

The Calculation of Accurate Harmonic Frequencies of Large Molecules: The Polycyclic Aromatic Hydrocarbons, a Case Study

The vibrational frequencies and infrared intensities of naphthalene neutral and cation are studied at the self-consistent-field (SCF), second-order Moller-Plesset (MP2), and density functional theory (DFT) levels using a variety of one-particle basis sets. Very accurate frequencies can be obtained at the DFT level in conjunction with large basis sets if they are scaled with two factors, one for the C-H stretches and a second for all other modes. We also find remarkably good agreement at the B3LYP/4-31G level using only one scale factor. Unlike the neutral PAHs where all methods do reasonably well for the intensities, only the DFT results are accurate for the PAH cations. The failure of the SCF and MP2 methods is caused by symmetry breaking and an inability to describe charge delocalization. We present several interesting cases of symmetry breaking in this study. An assessment is made as to whether an ensemble of PAH neutrals or cations could account for the unidentified infrared bands observed in many astronomical sources.

Bauschlicher, Charles W., Jr.↗
NASA NTRS2002

Nanostructured Composites: Effective Mechanical Property Determination of Nanotube Bundles

Carbon nanotubes naturally tend to form crystals in the form of hexagonally packed bundles or ropes that should exhibit a transversely isotropic constitutive behavior. Although the intratube axial stiffness is on the order of 1 TPa due to a strong network of delocalized bonds, the intertube cohesive strength is orders of magnitude less controlled by weak, nonbonding van der Waals interactions. An accurate determination of the effective mechanical properties of nanotube bundles is important to assess potential structural applications such as reinforcement in future composite material systems. A direct method for calculating effective material constants is developed in the present study. The Lennard-Jones potential is used to model the nonbonding cohesive forces. A complete set of transverse moduli are obtained and compared with existing data.

Saether, E.↗
NASA NTRS1997

Supersonic Quadrupole Noise Theory for High-Speed Helicopter Rotors

High-speed helicopter rotor impulsive noise prediction is an important problem of aeroacoustics. The deterministic quadrupoles have been shown to contribute significantly to high-speed impulsive (HSI) noise of rotors, particularly when the phenomenon of delocalization occurs. At high rotor-tip speeds, some of the quadrupole sources lie outside the sonic circle and move at supersonic speed. Brentner has given a formulation suitable for efficient prediction of quadrupole noise inside the sonic circle. In this paper, we give a simple formulation based on the acoustic analogy that is valid for both subsonic and supersonic quadrupole noise prediction. Like the formulation of Brentner, the model is exact for an observer in the far field and in the rotor plane and is approximate elsewhere. We give the full analytic derivation of this formulation in the paper. We present the method of implementation on a computer for supersonic quadrupoles using marching cubes for constructing the influence surface (Sigma surface) of an observer space- time variable (x; t). We then present several examples of noise prediction for both subsonic and supersonic quadrupoles. It is shown that in the case of transonic flow over rotor blades, the inclusion of the supersonic quadrupoles improves the prediction of the acoustic pressure signature. We show the equivalence of the new formulation to that of Brentner for subsonic quadrupoles. It is shown that the regions of high quadrupole source strength are primarily produced by the shock surface and the flow over the leading edge of the rotor. The primary role of the supersonic quadrupoles is to increase the width of a strong acoustic signal.

Farassat, F.↗
NASA NTRS2008

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Reddy, V. Prakash↗
NASA NTRS2016

Nanocomposites from Stable Dispersions of Carbon Nanotubes in Polymeric Matrices Using Dispersion Interaction

Stable dispersions of carbon nanotubes (CNTs) in polymeric matrices include CNTs dispersed in a host polymer or copolymer whose monomers have delocalized electron orbitals, so that a dispersion interaction results between the host polymer or copolymer and the CNTs dispersed therein. Nanocomposite products, which are presented in bulk, or when fabricated as a film, fiber, foam, coating, adhesive, paste, or molding, are prepared by standard means from the present stable dispersions of CNTs in polymeric matrices, employing dispersion interactions, as presented hereinabove.

Wise, Kristopher Eric↗
NASA NTRS2020

Dual Anion-Cation Crosslinked Poly(ionic liquid) Composite Membranes for Enhanced CO2 Separation

Herein, we propose a strategy of developing novel dual anionic-cationic crosslinked poly(IL)-IL composite membranes via a photopolymerization method for enhanced CO2 separations. These are the first examples of dually photopolymerized anionic-cationic poly(IL)-IL composite systems, in which the backbones of poly(IL)s feature both pendant anions and cations without any mobile counterions unlike poly(IL) reported so far in the literature. A new type of dual photopolymerizable anionic-cationic IL (DIL) monomer having methacrylate functional group tethered with highly delocalized sulfonimide anion (–SO2–N(-)–SO2–C7H7) and a vinylimidazolium counterion ([C4(vim)](+)) was successfully synthesized and photopolymerized with four distinct amounts of free IL with a structurally analogous cation ([C4(mim)][Tf2N]) and 20 wt% PEGDA crosslinker, offering novel composite matrices. Further, the structure-property relationships as well as gas separation behaviors of the four newly developed dual anioniccationic poly(IL)-IL composite membranes were extensively characterized by FT-IR, DSC, and XRD. All of the newly developed dual anionic-cationic poly(IL)-IL composite membranes displayed outstanding permselectivites for CO2/CH4, CO2/N2, and CO2/H2 gas pairs together with reasonable CO2 permeabilities. As a result, all the dual anionic-cationic poly(IL)-IL composite membranes outperformed the common poly(IL)-IL systems in the upper bound limit plots with best CO2 permeability of 40 barrer and CO2/CH4 permselectivity of 85. This study may pave a new platform to explore countless potential poly(IL)-IL composites for selective separation of CO2 from flue gas, natural gas, and syngas streams.

Irshad Kammakakam↗
DOE OSTI2020

Dynamic clay microstructures emerge via ion complexation waves

Clays control carbon, water and nutrient transport in the lithosphere, promote cloud formation5 and lubricate fault slip through interactions among hydrated mineral interfaces. Clay mineral properties are difficult to model because their structures are disordered, curved and dynamic. Consequently, interactions at the clay mineral-aqueous interface have been approximated using electric double layer models based on single crystals of mica and atomistic simulations. We discover that waves of complexation dipoles at dynamically curving interfaces create an emergent long-range force that drives exfoliation and restacking over time- and length-scales that are not captured in existing models. Curvature delocalizes electrostatic interactions in ways that fundamentally differ from planar surfaces, altering the ratio of ions bound to the convex and concave sides of a layer. Multiple-scattering reconstruction of low-dose energy-filtered cryo electron tomography enabled direct imaging of ion complexes and electrolyte distributions at hydrated and curved mineral interfaces with {\aa}ngstrom resolution over micron length scales. Layers exfoliate and restack abruptly and repeatedly over timescales that depend strongly on the counterion identity, demonstrating that the strong coupling between elastic, electrostatic and hydration forces in clays promote collective reorganization previously thought to be a feature only of active matter.

Whittaker, Michael L↗
DOE OSTI2024

Impacts of Neodymium Complexation on Radiolysis of Tetramethyl Diglycolamide (TMDGA) in Aqueous Solutions

Hydrophilic diglycolamides (DGA) ligands have been explored for use as stripping agents in various lanthanide and actinide partitioning processes.1 The separation of lanthanide fission products and transplutonic actinides can serve multifaceted advantages, in that the separation of neutron poisoning rare earth element (REE) fission products from the minor actinides in used nuclear fuel (UNF) can be mutually beneficial to the fundamental research behind REE separations and UNF separations. Considerable efforts have been devoted to understanding the radiation chemistry of hydrophilic DGAs. However, recent studies with lipophilic DGAs have shown that metal ion complexation can promote significant changes in their radiolytic susceptibility.2,3 These effects have been attributed to various parameters, including delocalization of electron density, the presence of radiolytically more susceptible counter ions, and steric hindrance. As such, it is pivotal for these complexation effects to be more thoroughly probed to establish mechanistic knowledge for their effects on hydrophilic DGA molecules. Here we present a time-resolved electron pulse and accumulated gamma dose irradiation study on neodymium ion complexes of tetramethyl diglycolamide (TMDGA) under aqueous solution conditions. References (1) Rostaing, C.; Poinssot, C.; Warin, D.; Baron, P.; Lorrain, B. Development and Validation of the EXAm Separation Process for Single Am Recycling. Procedia Chem. 2012, 7, 367–373. https://doi.org/doi: 10.1016/j.proche.2012.10.057. (2) Horne, G. P.; Conrad, J. K.; McLachlan, J. R.; Rotermund, B. M.; Cook, A. R.; Celis-Barros, C.; Mezyk, S. P. Impact of Lanthanide Complexation and Temperature on the Chemical Reactivity of N,N,N’,N’-Tetraoctyl Diglycolamide (TODGA) with the Dodecane Radical Cation. Phys. Chem. Chem. Phys. 2023, Under Review. (3) Kimberlin, A.; Saint-Louis, G.; Guillaumont, D.; Camès, B.; Guilbaud, P.; Berthon, L. Effect of Metal Complexation on Diglycolamide Radiolysis: A Comparison between Ex Situ Gamma and in Situ Alpha Irradiation. Phys. Chem. Chem. Phys. PCCP 2022, 24 (16), 9213–9228. https://doi.org/10.1039/d1cp05731f.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

Microstructure‐Informed Analysis Framework for Lattice Structures: Guiding Topology‐Material Synergy in Titanium Alloys

In this work we discuss a microstructure‐informed analysis framework for lattice structures that maps the material's microstructural response to guide topology selection and mechanical performance optimization. By coupling geometrical topology with intrinsic material behavior, we demonstrate how anisotropic microstructural response can inform the design of optimized lattice structures. To illustrate this concept, we focus on two distinct classes of titanium alloys: Ti5553 (Ti‐5Al‐5Mo‐5V‐3Cr wt%), which exhibits a predominantly ‐phase microstructure, and Ti64 (Ti‐6Al‐4V wt%), which features a dual‐phase structure. These alloys exhibit markedly different mechanical responses under multiaxial loading in “fully dense” solid form. The strut‐level stress analysis of these alloys reveals how specific microstructural characteristics can guide the selection of appropriate lattice topologies. Two representative lattice configurations, one stretching‐dominated and one bending‐dominated, are evaluated under identical loading conditions to explore how microstructure‐driven design can lead to topology choices that are better suited to accommodate shear or other critical local stress states, thereby enhancing mechanical performance. A strut‐level mechanics‐based analysis is performed to evaluate shear stress distribution and highlight the role of topology‐microstructure synergy and compatibility in determining overall lattice behavior. The findings emphasize the importance of designing structures that are both load‐aware and microstructure‐responsive, enabling more effective material utilization in advanced engineering applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Machine learning for accuracy in density functional approximations

Machine learning techniques have found their way into computational chemistry as indispensable tools to accelerate atomistic simulations and materials design. In addition, machine learning approaches hold the potential to boost the predictive power of computationally efficient electronic structure methods, such as density functional theory, to chemical accuracy and to correct for fundamental errors in density functional approaches. In this paper, recent progress in applying machine learning to improve the accuracy of density functional and related approximations is reviewed. Promises and challenges in devising machine learning models transferable between different chemistries and materials classes are discussed with the help of examples applying promising models to systems far outside their training sets.

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

Coherence in Chemistry: Foundations and Frontiers

Coherence refers to correlations in waves. Because matter has a wave-particle nature, it is unsurprising that coherence has deep connections with the most contemporary issues in chemistry research (e.g., energy harvesting, femtosecond spectroscopy, molecular qubits and more). But what does the word "coherence" really mean in the context of molecules and other quantum systems? We provide a review of key concepts, definitions, and methodologies, surrounding coherence phenomena in chemistry, and we describe how the terms "coherence" and "quantum coherence" refer to many different phenomena in chemistry. Moreover, we show how these notions are related to the concept of an interference pattern. Coherence phenomena are indeed complex, and ambiguous definitions may spawn confusion. By describing the many definitions and contexts for coherence in the molecular sciences, we aim to enhance understanding and communication in this broad and active area of chemistry.

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

Nonempirical Prediction of the Length-Dependent Ionization Potential in Molecular Chains

The ionization potential of molecular chains is well-known to be a tunable nanoscale property that exhibits clear quantum confinement effects. State-of-the-art methods can accurately predict the ionization potential in the small molecule limit and in the solid-state limit, but for intermediate, nanosized systems prediction of the evolution of the electronic structure between the two limits is more difficult. Recently, optimal tuning of range-separated hybrid functionals has emerged as a highly accurate method for predicting ionization potentials. This was first achieved for molecules using the ionization potential theorem (IPT) and more recently extended to solid-state systems, based on an ansatz that generalizes the IPT to the removal of charge from a localized Wannier function. Here, we study one-dimensional molecular chains of increasing size, from the monomer limit to the infinite polymer limit using this approach. By comparing our results with other localization-based methods and where available with experiment, we demonstrate that Wannier-localization-based optimal tuning is highly accurate in predicting ionization potentials for any chain length, including the nanoscale regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗