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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 1,801 records · Page 100
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Effect of the V{sub As}V{sub Ga} complex defect doping on properties of the semi-insulating GaAs

The different position V{sub As}V{sub Ga} cluster defect doping in semi-insulating (SI) GaAs has been studied by first-principles calculation based on hybrid density functional theory. Our calculated results show that EL6 level is formed due to the V{sub As}V{sub Ga} complex defect, which is very close to the experimental result. It provides the explanation of the absorption of laser with the wavelength beyond in semi-insulating GaAs. The formation energy of V{sub As}V{sub Ga} complex defect is found to decrease from surface to interior gradually. The conduction band minima and valence band maxima of GaAs (001) surface with the V{sub As}V{sub Ga} complex defect are all located at Γ point, and some defect levels are produced in the forbidden band. In contrast, the conduction band minima and valence band maxima of GaAs with the interior V{sub As}V{sub Ga} complex defect are not located at the same k-point, so it might involve the change of momentum in the electron transition process. The research will help strengthen the understanding of photoelectronic properties and effectively guide the preparation of the SI-GaAs materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Formation of a dinuclear copper(II) complex through the cleavage of C N bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-(3-(pyridin-2-yl)-pyrazolato) and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the C{sub benzoyl} N bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the (3-(pyridin-2-yl)-pyrazolato)(3-(pyridin-2-yl)-1H-pyrazole)Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ε = 116 dm{sup 3} mol{sup −1} cm{sup −1}) supports the presence of Cu(II) centres.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Synthesis and characterisation of platinum (II) salphen complex and its interaction with calf thymus DNA

A platinum (II) salphen complex was synthesised by condensation reaction of 2,4-dihydroxylbenzaldehyde and o-phenylenediamine with potassium tetrachloroplatinate to obtain N,N′-Bis-4-(hydroxysalicylidene)-phenylenediamine-platinum (II). The structure of the complex was confirmed by {sup 1}H and {sup 13}C NMR spectroscopy, FTIR spectroscopy, CHN elemental analyses and ESI-MS spectrometry. The platinum (II) salphen complex with four donor atoms N{sub 2}O{sub 2} from its salphen ligand coordinated to platinum (II) metal centre were determined. The binding mode and interaction of this complex with calf thymus DNA was determined by UV/Vis DNA titration and emission titration. The intercalation between the DNA bases by π-π stacking due to its square planar geometry and aromatic rings structures was proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

H{sub 2}—AgCl: A spectroscopic study of a dihydrogen complex

H{sub 2}—AgCl has been observed on a Fourier transform microwave spectrometer equipped with laser ablation source and determined to be a dihydrogen complex. Transitions up to J = 3–2 have been measured and analyzed for four isotopologues of the complex containing ortho and para H{sub 2}. The ortho and para spin states have been included in one fit, a deviation from the typical H{sub 2} complex. Rotational constants B and C, centrifugal distortion constants Δ{sub J} and Δ{sub JK}, nuclear electric quadrupole coupling constants χ{sub aa}, χ{sub bb}, and χ{sub cc} for {sup 35}Cl and {sup 37}Cl have been fit for both spin states while nuclear spin-nuclear spin constants D{sub aa}, D{sub bb}, and D{sub cc}, and nuclear spin-rotation constant C{sub aa} have been reported for the ortho spin state. Quantum chemical calculations predict a strong bonding interaction and the strength of the complex has been related to reported χ{sub aa} and Δ{sub J} values amongst a host of comparable species, including the AgCl monomer itself. Bond lengths have been determined for Ag—Cl, Ag—H{sub 2} center-of-mass, and H—H and are reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Mathematical model and software complex for computer simulation of field emission electron sources

The software complex developed in MATLAB allows modelling of function of diode and triode structures based on field emission electron sources with complex sub-micron geometry, their volt-ampere characteristics, calculating distribution of electric field for educational and research needs. The goal of this paper is describing the physical-mathematical model, calculation methods and algorithms the software complex is based on, demonstrating the principles of its function and showing results of its work. For getting to know the complex, a demo version with graphical user interface is presented.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Intramolecular competition between n-pair and π-pair hydrogen bonding: Microwave spectrum and internal dynamics of the pyridine–acetylene hydrogen-bonded complex

a-type rotational spectra of the hydrogen-bonded complex formed from pyridine and acetylene are reported. Rotational and {sup 14}N hyperfine constants indicate that the complex is planar with an acetylenic hydrogen directed toward the nitrogen. However, unlike the complexes of pyridine with HCl and HBr, the acetylene moiety in HCCH—NC{sub 5}H{sub 5} does not lie along the symmetry axis of the nitrogen lone pair, but rather, forms an average angle of 46° with the C{sub 2} axis of the pyridine. The a-type spectra of HCCH—NC{sub 5}H{sub 5} and DCCD—NC{sub 5}H{sub 5} are doubled, suggesting the existence of a low lying pair of tunneling states. This doubling persists in the spectra of HCCD—NC{sub 5}H{sub 5}, DCCH—NC{sub 5}H{sub 5}, indicating that the underlying motion does not involve interchange of the two hydrogens of the acetylene. Single {sup 13}C substitution in either the ortho- or meta-position of the pyridine eliminates the doubling and gives rise to separate sets of spectra that are well predicted by a bent geometry with the {sup 13}C on either the same side (“inner”) or the opposite side (“outer”) as the acetylene. High level ab initio calculations are presented which indicate a binding energy of 1.2 kcal/mol and a potential energy barrier of 44 cm{sup −1} in the C{sub 2v} configuration. Taken together, these results reveal a complex with a bent hydrogen bond and large amplitude rocking of the acetylene moiety. It is likely that the bent equilibrium structure arises from a competition between a weak hydrogen bond to the nitrogen (an n-pair hydrogen bond) and a secondary interaction between the ortho-hydrogens of the pyridine and the π electron density of the acetylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Character of intermolecular interaction in pyridine-argon complex: Ab initio potential energy surface, internal dynamics, and interrelations between SAPT energy components

The pyridine-Ar (PAr) van der Waals (vdW) complex is studied using a high level ab initio method. Its structure, binding energy, and intermolecular vibrational states are determined from the analytical potential energy surface constructed from interaction energy (IE) values computed at the coupled cluster level of theory with single, double, and perturbatively included triple excitations with the augmented correlation consistent polarized valence double-ζ (aug-cc-pVDZ) basis set complemented by midbond functions. The structure of the complex at its global minimum with Ar at a distance of 3.509 Å from the pyridine plane and shifted by 0.218 Å from the center of mass towards nitrogen agrees well with the corresponding equilibrium structure derived previously from the rotational spectrum of PAr. The PAr binding energy D{sub e} of 392 cm{sup −1} is close to that of 387 cm{sup −1} calculated earlier at the same ab initio level for the prototypical benzene-Ar (BAr) complex. However, under an extension of the basis set, D{sub e} for PAr becomes slightly lower than D{sub e} for BAr. The ab initio vdW vibrational energy levels allow us to estimate the reliability of the methods for the determination of the vdW fundamentals from the rotational spectra. To disclose the character of the intermolecular interaction in PAr, the symmetry-adapted perturbation theory (SAPT) is employed for the analysis of different physical contributions to IE. It is found that SAPT components of IE can be approximately expressed in the binding region by only two of them: the exchange repulsion and dispersion energy. The total induction effect is negligible. The interrelations between various SAPT components found for PAr are fulfilled for a few other complexes involving aromatic molecules and Ar or Ne, which indicates that they are valid for all rare gas (Rg) atoms and aromatics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Point-in-convex polygon and point-in-convex polyhedron algorithms with O(1) complexity using space subdivision

There are many space subdivision and space partitioning techniques used in many algorithms to speed up computations. They mostly rely on orthogonal space subdivision, resp. using hierarchical data structures, e.g. BSP trees, quadtrees, octrees, kd-trees, bounding volume hierarchies etc. However in some applications a non-orthogonal space subdivision can offer new ways for actual speed up. In the case of convex polygon in E{sup 2} a simple Point-in-Polygon test is of the O(N) complexity and the optimal algorithm is of O(log N) computational complexity. In the E{sup 3} case, the complexity is O(N) even for the convex polyhedron as no ordering is defined. New Point-in-Convex Polygon and Point-in-Convex Polyhedron algorithms are presented based on space subdivision in the preprocessing stage resulting to O(1) run-time complexity. The presented approach is simple to implement. Due to the principle of duality, dual problems, e.g. line-convex polygon, line clipping, can be solved in a similarly.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2016

Structural complexity of quantum networks

Quantum network is a set of nodes connected with channels, through which the nodes communicate photons and classical information. Classical structural complexity of a quantum network may be defined through its physical structure, i.e. mutual position of nodes and channels connecting them. We show here that the classical structural complexity of a quantum network does not restrict the structural complexity of entanglement graphs, which may be created in the quantum network with local operations and classical communication. We show, in particular, that 1D quantum network can simulate both simple entanglement graphs such as lattices and random graphs and complex small-world graphs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Vibrational analysis of methyl cation—Rare gas atom complexes: CH + 3 —Rg (Rg = He, Ne, Ar, Kr)

The vibrational spectra of simple CH + 3 —Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory, which is a generalization of standard vibrational self-consistent field theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-order coupled-cluster terms, e.g., quadruple excitations, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH + 3 —He has been investigated on the basis of semiclassical instanton theory. Furthermore these calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates with that of the hydronium cation, H 3 O + , suggest that tunneling effects for vibrationally excited states should be very small.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Two single-reference approaches to singlet biradicaloid problems: Complex, restricted orbitals and approximate spin-projection combined with regularized orbital-optimized Møller-Plesset perturbation theory

We present a comprehensive study of two single-reference approaches to singlet biradicaloids. These two approaches are based on the recently developed regularized orbital-optimized Møller-Plesset method (κ-OOMP2). The first approach is to combine Yamaguchi's approximate projection (AP) scheme and κ-OOMP2 with unrestricted (U) orbitals (κ-UOOMP2). By capturing only essential symmetry breaking, κ-UOOMP2 can serve as a suitable basis for AP. The second approach is κ-OOMP2 with complex, restricted (cR) orbitals (κ-cROOMP2). Although its applicability is more limited due to the comparative rarity of cR solutions, κ-cROOMP2 offers a simple framework for describing singlet biradicaloids with complex polarization while removing artificial spatial symmetry breaking. We compare the scope of these two methods with numerical studies. We show that AP+κ-UOOMP2 and κ-cROOMP2 can perform similarly well in the TS12 set, a dataset that includes 12 data points for triplet-singlet gaps of several atoms and diatomic molecules with a triplet ground state. This was also found to be true for the barrier height of a reaction involving attack on a cysteine ion by a singlet oxygen molecule. However, we also demonstrate that in highly symmetric systems like C 30 (D 5h ), κ-cROOMP2 is more suitable as it conserves spatial symmetry. Finally, we present an organic biradicaloid that does not have a κ-cROOMP2 solution in which case only AP+κ-UOOMP2 is applicable. Here, we recommend κ-cROOMP2 whenever complex polarization is essential and AP+κ-UOOMP2 for biradicaloids without essential complex polarization but with essential spin-polarization.

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

Exploring the Light-induced Dynamics in Solvated Metallogrid Complexes with Femtosecond Pulses Across the Electromagnetic Spectrum

Oligonuclear complexes of d 4 -d 7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to their mononuclear congeners is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2x2] iron(II) metallogrid complex are characterized by combining transient optical, infrared absorption and X-ray emission spectroscopic measurements on the femtosecond timescale. The analysis is supported by DFT calculations. The photocycle can be described in terms of intra-site transitions, where the Fe II in the low-spin (LS) state are independently photoexcited. The Franck-Condon state decays via the formation of a vibrationally-hot high-spin (HS) state that displays coherent behavior within a few picoseconds and thermalizes within tens of picosecond to yield a metastable HS state living for several hundreds of nanoseconds. Additionally, systematic comparison with the closely related mononuclear complex [Fe(terpy) 2 ] 2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. Finally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.

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

Spin-orbit coupling in molecular complexes beyond van der Waals regime: Key factors for further splitting of 2 P 3/2 ground state

Here, we report a joint spectroscopic and theoretical study probing spin-orbit coupling (SOC) in a variety of molecular complexes between an iodine atom and a ligand (L) with L ranging from Ar, HF to formic/acetic acids, and glycine/N-methylated glycine derivatives. Cryogenic photoelectron spectroscopy of L·I - (L=HCOOH, CH 3 COOH) reveals three distinct peaks, identified as three SOC states, denoted as X(1/2), A(3/2), and B(l/2) for the corresponding neutrals. The X and A separation ΔE XA is measured to be 0.10 eV for both, whereas the X and B gap ΔE XB is 0.98 and 0.97 eV for formic and acetic acid, respectively. These new ΔE XA values are compared with the previously reported values for the molecular complexes L·I· with L=Ar, HF, glycine, and A-methylated glycines. All together these complexes encompass a diversity of intermolecular interactions, from van der Waals to weak and strong hydrogen bonding. While the ΔE XB remains similar, the ΔE XA is shown to be extremely sensitive to the type of ligands and interactions, spanning from 5 meV to 150 meV. High-level relativistic quantum calculations including explicit SOC formulism nicely reproduce all experimental SOC splitting. A direct correlation between the magnitude of ΔE XA with the intermolecular interaction strength or bond distance of the neutral complexes—the stronger interaction (shorter bond length), the greater splitting, is established.

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

Amplified spontaneous emission from europium-based molecular complexes coupled to photonic crystal cavities

Rare-earth ion-based materials bear many remarkable optical properties that render them highly appealing for lighting and quantum-related applications. However, their small oscillator strength and weak emission often pose limitations. Here, in this work, we synthesize and couple Eu(III)-based molecular complexes to nanobeam photonic crystals supporting air modes. A reasonable spatial overlap between the molecular complexes and cavity modes leads to an average spontaneous emission coupling efficiency of 0.19. Our pump power-dependent photoluminescence measurements evidence amplified spontaneous emission from the molecular complexes with an amplification threshold as low as 4.4 W/cm 2 , likely benefiting from the efficient coupling. These findings suggest that integrating rare-earth ion-based molecular complexes with photonic structures could be a viable approach for regulating their emission characteristics for particular applications.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Structure of a trimeric nucleoporin complex reveals alternate oligomerization states

The heptameric Nup84 complex constitutes an evolutionarily conserved building block of the nuclear pore complex. Here, we present the crystal structure of the heterotrimeric Sec13 {center_dot} Nup145C {center_dot} Nup84 complex, the centerpiece of the heptamer, at 3.2-{angstrom} resolution. Nup84 forms a U-shaped {alpha}-helical solenoid domain, topologically similar to two other members of the heptamer, Nup145C and Nup85. The interaction between Nup84 and Nup145C is mediated via a hydrophobic interface located in the kink regions of the two solenoids that is reinforced by additional interactions of two long Nup84 loops. The Nup84 binding site partially overlaps with the homo-dimerization interface of Nup145C, suggesting competing binding events. Fitting of the elongated Z-shaped heterotrimer into electron microscopy (EM) envelopes of the heptamer indicates that structural changes occur at the Nup145C {center_dot} Nup84 interface. Docking the crystal structures of all heptamer components into the EM envelope constitutes a major advance toward the completion of the structural characterization of the Nup84 complex.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Structure and function of the polymerase core of TRAMP, a RNA surveillance complex

The Trf4p/Air2p/Mtr4p polyadenylation (TRAMP) complex recognizes aberrant RNAs in Saccharomyces cerevisiae and targets them for degradation. A TRAMP subcomplex consisting of a noncanonical poly(A) RNA polymerase in the Pol {beta} superfamily of nucleotidyl transferases, Trf4p, and a zinc knuckle protein, Air2p, mediates initial substrate recognition. Trf4p and related eukaryotic poly(A) and poly(U) polymerases differ from other characterized enzymes in the Pol {beta} superfamily both in sequence and in the lack of recognizable nucleic acid binding motifs. Here we report, at 2.7-{angstrom} resolution, the structure of Trf4p in complex with a fragment of Air2p comprising two zinc knuckle motifs. Trf4p consists of a catalytic and central domain similar in fold to those of other noncanonical Pol {beta} RNA polymerases, and the two zinc knuckle motifs of Air2p interact with the Trf4p central domain. The interaction surface on Trf4p is highly conserved across eukaryotes, providing evidence that the Trf4p/Air2p complex is conserved in higher eukaryotes as well as in yeast and that the TRAMP complex may also function in RNA surveillance in higher eukaryotes. We show that Air2p, and in particular sequences encompassing a zinc knuckle motif near its N terminus, modulate Trf4p activity, and we present data supporting a role for this zinc knuckle in RNA binding. Finally, we show that the RNA 3{prime} end plays a role in substrate recognition.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2011

Mercury reduction and complexation by natural organic matter

Mercuric Hg(II) species form complexes with natural dissolved organic matter (DOM) such as humic acid (HA), and this binding is known to affect the chemical and biological transformation and cycling of mercury in aquatic environments. Dissolved elemental mercury, Hg(0), is also widely observed in sediments and water. However, reactions between Hg(0) and DOM have rarely been studied in anoxic environments. Here, under anoxic dark conditions we show strong interactions between reduced HA and Hg(0) through thiol-ligand induced oxidative complexation with an estimated binding capacity of about 3.5 umol Hg(0)/g HA and a partitioning coefficient greater than 10^6 mL/g. We further demonstrate that Hg(II) can be effectively reduced to Hg(0) in the presence of as little as 0.2 mg/L reduced HA, whereas production of purgeable Hg(0) is inhibited by complexation as HA concentration increases. This dual role played by DOM in the reduction and complexation of mercury is likely widespread in anoxic sediments and water and can be expected to significantly influence the mercury species transformations and biological uptake that leads to the formation of toxic methylmercury.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2015

The TWD40-2 protein and the AP2 complex cooperate in the clathrin-mediated endocytosis of cellulose synthase to regulate cellulose biosynthesis

Significance Our study advances the understanding of how plants make cellulose, a critical constituent of the plant cell wall and the most abundant organic polymer in the terrestrial biosphere. Cellulose is synthesized at the plasma membrane by cellulose synthase (CESA) complexes. Here we highlight the importance of regulated CESA endocytosis in cellulose biosynthesis in Arabidopsis . Furthermore, we show that the TWD40-2 protein, a putative member of the TPLATE complex, functions in clathrin-mediated endocytosis (CME) in ways that are both distinct from and cooperative with the functionally conserved CME adaptor protein 2 (AP2) complex. Because the TPLATE complex of plants is not conserved in animals, our characterization of TWD40-2 offers the opportunity to provide insight into the evolution of eukaryotic trafficking machinery.

59 BASIC BIOLOGICAL SCIENCES↗

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