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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Quantum theory of atoms in molecules/charge-charge flux-dipole flux models for fundamental vibrational intensity changes on H-bond formation of water and hydrogen fluoride

The Quantum Theory of Atoms In Molecules/Charge-Charge Flux-Dipole Flux (QTAIM/CCFDF) model has been used to investigate the electronic structure variations associated with intensity changes on dimerization for the vibrations of the water and hydrogen fluoride dimers as well as in the water-hydrogen fluoride complex. QCISD/cc-pVTZ wave functions applied in the QTAIM/CCFDF model accurately provide the fundamental band intensities of water and its dimer predicting symmetric and antisymmetric stretching intensity increases for the donor unit of 159 and 47 km mol{sup −1} on H-bond formation compared with the experimental values of 141 and 53 km mol{sup −1}. The symmetric stretching of the proton donor water in the dimer has intensity contributions parallel and perpendicular to its C{sub 2v} axis. The largest calculated increase of 107 km mol{sup −1} is perpendicular to this axis and owes to equilibrium atomic charge displacements on vibration. Charge flux decreases occurring parallel and perpendicular to this axis result in 42 and 40 km mol{sup −1} total intensity increases for the symmetric and antisymmetric stretches, respectively. These decreases in charge flux result in intensity enhancements because of the interaction contributions to the intensities between charge flux and the other quantities. Even though dipole flux contributions are much smaller than the charge and charge flux ones in both monomer and dimer water they are important for calculating the total intensity values for their stretching vibrations since the charge-charge flux interaction term cancels the charge and charge flux contributions. The QTAIM/CCFDF hydrogen-bonded stretching intensity strengthening of 321 km mol{sup −1} on HF dimerization and 592 km mol{sup −1} on HF:H{sub 2}O complexation can essentially be explained by charge, charge flux and their interaction cross term. Atomic contributions to the intensities are also calculated. The bridge hydrogen atomic contributions alone explain 145, 237, and 574 km mol{sup −1} of the H-bond stretching intensity enhancements for the water and HF dimers and their heterodimer compared with total increments of 149, 321, and 592 km mol{sup −1}, respectively.

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

High-energy X-ray detection by hafnium-doped organic-inorganic hybrid scintillators prepared by sol-gel method

With the aim of enhancing the efficiency with which plastic scintillators detect high-energy X-rays, hafnium-doped organic-inorganic hybrid scintillators were fabricated via a sol-gel method. Transmission electron microscopy of sampled material reveals the presence of Hf{sub x}Si{sub 1−x}O{sub 2} nanoparticles, dispersed in a polymer matrix that constitutes the active material of the X-ray detector. With Hf{sub x}Si{sub 1−x}O{sub 2} nanoparticles incorporated in the polymer matrix, the absorption edge and the luminescence wavelength is shifted, which we attribute to Mie scattering. The detection efficiency for 67.4-keV X-rays in a 0.6-mm-thick piece of this material is two times better than the same thickness of a commercial plastic scintillator-NE142.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Vertically aligned crystalline silicon nanowires with controlled diameters for energy conversion applications: Experimental and theoretical insights

Vertically orientated single crystalline silicon nanowire (SiNW) arrays with controlled diameters are fabricated via a metal-assisted chemical etching method. The diameter of the fabricated nanowires is controlled by simply varying the etching time in HF/H{sub 2}O{sub 2} electrolytes. The fabricated SiNWs have diameters ranging from 117 to 650 nm and lengths from 8 to 18 μm. The optical measurements showed a significant difference in the reflectance/absorption of the SiNWs with different diameters, where the reflectance increases with increasing the diameter of the SiNWs. The SiNWs showed significant photoluminescence (PL) emission spectra with peaks lying between 380 and 670 nm. The PL intensity increases as the diameter increases and shows red shift for peaks at ∼670 nm. The increase or decrease of reflectivity is coincident with PL intensity at wavelength ∼660 nm. The x-ray diffraction patterns confirm the high crystallinity of the fabricated SiNWs. In addition, the Raman spectra showed a shift in the first order transverse band toward lower frequencies compared to that usually seen for c-Si. Finite difference time domain simulations have been performed to confirm the effect of change of diameter on the optical properties of the nanowires. The simulation results showed good agreement with the experimental results for the SiNWs of different diameters.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Effects of strain on effective work function for Ni/HfO{sub 2} interfaces

The effective work functions for Ni/HfO{sub 2} interfaces under two strain modes (uniaxial and triaxial strains) were studied by using first-principles methods based on density functional theory. The calculated results indicate that the effective work functions are strongly affected by the type of interface and the strain states (tensile and compressive strains). For the both above strain states, the changed value of the effective work functions linearly increases with increasing strain. Moreover, it is observed that for a certain strain, the variation of the effective work function for triaxial strain state is almost larger than that for uniaxial strain state. Finally, the electrons gas model, the interface dipole, and screening role of HfO{sub 2} were used to analyze and explain the strain and interface effects in metal-oxide interfaces. The evident difference between the effective work functions of Ni-Hf and Ni-O interfaces is found to be attributed to different metallic bondings and ionic bondings via the analysis of the charge density distributions. Our work strongly suggests that controlling the strain and interface structure is a promising way for modulating the work function of Ni/HfO{sub 2} interfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Determination of the density of the defect states in Hf{sub 0.5}Zr{sub 0.5}O{sub 2} high-k film Deposited by using rf-magnetron sputtering technique

A memory structure Pt/Al{sub 2}O{sub 3}/Hf{sub 0.5}Zr{sub 0.5}O{sub 2}/Al{sub 2}O{sub 3}/p-Si was fabricated by using atomic layer deposition and rf-magnetron sputtering techniques, and its microstructure has been investigated by using the high resolution transmission electron microscopy (HRTEM). By measuring the applied gate voltage dependence of the capacitance for the memory structure, the planar density of the trapped charges in Hf{sub 0.5}Zr{sub 0.5}O{sub 2} high-k film was estimated as 6.63 × 10{sup 12} cm{sup −2}, indicating a body defect density of larger than 2.21 × 10{sup 19} cm{sup −3}. It is observed that the post-annealing in N{sub 2} can reduces the defect density in Hf{sub 0.5}Zr{sub 0.5}O{sub 2} film, which was ascribed to the occupancy of oxygen vacancies by nitrogen atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2014

K isomers as probes of nuclear structure

K isomers are studied in Pu and Cm isotopes, and also in Hf and W nuclei. Many high-K states, several of which are isomeric, are identified. Lifetime measurements spanning the ns-s range have been performed, and decay paths of isomers established. Rotational bands built on high-K states are also identified in many cases. Isomer decays are considerably hindered in many instances, both in the A≈180 and 250 regions indicating that K is an approximately conserved quantum number. High-K states become the favored excitation mode at high spins in the A≈180 region. The energies of the 2-quasiparticle high-K states in Cm isotopes suggest the presence of a deformed subshell gap at N=152.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

In-situ spectroscopic ellipsometry and structural study of HfO{sub 2} thin films deposited by radio frequency magnetron sputtering

We have investigated the reduction of unwanted interfacial SiO{sub 2} layer at HfO{sub 2}/Si interface brought about by the deposition of thin Hf metal buffer layer on Si substrate prior to the deposition of HfO{sub 2} thin films for possible direct contact between HfO{sub 2} thin film and Si substrate, necessary for the future generation devices based on high-κ HfO{sub 2} gate dielectrics. Reactive rf magnetron sputtering system along with the attached in-situ spectroscopic ellipsometry (SE) was used to predeposit Hf metal buffer layer as well as to grow HfO{sub 2} thin films and also to undertake the in-situ characterization of the high-κ HfO{sub 2} thin films deposited on n-type 〈100〉 crystalline silicon substrate. The formation of the unwanted interfacial SiO{sub 2} layer and its reduction due to the predeposited Hf metal buffer layer as well as the depth profiling and also structure of HfO{sub 2} thin films were investigated by in-situ SE, Fourier Transform Infrared spectroscopy, and Grazing Incidence X-ray Diffraction. The study demonstrates that the predeposited Hf metal buffer layer has played a crucial role in eliminating the formation of unwanted interfacial layer and that the deposited high-κ HfO{sub 2} thin films are crystalline although they were deposited at room temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Communication: Hartree-Fock description of excited states of H{sub 2}

Hartree-Fock (HF) theory is most often applied to study the electronic ground states of molecular systems. However, with the advent of numerical techniques for locating higher solutions of the self-consistent field equations, it is now possible to examine the extent to which such mean-field solutions are useful approximations to electronic excited states. In this Communication, we use the maximum overlap method to locate 11 low-energy solutions of the HF equation for the H{sub 2} molecule and we find that, with only one exception, these yield surprisingly accurate models for the low-lying excited states of this molecule. This finding suggests that the HF solutions could be useful first-order approximations for correlated excited state wavefunctions.

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

Analytic calculations of hyper-Raman spectra from density functional theory hyperpolarizability gradients

We present the first analytic calculations of the geometrical gradients of the first hyperpolarizability tensors at the density-functional theory (DFT) level. We use the analytically calculated hyperpolarizability gradients to explore the importance of electron correlation effects, as described by DFT, on hyper-Raman spectra. In particular, we calculate the hyper-Raman spectra of the all-trans and 11-cis isomers of retinal at the Hartree-Fock (HF) and density-functional levels of theory, also allowing us to explore the sensitivity of the hyper-Raman spectra on the geometrical characteristics of these structurally related molecules. We show that the HF results, using B3LYP-calculated vibrational frequencies and force fields, reproduce the experimental data for all-trans-retinal well, and that electron correlation effects are of minor importance for the hyper-Raman intensities.

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

Mode specificity in the HF + OH → F + H{sub 2}O reaction

Full-dimensional quantum dynamics and quasi-classical trajectory calculations are reported for the title reaction on a recently constructed ab initio based global potential energy surface. Strong mode specificity was found, consistent with the prediction of the sudden vector projection model. Specifically, the HF vibration strongly promotes the reaction while the OH vibration has little effect. Rotational excitations of both reactants slightly enhance the reaction.

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

An accurate potential energy surface for the F + H{sub 2} → HF + H reaction by the coupled-cluster method

A three dimensional potential energy surface for the F + H{sub 2} → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2){sub Q}] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H{sub 2} reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface.

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

Morphology and chemical termination of HF-etched Si{sub 3}N{sub 4} surfaces

Several reports on the chemical termination of silicon nitride films after HF etching, an important process in the microelectronics industry, are inconsistent claiming N-H{sub x}, Si-H, or fluorine termination. An investigation combining infrared and x-ray photoelectron spectroscopies with atomic force and scanning electron microscopy imaging reveals that under some processing conditions, salt microcrystals are formed and stabilized on the surface, resulting from products of Si{sub 3}N{sub 4} etching. Rinsing in deionized water immediately after HF etching for at least 30 s avoids such deposition and yields a smooth surface without evidence of Si-H termination. Instead, fluorine and oxygen are found to terminate a sizeable fraction of the surface in the form of Si-F and possibly Si-OH bonds. The relatively unique fluorine termination is remarkably stable in both air and water and could lead to further chemical functionalization pathways.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Nitrogen diffusion in hafnia and the impact of nitridation on oxygen and hydrogen diffusion: A first-principles study

Using first-principles simulations, we have computed incorporation energies and diffusion barriers of ammonia, the nitrogen molecule and atomic nitrogen in monoclinic hafnia (m-HfO{sub 2}). Our calculations show that ammonia is likely to dissociate into an NH{sub 2} molecular unit, whereas the nitrogen molecule remains as a molecule either in the interstitial space or at an oxygen lattice site. The lowest energy pathway for the diffusion of atomic nitrogen interstitials consists of the hopping of the nitrogen interstitial between neighboring three-coordinated lattice oxygen atoms that share a single Hf atom, and the barrier for such hops is determined by a switching mechanism. The substitutional nitrogen atom shows a preference for diffusion through the doubly positive oxygen vacancy-mediated mechanism. Furthermore, we have investigated the impact of nitrogen atoms on the diffusion barriers of oxygen and hydrogen interstitials in m-HfO{sub 2}. Our results show that nitrogen incorporation has a significant impact on the barriers for oxygen and hydrogen diffusion: nitrogen atoms attract oxygen and hydrogen interstitials diffusing in the vicinity, thereby slowing down (reducing) their diffusion (diffusion length)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Efficient calculation of integrals in mixed ramp-Gaussian basis sets

Algorithms for the efficient calculation of two-electron integrals in the newly developed mixed ramp-Gaussian basis sets are presented, alongside a Fortran90 implementation of these algorithms, RAMPITUP. These new basis sets have significant potential to (1) give some speed-up (estimated at up to 20% for large molecules in fully optimised code) to general-purpose Hartree-Fock (HF) and density functional theory quantum chemistry calculations, replacing all-Gaussian basis sets, and (2) give very large speed-ups for calculations of core-dependent properties, such as electron density at the nucleus, NMR parameters, relativistic corrections, and total energies, replacing the current use of Slater basis functions or very large specialised all-Gaussian basis sets for these purposes. This initial implementation already demonstrates roughly 10% speed-ups in HF/R-31G calculations compared to HF/6-31G calculations for large linear molecules, demonstrating the promise of this methodology, particularly for the second application. As well as the reduction in the total primitive number in R-31G compared to 6-31G, this timing advantage can be attributed to the significant reduction in the number of mathematically complex intermediate integrals after modelling each ramp-Gaussian basis-function-pair as a sum of ramps on a single atomic centre.

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

Surface treatment effect on Si (111) substrate for carbon deposition using DC unbalanced magnetron sputtering

In this work, we studied the effect of HF treatment in silicon (111) substrate surface for depositing thin layer carbon. We performed the deposition of carbon by using DC Unbalanced Magnetron Sputtering with carbon pallet (5% Fe) as target. From SEM characterization results it can be concluded that the carbon layer on HF treated substrate is more uniform than on substrate without treated. Carbon deposition rate is higher as confirmed by AFM results if the silicon substrate is treated by HF solution. EDAX characterization results tell that silicon (111) substrate with HF treatment have more carbon fraction than substrate without treatment. These results confirmed that HF treatment on silicon Si (111) substrates could enhance the carbon deposition by using DC sputtering. Afterward, the carbon atomic arrangement on silicon (111) surface is studied by performing thermal annealing process to 900 °C. From Raman spectroscopy results, thin film carbon is not changing until 600 °C thermal budged. But, when temperature increase to 900 °C, thin film carbon is starting to diffuse to silicon (111) substrates.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Mode specificity in bond selective reactions F + HOD → HF + OD and DF + OH

The influence of vibrational excitations in the partially deuterated water (HOD) reactant on its bond selective reactions with F is investigated using a full-dimensional quantum wave packet method on an accurate global potential energy surface. Despite the decidedly early barrier of the F + H{sub 2}O reaction, reactant vibrational excitation in each local stretching mode of HOD is found to significantly enhance the reaction which breaks the excited bond. In the mean time, excitation of the HOD bending mode also enhances the reaction, but with much lower efficacy and weaker bond selectivity. Except for low collision energies, all vibrational modes are more effective in promoting the bond selective reactions than the translational energy. These results are compared with the predictions of the recently proposed sudden vector projection model.

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

A method for the formation of Pt metal nanoparticle arrays using nanosecond pulsed laser dewetting

Nanosecond pulsed laser dewetting of Pt thin films, deposited on a dimpled Ta (DT) surface, has been studied here in order to form ordered Pt nanoparticle (NP) arrays. The DT substrate was fabricated via a simple electrochemical anodization process in a highly concentrated H{sub 2}SO{sub 4} and HF solution. Pt thin films (3–5 nm) were sputter coated on DT and then dewetted under vacuum to generate NPs using a 355 nm laser radiation (6–9 ns, 10 Hz). The threshold laser fluence to fully dewet a 3.5 nm thick Pt film was determined to be 300 mJ/cm{sup 2}. Our experiments have shown that shorter irradiation times (≤60 s) produce smaller nanoparticles with more uniform sizes, while longer times (>60 s) give large nanoparticles with wider size distributions. The optimum laser irradiation time of 1 s (10 pulses) has led to the formation of highly ordered Pt nanoparticle arrays with an average nanoparticle size of 26 ± 3 nm with no substrate deformation. At the optimum condition of 1 s and 500 mJ/cm{sup 2}, as many as 85% of the dewetted NPs were found neatly in the well-defined dimples. This work has demonstrated that pulsed laser dewetting of Pt thin films on a pre-patterned dimpled substrate is an efficient and powerful technique to produce highly ordered Pt nanoparticle arrays. This method can thus be used to produce arrays of other high-melting-point metal nanoparticles for a range of applications, including electrocatalysis, functionalized nanomaterials, and analytical purposes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Communication: Creation of molecular vibrational motions via the rotation-vibration coupling

Building on recent advances in the rotational excitation of molecules, we show how the effect of rotation-vibration coupling can be switched on in a controlled manner and how this coupling unfolds in real time after a pure rotational excitation. We present the first examination of the vibrational motions which can be induced via the rotation-vibration coupling after a pulsed rotational excitation. A time-dependent quantum wave packet calculation for the HF molecule shows how a slow (compared to the vibrational period) rotational excitation leads to a smooth increase in the average bond length whereas a fast rotational excitation leads to a non-stationary vibrational motion. As a result, under field-free postpulse conditions, either a stretched stationary bond or a vibrating bond can be created due to the coupling between the rotational and vibrational degrees of freedom. The latter corresponds to a laser-induced breakdown of the adiabatic approximation for rotation-vibration coupling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗