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At least 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
NASA NTRS1986

Two contrasting metamorphosed ultramafic-mafic complexes from greenstone belts, the northern Kaapvaal Craton and their significance in Archaen tectonics

The character of Archaean ultramafic-mafic complexes can, given their prominance in greenstone belts, provide critical clues to help deduce the tectonic setting of these belts. Here are described two contrasting, metamorphosed, ultramafic-mafic complexes, the first a partially serpentinized dunitic body with associated chromite from Lemoenfontein, one of several peridotitic bodies occurring as discrete lenses and pods in granulite facies gneisses of the northern Kaapvaal craton. The second, the Rooiwater complex is a major layered igneous body, now metamorphosed in the amphibolite facies, but without pervasive deformation, which crops out in the northern Murchison greenstone belt. The Lemoenfontein chromites and associated ultramafic rocks are lithologically and chemically similar to their Phanerozoic equivalents of ophiolitic origin, interpreted as obducted oceanic crust. The Lemoenfontein complex is a remnant of Archaean oceanic material. In contrast, the Rooiwater complex is, despite the lack of exposed intrusive contacts, similar to layered igneous complexes such as Ushushwana or Bushveld. These complexes are intrusive in continental environments. It is concluded that contrasting ultramafic-mafic complexes represent a heterogeneity in greenstone belts with either oceanic or continental environments involved.

Smit, C. A.↗
NASA NTRS1986

The largest molecular cloud complexes in the first galactic quadrant

The Columbia CO survey of the first Galactic quadrant was used to determine the locations and physical properties of the largest molecular complexes in the inner Galaxy. Within the range of the survey (l = 12-60 deg), 26 complexes were detected with masses greater than 5 x 10 to the 5th solar masses, and roughly several hundred such complexes are deduced to exist throughout the Galaxy within the solar circle. These complexes are the parent objects of much of the Population I in the Galaxy. Distances to most of the complexes were determined kinematically, the distance ambiguity being resolved with the aid of associated H II regions, OB associations, masers, and other early Population I objects. The largest complexes are good tracers of spiral structure, the Sagittarius arm in particular being delineated with unprecedented clarity. A total of 17 large complexes are distributed rather uniformly along a 15 kpc stretch of the arm with a spacing comparable to that of the strings of regularly spaced H Ii regions observed in external galaxies. Power-law relations exist between the line widths and sizes of the complexes and between their densities and sizes. The forms of these relations are in good agreement with those found previously and are extended by roughly an order of magnitude in cloud mass.

Dame, T. M.↗
NASA NTRS1996

Recrystallized Impact Glasses of the Onaping Formation and the Sudbury Igneous Complex, Sudbury Structure, Ontario, Canada

The origin of the Sudbury Structure and of the associated heterolithic breccias of the Onaping Formation and the Sudbury Igneous Complex have been controversial. While an impact origin of the structure has gained wide acceptance over the last 15 years, the origin of the recrystallized Onaping Formation glasses and of the igneous complex is still being debated. Recently the interpretation of the breccias of the Onaping Formation as suevitic fall-back impact breccias has been challenged. The igneous complex is interpreted either as a differentiated impact melt sheet or as a combination of an upper impact melt represented by the granophyre, and a lower, impact-triggered magmatic body consisting of the norite-sublayer formations. The Onaping Formation contains glasses as fluidal and nonfluidal fragments of various shapes and sizes. They are recrystallized, and our research indicates that they are petrographically heterogeneous and span a wide range of chemical compositions. These characteristics are not known from glasses of volcanic deposits. This suggests an origin by shock vitrification, an interpretation consistent with their association with numerous and varied country rock clasts that exhibit microscopic shock metamorphic features. The recrystallized glass fragments represent individual solid-state and liquid-state vitrified rocks or relatively small melt pods. The basal member lies beneath the Gray and Black members of the Onaping Formation and, where not metamorphic, has an igneous matrix. Igneous-textured melt bodies occur in the upper two members and above the Basal Member. A comparison of the chemical compositions of recrystallized glasses and of the matrices of the Basal Member and the melt bodies with the components and the bulk composition of the igneous complex is inconclusive as to the origin of the igneous complex. Basal Member matrix and Melt Bodies, on average, are chemically similar to the granophyre of the Sudbury Igneous Complex, suggesting that they are genetically related. Our chemical results allow interpretation of the entire igneous complex as a differentiated impact melt. However, they are also consistent with the granophyre alone being the impact melt and the nofite and quartz gabbro beneath it representing an impact-triggered magmatic body. This interpretation is preferred, as it is consistent with a number of field observations. A re-evaluation and extension of structural field studies and of geochemical data, as well as a systematic study of the contact relationships of the various igneous phases of the igneous complex, are needed to establish a Sudbury impact model consistent with all data and observations

Dressler, B. O.↗
NASA NTRS2010

Complexity Analysis of Traffic in Corridors-in-the-Sky

The corridors-in-the-sky concept imitates the highway system in ground transportation. The benefit expected from a corridor relies on its capability of handling high density traffic with negligible controller workload, the acceptance of extra fuel or distance, and the complexity reduction in underlying sectors. This work evaluates a selected corridor from these perspectives through simulations. To examine traffic inside the corridor, a corridor traffic simulation tool that can resolve conflicts is developed using C language. Prescribed conflict resolution maneuvers mimic corridor users behaviors and conflict resolution counts measure complexity. Different lane options and operational policies are proposed to examine their impacts on complexity. Fuel consumption is calculated and compared for corridor traffic. On the other hand, to investigate the complexity of non-corridor traffic in underlying sectors, the existing Airspace Concept Evaluation System tool is utilized along with the Automated Airspace Concept tool. The number of conflict resolutions is examined and treated as the complexity measurement. The results show heavy traffic can be managed with low complexity for a historical traffic schedule simulated with appropriate operational policies and lane options. For instance, with 608 flights and peak aircraft count of 100, only 84 actions need to be taken in a 24-hour period to resolve the conflicts for an 8-lane corridor. Compared with the fuel consumptions with great circle trajectories, the simulation of corridor traffic shows that the total extra fuel for corridor flights is 26,373 gallons, or 2.76%, which is 0.38% less than flying filed flight plans. Without taking climb and descent portions of corridor traffic, the complexity of underlying sectors is reduced by 17.71%. However the climb and descent portions will eliminate the reduction and the overall complexity of sectors is actually increased by 9.14%.

Xue, Min↗
NASA NTRS2014

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

humic acid↗
NASA NTRSDate not supplied

Applying the System Complexity Metric (SCM)

A fundamental cause of difficulty in larger engineering projects is their inherent complexity. An impression of complexity occurs if a system is simply difficult to understand, so that there is no obvious mental model that correctly predicts its behavior. Higher complexity is usually associated with higher cost and higher failure rate. Complexity is indicated by a system having more and diverse components, multiple interactions and feedback loops, transients and dynamic behavior, and often the emergence of unanticipated failure modes. Identifying and removing these signs of complexity should reduce complexity and improve performance. Here we limit complexity measurement to the number of components and their interactions. A System Complexity Metric (SCM) is defined as equal to the sum of the number of parts in a system, N, plus the sum of the one-way interconnections between them, I. SCM = N + I. The SCM is easily determined by direct inspection of system block diagrams. Previous work found that life support system cost was directly proportional to SCM and that failure rate increased faster than SCM squared. SCM can be used to compare systems or to guide their redesign to reduce cost and failure rate. Carbon dioxide removal systems will be analyzed using SCM, cost, and failure rate.

Harry W Jones↗
NASA NTRS2021

Vegetation structural complexity and biodiversity in the Great Smoky Mountains

Vegetation structural complexity and biodiversity tend to be positively correlated, but understanding of this relationship is limited in part by structural metrics tending to quantify only horizontal or vertical variation, and that do not reflect internal structure. We developed new metrics for quantifying internal vegetation structural complexity using terrestrial LiDAR scanning and applied them to 12 NEON forest plots across an elevational gradient in Great Smoky Mountains National Park, USA. We asked (1) How do our newly developed structure metrics compare to traditional metrics? (2) How does forest structure vary with elevation in a high-biodiversity, high topographic complexity region? (3) How do forest structural metrics vary in the strength of their relationships with vascular plant biodiversity? Our new measures of canopy density (Depth) and structural complexity (σDepth), and their canopy height-normalized counterparts, were sensitive to structural variations and effectively summarized horizontal and vertical dimensions of structural complexity. Forest structure varied widely across plots spanning the elevational range of GRSM, with taller, more structurally complex forests at lower elevation. Vascular plant biodiversity was negatively correlated with elevation and more strongly positively correlated with vegetation structure variables. The strong correlations we observed between canopy structural complexity and biodiversity suggest that structural complexity metrics could be used to assay plant biodiversity over large areas in concert with airborne and spaceborne platforms.

Jonathan A. Walter↗
DOE OSTI2014

Complex matrix multiplication operations with data pre-conditioning in a high performance computing architecture

Mechanisms for performing a complex matrix multiplication operation are provided. A vector load operation is performed to load a first vector operand of the complex matrix multiplication operation to a first target vector register. The first vector operand comprises a real and imaginary part of a first complex vector value. A complex load and splat operation is performed to load a second complex vector value of a second vector operand and replicate the second complex vector value within a second target vector register. The second complex vector value has a real and imaginary part. A cross multiply add operation is performed on elements of the first target vector register and elements of the second target vector register to generate a partial product of the complex matrix multiplication operation. The partial product is accumulated with other partial products and a resulting accumulated partial product is stored in a result vector register.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Binary Complex Neural Network Acceleration on FPGA

Being able to learn from complex data with phase information is imperative for many signal processing applications. Today’s real-valued deep neural networks (DNNs) have shown efficiency in latent information analysis but fall short when applied to the complex domain. Deep complex networks (DCN) , in contrast, can learn from complex data, but have high computational costs; therefore, they cannot satisfy the instant decision making requirements of many deployable systems dealing with short observations or short signal bursts. Recent, Binarized Complex Neural Network (BCNN), which integrates DCNs with binarized neural networks (BNN), shows great potential in classifying complex data in real-time. In this paper, we propose a structural pruning based accelerator of BCNN, which is able to provide more than 5000 frames/s inference throughput on edge devices. The high performance comes from both the algorithm and hardware sides. On the algorithm side, we conduct structural pruning to the original BCNN models and obtain 20 × pruning rates with negligible accuracy loss; on the hardware side, we propose a novel 2D convolution operation accelerator for the binary complex neural network. Experimental results show that the proposed design works with over 90% utilization and is able to achieve the inference throughput of 5882 frames/s and 4938 frames/s for complex NIN-Net and ResNet-18 using CIFAR-10 dataset and Alveo U280 Board.

Peng, Hongwu↗
DOE OSTI2013

Alternative Endpoints and Approaches for the Remediation of Contaminated Groundwater at Complex Sites - 13426

The goal of United States (U.S.) Department of Energy's (DOE)'s environmental remediation programs is to restore groundwater to beneficial use, similar to many other Federal and state environmental cleanup programs. Based on past experience, groundwater remediation to pre-contamination conditions (i.e., drinking water standards or non-detectable concentrations) can be successfully achieved at many sites. At a subset of the most complex sites, however, complete restoration is not likely achievable within the next 50 to 100 years using today's technology. This presentation describes several approaches used at complex sites in the face of these technical challenges. Many complex sites adopted a long-term management approach, whereby contamination was contained within a specified area using active or passive remediation techniques. Consistent with the requirements of their respective environmental cleanup programs, several complex sites selected land use restrictions and used risk management approaches to accordingly adopt alternative cleanup goals (alternative endpoints). Several sites used long-term management designations and approaches in conjunction with the alternative endpoints. Examples include various state designations for groundwater management zones, technical impracticability (TI) waivers or greater risk waivers at Superfund sites, and the use of Monitored Natural Attenuation (MNA) or other passive long-term management approaches over long time frames. This presentation will focus on findings, statistics, and case studies from a recently-completed report for the Department of Defense's Environmental Security Technology Certification Program (ESTCP) (Project ER-0832) on alternative endpoints and approaches for groundwater remediation at complex sites under a variety of Federal and state cleanup programs. The primary objective of the project was to provide environmental managers and regulators with tools, metrics, and information needed to evaluate alternative endpoints for groundwater remediation at complex sites. A statistical analysis of Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) sites receiving TI waivers will be presented as well as case studies of other types of alternative endpoints and alternative remedial strategies that illustrate the variety of approaches used at complex sites and the technical analyses used to predict and document cost, time frame, and potential remedial effectiveness. This presentation is intended to inform DOE program managers, state regulators, practitioners and other stakeholders who are evaluating technical cleanup challenges within their own programs, and establishing programmatic approaches to evaluating and implementing long-term management approaches. Case studies provide examples of long-term management designations and strategies to manage and remediate groundwater at complex sites. At least 13 states consider some designation for groundwater containment in their corrective action policies, such as groundwater management zones, containment zones, and groundwater classification exemption areas. Long-term management designations are not a way to 'do nothing' or walk away from a site. Instead, soil and groundwater within the zone is managed to be protective of human health and the environment. Understanding when and how to adopt a long-term management approach can lead to cost savings and the more efficient use of resources across DOE and at numerous other industrial and military sites across the U.S. This presentation provides context for assessing the use and appropriate role of alternative endpoints and supporting long-term management designations in final remedies. (authors)

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Chemical Complexity Controls Energy Dissipation and Defect Evolution

The development of metallic alloys is arguably one of the oldest sciences, dating back at least 3,000 years. Most research and applications have been focused on alloys with comprised multiple phases with one or two dominant elements, to which the addition of alloying elements in low concentrations leads to various performance improvements and changes in radiation resistance. In sharp contrast to traditional alloys, recent success in the synthesis of single phase concentrated solid solution alloys (SP-CSAs) has opened up new frontiers in materials research. In these alloys, a random arrangement of multiple elemental species on a lattice (fcc or bcc) results in unique site-to-site lattice distortions and local disordered chemical environments. Intense radiation in nuclear fission and fusion energy power systems, nuclear waste forms, high-energy accelerators and space exploration transfers energy to the electrons and atoms that make up the material, and thereby produces defects that ultimately compromise material strength and lifetime. A grand challenge in materials research is to understand complex electronic correlations and non-equilibrium atomic interactions, and how such intrinsic properties and dynamic processes affect energy transfer and defect evolution in irradiated materials. Since SP-CSAs possess unique links between intrinsic material properties (can be altered by alloy complexity), energy dissipation and various defect dynamic processes; they are ideal systems to fill knowledge gaps between electronic- /atomic-level interactions and radiation resistance mechanisms. In our work, we show that chemical disorder and compositional complexity in SP-CSAs have an enormous impact on defect dynamics through substantial modification of energy dissipation pathways. Based on a closely integrated computational and experimental study using a novel set of Ni-based SP-CSAs, we have explicitly demonstrated that increasing chemical disorder can lead to a substantial reduction in the electron mean free path and electrical and thermal conductivity. These reductions have a significant impact on energy dissipation and consequentially on defect evolution during ion irradiation. Considerable enhancement in radiation resistance with increasing chemical complexity from pure nickel to binary, and to more complex quaternary solid solutions, is observed under ion irradiation. Contrary to conventional alloys with low solute concentration but multiple phases, energy dissipation and defect evolution at the level of electrons and atoms in SP- CSA systems with extreme compositional disorder is an unexplored frontier in materials science. The integrated experimental/modeling effort provides new insights into defect dynamics at the level of atoms and electrons, and an innovative path forward towards solving a long-standing challenge in structural materials. Increasing chemical complexity achieved orders-of-magnitude reductions in electron mean free paths and electron and thermal conductivities of alloys of NiCo, NiFe and NiCoFeCr, compared to Ni, and suppressed damage accumulation under ion irradiation. This discovery provides insights to address the grand challenge of understanding complex electronic correlations and non-equilibrium atomic interactions, and the effect of these intrinsic properties and dynamic processes on energy transfer and defect evolution in irradiated materials. Understanding how material properties and defect dynamics can be tailored by alloy complexity may pave the way for new design principles of functional alloys. (authors)

36 MATERIALS SCIENCE↗
DOE OSTI2015

One-dimensional Co(II)/Ni(II) complexes of 2-hydroxyisophthalate: Structures and magnetic properties

The solvothermal reactions of 2-hydroxyisophthalic acid (H{sub 3}ipO) with M(NO{sub 3}){sub 2}∙6H{sub 2}O (M=Co, Ni) afforded two complexes [Co{sub 2}(HipO){sub 2}(Py){sub 2}(H{sub 2}O){sub 2}] (1) and [Ni(HipO)(Py)H{sub 2}O] (2) (Py=pyridine). They exhibit similar zig-zag chain structures with the adjacent two metal centers connected by a anti-syn bridging carboxylate group from the HipO{sup 2−} ligand. The magnetic measurements reveal the dominant antiferromagnetic interactions and spin-canting in 1 while ferromagnetic interactions in 2. Both of them exhibit magnetocaloric effect (MCE) with the resulting entropy changes (−ΔS{sub m}) of 12.51 J kg{sup −1} K{sup −1} when ΔH=50 kOe at 3 K for 1 and 11.01 J kg{sup −1} K{sup −1} when ΔH=50 kOe at 3 K for 2, representing the rare examples of one-dimensional complexes with MCE. - Graphical abstract: Synopsis: Two Co(II)/Ni(II) complexes with zig-zag chain structures have been reported. 1-Co shows cant-antiferromagnetism while 2-Ni shows ferromagnetism. Magnetocaloric effect is also found in both of them. - Highlights: • Two one-dimensional Co(II)/Ni(II) complexes were solvothermally synthesized. • The Co-complex exhibits canted antiferromagnetism. • The Ni-complex exhibits ferromagnetism. • Both of the complexes display magnetocaloric effect.

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

Synthesis and Characterization of Uranium Complexes Supported by Substituted Aryldimethylsilylanilide Ligands

Here, we report the synthesis and characterization of substituted aryldimethylsilyldiisopropylanilide ligands and their respective bisamido complexes of U(III), (3,5-R 2 -PhMe 2 SiNDipp) 2 UI(dioxane) x (1, R = H, x= 0; 2, R = Me, x = 0; 3, R = t Bu, x = 1). We found that the steric bulk of the 3,5-R 2 -Ph ring affects the hapticity of the U–arene interaction. In the solid-state, 1 is a U–(η 6 -arene) complex, while 2 is a bis(U–(η 1 -arene)) complex. Theoretically calculated bond orders at PBE0 and PBE0-D3 levels of theory support these hapticity assignments. The 3,5- t Bu 2 -Ph rings of 3 are too bulky to interact with U and solid-state metrical parameters initially suggested a U–(η 1 -arene) interaction with one of the Dipp rings. However, bond order calculations show that this interaction is even weaker than in the previously reported ((PhMe 2 Si) 2 N) 3 U complex, leading to the conclusion that 3 is best described as a U–(η o -arene) complex. Molecular orbital analyses in conjunction with electron localization methods reveal that the U–(η 6 -arene) bonding in 1 is primarily electrostatic in nature. Some charge transfer takes place from the arene π orbitals to the U 6d/5f hybrid orbitals in addition to subtle δ-back-bonding. In 2 and 3, both π and δ interactions are substantially weaker, in agreement with the differences in the U–arene coordination modes. Surprisingly, attempts to generate less sterically bulky (3,5-R 2 -PhMe 2 SiNPh) 2 UI complexes results in disproportionation to homoleptic tetraamido (3,5-R 2 -PhMe 2 SiNPh) 4 U(IV) (4, R = H; 5, R = Me) complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

A QUALITATIVE METHOD TO ESTIMATE HSI DISPLAY COMPLEXITY

There is mounting evidence that complex computer system displays in control rooms contribute to cognitive complexity and, thus, to the probability of human error. Research shows that reaction time increases and response accuracy decreases as the number of elements in the display screen increase. However, in terms of supporting the control room operator, approaches focusing on addressing display complexity solely in terms of information density and its location and patterning, will fall short of delivering a properly designed interface. This paper argues that information complexity and semantic complexity are mandatory components when considering display complexity and that the addition of these concepts assists in understanding and resolving differences between designers and the preferences and performance of operators. This paper concludes that a number of simplified methods, when combined, can be used to estimate the impact that a particular display may have on the operator's ability to perform a function accurately and effectively. We present a mixed qualitative and quantitative approach and a method for complexity estimation.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2021

Preparation, characterization, and structural studies of new ruthenium(II) and ruthenium(III) complexes incorporating pyrazole ligands

Multimetallic complexes containing disparate metals have been established to have practical utilities. We previously reported a strategy for preparing such species by using combinations of neutral pyrazole (Hpyz, C 3 N 2 H 4 ) and anionic pyrazolyl ligands (pyz, C 3 N 2 H 3 – ), and herein are reported several new complexes that should be capable of incorporating a second metal center. Two of the complexes, [Ru(1,5-cod)(Hpyz) 3 Cl][BPh 4 ] and Ru(1,5-cod)(Hpyz) 2 (pyz) 2 (cod = cyclooctadiene), were prepared from [Ru(cod)Cl 2 ] 2 , while [Ru(tmeda)(Hpyz) 2 Cl 2 ][BF 4 ] (tmeda = tetramethylethylenediamine) was prepared from the neutral Ru(II) complex Ru(tmeda)(Hpyz) 2 Cl 2 via one electron oxidation by the ferricinium ion. The first two complexes, one cationic and the other uncharged, involve Ru(II), while the tmeda complex involves Ru(III). Finally, all three species have been structurally characterized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Synthesis, Photoluminescence Behavior of Green Light Emitting Tb(III) Complexes and Mechanistic Investigation of Energy Transfer Process

A series of five new terbium(III) ion complexes with 4,4-difluoro-1-phenylbutane-1,3-dione (HDPBD) and anciliary ligands was synthesized. The composition and properties of complexes were analyzed by elemental analysis, IR, NMR, powder X-ray diffaraction, TG-DTG and photoluminescence spectroscopy. These complexes exhibited ligand sensitized green emission at 546 nm associated with {sup 5}D{sub 4} → {sup 7}F{sub 5} transitions of terbium ion in the emission spectra. The photoluminescence study manifested that the organic ligands act as antenna and facilitate the absorbed energy to emitting levels of Tb(III) ion efficiently. The enhanced luminescence intensity and decay time of ternary C2-C5 complexes observed due to synergistic effect of anciliary ligands. The CIE color coordinates of complexes came under the green region of chromaticity diagram. The mechanistic investigation of intramolecular energy transfer in the complexes was discussed in detail. These terbium(III) complexes can be thrivingly used as one of the green component in light emitting material and in display devices. .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2017

Photo-induced reduction of Cr{sup 6+} by the hybrid systems “Cu{sup II} complex with Schiff base and TiO{sub 2}”: dependence on irradiation wavelength

The synthesis of novel Cu{sup II} complexes with a Schiff base obtained by condensation of salicylaldehyde and an L-aspartic acid ester are described. The physicochemical properties of the complexes were compared with those of related Cu{sup II} complexes obtained earlier. All the complexes studied were characterized by elemental analysis as well as by IR, UV-Vis, and EPR spectroscopies. The activity of the complexes and their hybrid systems (HS) with TiO{sub 2} in visible-light-driven photocatalysis in organic solvents was investigated. After irradiation with visible light, the complexes and corresponding HS reduce Cr{sup 6+} to Cr{sup 3+} more efficiently than bare TiO{sub 2}. To determine the molecular orbital compositions and energies and to explain the electronic spectra and redox properties of the systems studied, density functional calculations of the optimized structures of representative model complexes were performed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Self-diffusion of Ti interstitial based point defects and complexes in TiC

To date, the mechanism of Ti atom self-diffusion is unproven. Prior theoretical work mostly focused on Ti vacancy based mediators, but these do not reproduce the experimental activation energy or entropy. In this work, in density functional theory calculations, Ti interstitials and related defect complexes are systematically considered as possible mediators of Ti self-diffusion. Among these defects, the defect complex of two C vacancies tightly bound to a Ti dumbbell is found to have the lowest formation energy. A sustainable migration of the complex, in a translational or rotational fashion, is enabled in the presence of another (free) carbon vacancy nearby the complex, and thus the rate of Ti self-diffusion by this mechanism is dependent on the concentration of carbon vacancies. The calculated activation energy of the complex agrees well with the experimental value in TiC 0.97 . Similar analyses of the Ti self-diffusion mechanisms mediated by Ti interstitials or dumbbells yield much higher activation energies, but the corresponding migration energies are evaluated to be less than 1 eV, which suggests they can be possible mediators of the radiation-enhanced Ti self-diffusion in TiC. To fully enable the comparison with experiments that are typically conducted at temperatures as high as 2500 K, we also consider the temperature dependent vibrational contribution to the activation energy of the defect complex. The vibrational contribution imposes an additive effect on the defect formation energy, while the migration energies are lowered due to the thermal expansion of the lattice. When combined, these factors give an excellent agreement with the experiments. Furthermore, this work gives strong support to the concept that Ti interstitial based defect complexes are likely diffusion mediators for Ti atom self-diffusion in TiC, further establishes a solid basis for large-scale modeling, and may eventually pave the way to accurately predicting defect-controlled diffusional processes.

36 MATERIALS SCIENCE↗