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At least 757 records · Page 42

Excited-State Dynamics and Nonlinear Optical Properties of Hyperpolarizable Chromophores Based on Conjugated Bis(terpyridyl)Ru(II) and Palladium and Platinum Porphyrinic Components: Impact of Heavy Metals upon Supermolecular Electro-Optic Properties

A new series of strongly coupled oscillators based upon (porphinato)Pd, (porphinato)Pt, and bis(terpyridyl)-ruthenium(II) building blocks is described. These RuPPd, RuPPt, RuPPdRu, and RuPPtRu chromophores feature bis- (terpyridyl)Ru(II) moieties connected to the (porphinato)metal unit via an ethyne linker that bridges the 4!-terpyridyl and porphyrin macrocycle meso-carbon positions. Pump–probe transient optical data demonstrate sub-picosecond excited singlet-to-triplet-state relaxation. The relaxed lowest-energy triplet (T 1 ) excited states of these chromophores feature absorption manifolds that span the 800–1200 nm spectral region, microsecond triplet-state lifetimes, and large absorptive extinction coefficients [ε(T 1 → T n ) > 4 × 10 4 M –1 cm –1 ]. Dynamic hyperpolarizability (β λ ) values were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at several incident irradiation wavelengths over the 800–1500 nm spectral region. Relative to benchmark RuPZn and RuPZnRu chromophores which showed large βHRS values over the 1200–1600 nm range, RuPPd, RuPPt, RuPPdRu, and RuPPtRu displayed large βHRS values over the 850–1200 nm region. Generalized Thomas–Kuhn sum (TKS) rules and experimental hyperpolarizability values were utilized to determine excited state-to-excited state transition dipole terms from experimental electronic absorption data and thus assessed frequency-dependent β λ values, including two- and three-level contributions for both β zzz and β xzx tensor components to the RuPPd, RuPPt, RuPPdRu, and RuPPtRu hyperpolarizability spectra. Furthermore, these analyses qualitatively rationalize how the βzzz and βxzx tensor elements influence the observed irradiation wavelength-dependent hyperpolarizability magnitudes. The TKS analysis suggests that supermolecules related to RuPPd, RuPPt, RuPPdRu, and RuPPtRu will likely feature intricate dependences of experimentally determined βHRS values as a function of irradiation wavelength that derive from substantial singlet–triplet mixing, and complex interactions among multiple different β tensor components that modulate the long wavelength regime of the nonlinear optical response.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Static and dynamic strain energy release rates in toughened thermosetting composite laminates

In this work, the static and dynamic fracture properties of several thermosetting resin based composite laminates are presented. Two classes of materials are explored. These are homogeneous, thermosetting resins and toughened, multi-phase, thermosetting resin systems. Multi-phase resin materials have shown enhancement over homogenous materials with respect to damage resistance. The development of new dynamic tests are presented for composite laminates based on Width Tapered Double Cantilevered Beam (WTDCB) for Mode 1 fracture and the End Notched Flexure (ENF) specimen. The WTDCB sample was loaded via a low inertia, pneumatic cylinder to produce rapid cross-head displacements. A high rate, piezo-electric load cell and an accelerometer were mounted on the specimen. A digital oscilloscope was used for data acquisition. Typical static and dynamic load versus displacement plots are presented. The ENF specimen was impacted in three point bending with an instrumented impact tower. Fracture initiation and propagation energies under static and dynamic conditions were determined analytically and experimentally. The test results for Mode 1 fracture are relatively insensitive to strain rate effects for the laminates tested in this study. The test results from Mode 2 fracture indicate that the toughened systems provide superior fracture initiation and higher resistance to propagation under dynamic conditions. While the static fracture properties of the homogeneous systems may be relatively high, the apparent Mode 2 dynamic critical strain energy release rate drops significantly. The results indicate that static Mode 2 fracture testing is inadequate for determining the fracture performance of composite structures subjected to conditions such as low velocity impact. A good correlation between the basic Mode 2 dynamic fracture properties and the performance is a combined material/structural Compression After Impact (CAI) test is found. These results underscore the importance of examining rate-dependent behavior for determining the longevity of structures manufactured from composite materials.

Cairns, Douglas S.↗

Examining future changes in coastal low-level jet properties offshore California through dynamical downscaling

The coastal low-level jet, or coastal low-level jet (CLLJ), is a synoptically-forced meteorological feature frequently present offshore the western United States (U.S.). Characterized by a wind speed maximum that resides at the top of the marine boundary layer, the CLLJ is largely controlled by the location and strength of the North Pacific High (NPH) as well as the coastal geometry. Considering the rich wind resource available in this offshore region, the Bureau of Ocean Energy Management identified wind energy lease areas offshore California and supported the deployment of two U.S. Department of Energy wind lidar buoys near Morro Bay and Humboldt. Despite our relatively good understanding of the fundamental mechanisms responsible for large-scale CLLJ properties offshore the western U.S., future changes in CLLJ characteristics are less clear. To address this research challenge, and ultimately to better inform future wind turbine deployments, we use simulations driven by three global climate models (GCMs). We apply self-organizing maps to the model outputs for a historical and two future climate periods to show the range of NPH regimes that support CLLJ conditions during the warm seasons, as well as the subtle contribution from land-falling cyclones approaching the mainland during the cold seasons. Compared to the historical period, the three GCM-driven simulations agree that CLLJ conditions will become more (less) prevalent from central California northward (southward). They agree less with respect to future changes in maximum CLLJ wind speeds and CLLJ heights. However, after considering model biases present during the historical period, wind speeds between the models are actually more similar during the 2070–2095 period than during the historical period. The potential combination of more frequent CLLJ conditions characterized by relatively consistent wind speeds occurring at lower heights across northern California suggests that the Humboldt lease area may be ideal for a long-term wind turbine deployment.

54 ENVIRONMENTAL SCIENCES↗

Evaluating dynamic thermal performance of building envelope components using small-scale calibrated hot box tests

The hot box test method has been applied to evaluate both the steady-state (U-value) and dynamic thermal properties of building envelopes. However, the high construction cost of full-scale hot box apparatus and the testing time required (usually several days) may prevent its wider adoption. To overcome the limitations of full-scale hot box tests, here we propose a novel method to evaluate the dynamic thermal performance of building envelope components using a small-scale calibrated hot box and scaled-down specimen. In this paper, the scaling relationships of thermal properties evaluated using a full-size specimen and a scaled-down specimen are established based on the Laplace transform of the heat transfer equations. In addition, dynamic thermal properties obtained from scaled-down experimental tests are compared to the values calculated by the EN ISO13768 (ISO) method. A small-scale hot box with a 355 mm × 355 mm metering area was constructed and calibrated to validate the correlations. Three scaled-down concrete sandwich wall panels were then tested and the scaling relationship was cross-validated using the experimental results, finite difference (FD) simulations, and the ISO method. The results indicate that the dynamic thermal properties obtained from a scaled-down hot box test can be correlated to its full-size counterpart when certain conditions are met. The scaled-down hot box test is demonstrated to be an effective yet economical alternative to a full-scale test with significantly reduced experimentation cost and turn-around time.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Surface Energy Dynamics and Canopy Structural Properties in Intact and Disturbed Forests in the Southern Amazon

The Brazilian Amazon has been a focus of land development with large swaths of forests converted to agriculture. Forest degradation by selective logging and fires has accompanied the agricultural frontier and has resulted in significant impacts on Amazonian ecosystems. Changes in forest structure resulting from forest disturbances have large impacts on the surface energy balance, including on land surface temperature (LST) and evapotranspiration (ET). This study's objective is to assess the effects of forest disturbances on water fluxes and forest structure in a transitional forest site in the Southern Amazon. We used ET and LST products from MODIS and Landsat 8 and GEDI-derived forest structure data to address our research questions. We found that disturbances induced seasonal water stress, more pronounced in croplands/pastures than in forests (differences up to 20% in the dry season), and more pronounced in second-growth and recently burned areas than in logged and intact forests (differences up to 12% in the dry season). Moreover, ET and LST were negatively related, with more consistent relationships across disturbance classes in the dry season (R 2 : 0.41–0.87) than in the wet season (R 2 : 0.18–0.49). Forest and cropland or pasture classes showed contrasting relationships in the dry season. Finally, we found that forest structure exhibited stronger relationships with ET and LST in the most disturbed forests (R 2 : 0.01–0.43) than in the least disturbed forests (R 2 < 0.05). Our findings help to elucidate degraded forests functioning under a changing climate and to improve estimates of water and energy fluxes in Amazonian degraded forests.

54 ENVIRONMENTAL SCIENCES↗

Structure and Dynamic and Nonlinear Optical Properties of Hg{sub 2}F{sub 2} Crystals

The structure of the Hg{sub 2}F{sub 2} compound was studied experimentally and theoretically within the density functional theory. X-ray diffraction studies enabled us to determine the space group of the crystal (I4/mmm), and the comparison of the experimentally obtained Raman spectra of these crystals with the theoretical ones enabled us to find and uniquely identify all bands in the spectra. The stability of the I4/mmm phase was analyzed in a wide range of uniaxial and hydrostatic pressures. It is shown that the uniaxial compression of a crystal along a tetrad axis results in a phase transition to the Cmcm structure at P{sub c} = 8 GPa, whereas the hydrostatic compression results in a previously unknown phase transition to the Cmca phase at P{sub c} = 9 GPa. The calculations of the cubic nonlinear susceptibility of Hg{sub 2}F{sub 2} predict a giant value of this quantity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Pragmatic Uncertainty Quantification and Propagation in Inverse Estimation of Structural Dynamics Parameters given Material Property Uncertainties and Limited Sensor Data

In this report we demonstrate some relatively simple and inexpensive methods to effectively account for various sources of epistemic lack-of-knowledge type uncertainty in inverse problems. The demonstration problem involves inverse estimation of six parameters of a bolted joint that attaches a kettlebell shaped object to a thick plate. The parameters are efficiently inverted in a modal-based model calibration using gradient-based optimization. Two material properties of the kettlebell are treated as uncertain to within given epistemic uncertainty bounds. We apply and test interval and sparse-sample probabilistic approaches to account for uncertainty in the estimated parameters (and various scalar functionals of the parameters as generic quantities of interest, QOIs) due to uncertainties in the material properties. We also investigate the error effects of limited numbers of vibration sensors (accelerometers) on the kettlebell and plate, and therefore abbreviated excitation/response information in the parameter inversions. We propose and demonstrate a Leave-K-Sensors-Out “cross-prediction” UQ approach to estimate related uncertainties on the parameters and QOI functionals. We indicate how uncertainties from material properties and limited sensors are treated in a combined manner. The economical combined UQ approach involves just three to five samples (i.e. three to five inverse simulations), with no added complication or error/uncertainty from use of surrogate models for affordability. Finally, we describe a related economical UQ approach for handling potential parameter solution non-uniqueness and numerical optimization related precision uncertainties in the estimated parameter values. Indicated further research is identified.

36 MATERIALS SCIENCE↗

Mars dynamics, atmospheric and surface properties - Determination from Viking tracking data

Approximately three months of radio tracking data from the Viking landers have been analyzed to determine the lander locations, the orientation of the spin axis of Mars, and a first estimate from Viking data of the planet's spin rate. Preliminary results have also been obtained for atmospheric parameters and radii at occultation points and for properties of the surface in the vicinity of lander 1.

Michael, W. H., Jr.↗

Dynamic measurements of thermophysical properties of metals and alloys at high temperatures by subsecond pulse heating techniques

Rapid (subsecond) heating techniques developed at the National Institute of Standards and Technology for the measurements of selected thermophysical and related properties of metals and alloys at high temperatures (above 1000 C) are described. The techniques are based on rapid resistive self-heating of the specimen from room temperature to the desired high temperature in short times and measuring the relevant experimental quantities, such as electrical current through the specimen, voltage across the specimen, specimen temperature, length, etc., with appropriate time resolution. The first technique, referred to as the millisecond-resolution technique, is for measurements on solid metals and alloys in the temperature range 1000 C to the melting temperature of the specimen. It utilizes a heavy battery bank for the energy source, and the total heating time of the specimen is typically in the range of 100-1000 ms. Data are recorded digitally every 0.5 ms with a full-scale resolution of about one part in 8000. The properties that can be measured with this system are as follows: specific heat, enthalpy, thermal expansion, electrical resistivity, normal spectral emissivity, hemispherical total emissivity, temperature and energy of solid-solid phase transformations, and melting temperature (solidus). The second technique, referred to as the microsecond-resolution technique, is for measurements on liquid metals and alloys in the temperature range 1200 to 6000 C. It utilizes a capacitor bank for the energy source, and the total heating time of the specimen is typically in the range 50-500 micro-s. Data are recorded digitally every 0.5 micro-s with a full-scale resolution of about one part in 4000. The properties that can be measured with this system are: melting temperature (solidus and liquidus), heat of fusion, specific heat, enthalpy, and electrical resistivity. The third technique is for measurements of the surface tension of liquid metals and alloys at their melting temperature. It utilizes a modified millisecond-resolution heating system designed for use in a microgravity environment.

Cezairliyan, Ared↗

A conceptual framework for evaluating variable speed generator options for wind energy applications

Interest in variable speed generating technology has accelerated as greater emphasis on overall efficiency and superior dynamic and control properties in wind-electric generating systems are sought. This paper reviews variable speed technology options providing advantages and disadvantages of each. Furthermore, the dynamic properties of variable speed systems are contrasted with synchronous operation. Finally, control properties of variable speed systems are examined.

Reddoch, T. W.↗