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At least 127 records · Page 7

Ultrafast conformational dynamics of Rydberg-excited N -methyl piperidine

We have observed the ultrafast conformational dynamics of electronically excited N-methyl piperidine (NMP) using time-resolved Rydberg fingerprint spectroscopy. Optical excitation at various wavelengths ranging from 212 nm to 229 nm leads to the 3s or 3p Rydberg states and induces coherent oscillatory motions with periods of about 700 fs. Furthermore, these coherent motions survive the internal conversion from 3p to 3s but then dephase on a time scale of a few oscillations. Intramolecular vibrational energy redistribution on a picosecond time scale leads to an equilibrium between two conformeric structures that are separated in binding energy by 0.09 eV. Model calculations using the DFT-SIC method are in excellent agreement with the experiments and identify the conformers as the chair and twist structures of NMP. The analysis of the equilibrium parameters at long time delays as a function of excitation wavelength allows for the extraction of thermodynamic parameters for the conformeric transformation. We derive an enthalpy of the chair to twist reaction in the 3s excited state of 62 meV with an entropy of 19.70 J mol –1 K –1 . An activation energy of 276 meV is also obtained with a kinetic model.

74 ATOMIC AND MOLECULAR PHYSICS↗

Assessment of Postflight Locomotor Performance Utilizing a Test of Functional Mobility: Strategic and Adaptive Responses

Space flight induces adaptive modification in sensorimotor function, allowing crewmembers to operate in the unique microgravity environment. This adaptive state, however, is inappropriate for a terrestrial environment. During a re-adaptation period upon their return to Earth, crewmembers experience alterations in sensorimotor function, causing various disturbances in perception, spatial orientation, posture, gait, and eye-head coordination. Following long duration space flight, sensorimotor dysfunction would prevent or extend the time required to make an emergency egress from the vehicle; compromising crew safety and mission objectives. We are investigating two types of motor learning that may interact with each other and influence a crewmember's ability to re-adapt to Earth's gravity environment. In strategic learning, crewmembers make rapid modifications in their motor control strategy emphasizing error reduction. This type of learning may be critical during the first minutes and hours after landing. In adaptive learning, long-term plastic transformations occur, involving morphological changes and synaptic modification. In recent literature these two behavioral components have been associated with separate brain structures that control the execution of motor strategies: the strategic component was linked to the posterior parietal cortex and the adaptive component was linked to the cerebellum (Pisella, et al. 2004). The goal of this paper was to demonstrate the relative contributions of the strategic and adaptive components to the re-adaptation process in locomotor control after long duration space flight missions on the International Space Station (ISS). The Functional Mobility Test (FMT) was developed to assess crewmember s ability to ambulate postflight from an operational and functional perspective. Sixteen crewmembers were tested preflight (3 sessions) and postflight (days 1, 2, 4, 7, 25) following a long duration space flight (approx 6 months) on the ISS. We have further analyzed the FMT data to characterize strategic and adaptive components during the postflight readaptation period. Crewmembers walked at a preferred pace through an obstacle course set up on a base of 10 cm thick medium density foam (Sunmate Foam, Dynamic Systems, Inc., Leicester, NC). The 6.0m X 4.0m course consisted of several pylons made of foam; a Styrofoam barrier 46.0cm high that crewmembers stepped over; and a portal constructed of two Styrofoam blocks, each 31cm high, with a horizontal bar covered by foam and suspended from the ceiling which was adjusted to the height of the crewmember s shoulder. The portal required crewmembers to bend at the waist and step over a barrier simultaneously. All obstacles were lightweight, soft and easily knocked over. Crewmembers were instructed to walk through the course as quickly and as safely as possible without touching any of the objects on the course. This task was performed three times in the clockwise direction and three times in the counterclockwise direction that was randomly chosen. The dependent measures for each trial were: time to complete the course (seconds) and the number of obstacles touched or knocked down. For each crewmember, the time to complete each FMT trial from postflight days 1, 2, 4, 7 and 25 were further analyzed. A single logarithmic curve using a least squares calculation was fit through these data to produce a single comprehensive curve (macro). This macro curve composed of data spanning 25 days, illustrates the re-adaptive learning function over the longer time scale term. Additionally, logarithmic curves were fit to the 6 data trials within each individual post flight test day to produce 5 separate daily curves. These micro curves, produced from data obtained over the course of minutes, illustrates the strategic learning function exhibited over a relative shorter time scale. The macro curve for all subjects exhibited adaptive motor learning patterns over the 25 day period. Howev, 9/16 crewmembers exhibited significant strategic motor learning patterns in their micro curves, as defined by m > 1 in the equation of the line y=m*LN(x) +b. These data indicate that postflight recovery in locomotor function involves both strategic and adaptive mechanisms. Future countermeasures will be designed to enhance both recovery processes.

Warren, L. E.↗

Facilitating Analysis of Multiple Partial Data Streams

Robotic Operations Automation: Mechanisms, Imaging, Navigation report Generation (ROAMING) is a set of computer programs that facilitates and accelerates both tactical and strategic analysis of time-sampled data especially the disparate and often incomplete streams of Mars Explorer Rover (MER) telemetry data described in the immediately preceding article. As used here, tactical refers to the activities over a relatively short time (one Martian day in the original MER application) and strategic refers to a longer time (the entire multi-year MER missions in the original application). Prior to installation, ROAMING must be configured with the types of data of interest, and parsers must be modified to understand the format of the input data (many example parsers are provided, including for general CSV files). Thereafter, new data from multiple disparate sources are automatically resampled into a single common annotated spreadsheet stored in a readable space-separated format, and these data can be processed or plotted at any time scale. Such processing or plotting makes it possible to study not only the details of a particular activity spanning only a few seconds, but also longer-term trends. ROAMING makes it possible to generate mission-wide plots of multiple engineering quantities [e.g., vehicle tilt as in Figure 1(a), motor current, numbers of images] that, heretofore could be found only in thousands of separate files. ROAMING also supports automatic annotation of both images and graphs. In the MER application, labels given to terrain features by rover scientists and engineers are automatically plotted in all received images based on their associated camera models (see Figure 2), times measured in seconds are mapped to Mars local time, and command names or arbitrary time-labeled events can be used to label engineering plots, as in Figure 1(b).

Maimone, Mark W.↗

Control of leading-edge vortices on a delta wing

The unsteady flow structure of leading-edge vortices on a delta wing has been investigated using new types of experimental techniques, in order to provide insight into the consequences of various forms of active control. These investigations involve global control of the entire wing and local control applied at crucial locations on or adjacent to the wing. Transient control having long and short time-scales, relative to the convective time-scale C/U(sub infinity), allows substantial modification of the unsteady and time-mean flow structure. Global control at long time-scale involves pitching the wing at rates an order of magnitude lower than the convective time-scale C/U(sub infinity), but at large amplitudes. The functional form of the pitching maneuver exerts a predominant influence on the trajectory of the feeding sheet, the instantaneous vorticity distribution, and the instantaneous location of vortex breakdown. Global control at short time-scales of the order of the inherent frequency of the shear layer separating from the leading-edge and the natural frequency of vortex breakdown shows that 'resonant' response of the excited shear layer-vortex breakdown system is attainable. The spectral content of the induced disturbance is preserved not only across the entire core of the vortex, but also along the axis of the vortex into the region of vortex breakdown. This unsteady modification results in time-mean alteration of the axial and swirl velocity fields and the location of vortex breakdown. Localized control at long and short time-scales involves application of various transient forms of suction and blowing using small probes upstream and downstream of the location of vortex breakdown, as well as distributed suction and blowing along the leading-edge of the wing applied in a direction tangential to the feeding sheet. These local control techniques can result in substantial alteration of the location of vortex breakdown; in some cases, it is possible to accomplish this without net mass addition to the flow field.

Magness, C.↗

Relative Time-scale for Channeling Events Within Chaotic Terrains, Margaritifer Sinus, Mars

A relative time scale for ordering channel and chaos forming events was constructed for areas within the Margaritifer Sinus region of Mars. Transection and superposition relationships of channels, chaotic terrain, and the surfaces surrounding them were used to create the relative time scale; crater density studies were not used. Channels and chaos in contact with one another were treated as systems. These systems were in turn treated both separately (in order to understand internal relationships) and as members of the suite of Martian erosional forms (in order to produce a combined, master time scale). Channeling events associated with chaotic terrain development occurred over an extended geomorphic period. The channels can be divided into three convenient groups: those that pre-date intercrater plains development post-plains, pre-chasma systems; and those associated with the development of the Vallis Marineris chasmata. No correlations with cyclic climatic changes, major geologic events in other regions on Mars, or triggering phenomena (for example, specific impact events) were found.

Janke, D.↗

Associations between coronal mass ejections and soft X-ray events

The association between white light coronal mass ejections (CMEs) and full-disk X ray events have been examined as a function of X ray duration during the recent years of high sunspot activity (1979-1981). On a time scale of hours, no duration interval has been found that separates X ray events into two distinct classes depending on whether or not they have associated CMEs. Rather, the tendency for long-duration X ray events to have associated CMEs reflects the fact that, as X ray duration increases, the differential distribution of events without CMEs falls off faster than the distriution of X ray events with CMEs.

Sheeley, N. R., Jr.↗

Computation of turbulent, separated, unswept compression ramp interactions

Examination of the literature shows that the comparison between experiment and computation for highly separated unswept compression ramp flows is generally poor, irrespective of the turbulence model used. In general, the upstream influence is not correct, the wall pressure rise through separation is too steep, and the pressures under the separated shear layer are too high. In the current study, the objective is to determine if these discrepancies might be attributed more to other factors such as flowfield unsteadiness or three-dimensionality, rather than to inadequate turbulence modeling. To examine this possibility, multichannel wall pressure fluctuations were measured under the unsteady separation shock wave in a 28-deg unswept compression ramp flow at Mach 5. The results show that the large scale, low frequency separation shock unsteadiness controls the distribution of time-averaged surface properties and that neglect of the unsteadiness is probably the primary cause of the discrepancy between experiment and computation.

Marshall, T. A.↗

Study of the Unsteady Flow Features on a Stalled Wing

The occurrence of large scale structures in the post stall flow over a rectangular wing at high angles of attack was investigated in a small-scale subsonic wind tunnel. Mean and time dependent measurements within the separated flow field suggest the existence of two distinct angle of attack regimes beyond wing stall. The shallow stall regime occurs over a narrow range of incidence angles (2-3 deg.) immediately following the inception of leading edge separation. In this regime, the principal mean flow structures, termed stall cells, are manifested as a distinct spanwise periodicity in the chordwise extent of the separated region on the model surface with possible lateral mobility not previously reported. Within the stall cells and on the wing surface, large amplitude pressure fluctuations occur with a frequency much lower than anticipated for bluff body shedding, and with minimum effect in the far wake. In the deep stall regime, stall cells are not observed and the separated region near the model is relatively free of large amplitude pressure disturbances.

Yon, Steven A.↗

Ultrafast Proton-Coupled Electron Transfer Reactions at Unit Quantum Yield

Proton-coupled electron transfer (PCET) reactions mediate essential biological energy-conversion processes, yet dynamical experiments that distinguish concerted electron/proton motion from sequential electron-transfer/proton-transfer pathways are unprecedented on ultrafast time scales. Here we report a tightly coupled donor–spacer–acceptor assembly, NDI-Sp-PhOH/BI, that enables direct interrogation of light-triggered and ultrafast PCET dynamics. Photoexcitation of the naphthalene diimide chromophore drives charge separation forming NDI radical anion and benzimidazolium phenoxy radical (PhO●/BIH+) products with a 440 fs time constant, followed by thermal charge recombination on a 5 ps time scale. Transient visible/near-infrared and mid-infrared spectroscopies independently track electron and proton motion and reveal coincident formation and decay of the charge-separated PCET products, excluding detectable phenol radical cation or phenoxide intermediates expected for sequential electron transfer-proton transfer (ET-PT) pathways. Surface-hopping quasiclassical trajectory simulations demonstrate rapid proton relocation coupled to evolution from locally excited to charge-transfer states, congruent with a concerted mechanism. These combined spectroscopic and computational results establish NDI-Sp-PhOH/BI as an archetype for ultrafast, concerted PCET occurring with unit quantum yield; further, because this platform provides distinct electronic and vibrational spectroscopic handles in its ground, electronically excited, and charge-separated states, it provides new opportunities to characterize mechanistic crossover in biomimetic PCET systems.

10 SYNTHETIC FUELS↗

Optical Detection of Crack Separation in Si PV Modules

Studying the mechanical behavior of silicon cell fractures is critical for understanding changes in PV module performance. Traditional methods of detecting cell cracks, e.g., electroluminescence (EL) imaging, utilize electrical changes and defects associated with cell fracture. Therefore, these methods reveal crack locations, but do not operate at the time or length scales required to accurately measure other physical properties of cracks, such as separation width and behavior under dynamic loads.

14 SOLAR ENERGY↗

The influence of cooling rate on condensation of iron, aluminum, and uranium oxide nanoparticles

Fundamental observations of particle size distributions are needed to develop models that predict the fate and transport of radioactive materials in the atmosphere following a nuclear incident. The extent of material transport is influenced by the time scales of particle formation processes (e.g., condensation, coagulation). In this study, we investigated the influence of cooling time scales on size distributions of uranium, aluminum, and iron oxide particles that are synthesized separately under identical run conditions inside the controlled environment of an argon plasma flow reactor. Two distinct temperature distributions are imposed along the flow reactor by varying the argon flow rate downstream of the plasma torch. The vaporized reactants of uranium, aluminum, and iron are cooled from about 5000K to 1000K before they are collected on silicon wafers for ex situ scanning electron microscope analysis. The microscope images show that the sizes of the largest aluminum and iron oxide particles heavily depend on the cooling time scales, whereas significant size variation with cooling rate is not observed for uranium oxide particles. In addition, the size distribution of aluminum oxide particles exhibits the broadest range among all three metal oxides studied. We performed simulations of particle size distributions using a kinetic model that couples gas phase oxidation chemistry with particle formation processes, including nucleation, condensation, and coagulation. The model results demonstrate the strong sensitivity of particle size distribution to different cooling histories (i.e., temperature vs residence time) along the flow reactor. In conclusion, the kinetic model also helps identify directions for future research to improve the predictions.

36 MATERIALS SCIENCE↗

Alsep data processing: How we processed Apollo Lunar Seismic Data

The Apollo lunar seismic station network gathered data continuously at a rate of 3 x 10 to the 8th power bits per day for nearly eight years until the termination in September, 1977. The data were processed and analyzed using a PDP-15 minicomputer. On the average, 1500 long-period seismic events were detected yearly. Automatic event detection and identification schemes proved unsuccessful because of occasional high noise levels and, above all, the risk of overlooking unusual natural events. The processing procedures finally settled on consist of first plotting all the data on a compressed time scale, visually picking events from the plots, transferring event data to separate sets of tapes and performing detailed analyses using the latter. Many problems remain especially for automatically processing extraterrestrial seismic signals.

Latham, G. V.↗

How we processed Apollo lunar seismic data

The Apollo lunar seismic station network gathered data continuously at a rate of 3 x 10 to the 8th bits per day for nearly eight years until termination in September, 1977. The data were processed and analyzed using a PDP-15 minicomputer. On average, 1500 long-period seismic events were detected yearly. Automatic event detection and identification schemes proved unsuccessful because of occasional high noise levels and, above all, the risk of overlooking unusual natural events. The processing procedures which were finally chosen consist of plotting all the data on a compressed time scale, visually picking events from the plots, transferring event data to separate sets of tapes and performing detailed analyses using the latter. Many problems remain, especially in the automatic processing of extraterrestrial seismic signals.

Nakamura, Y.↗

Temporal evolution of collisionless sheaths

Experimental measurements have been performed to determine the temporal evolution of Langmuir sheaths near an electrode to which a negative step bias is applied in a collisionless argon plasma. The plasma was produced by a hot-filament discharge in a multidipole device. Plasma potential data were obtained using emissive probes with two different techniques: time-resolved sampling and time-averaged techniques. The sheath is found to initially form close to the electrode, to extend to a maximum separation, and to contract to a steady-state value. The time scale required to reach a steady state is close to the time scale of the presheath relaxation. Characteristics of sheaths in RF plasmas are also measured using a parallel-plate plasma capacitor. It is observed that the plasma potential profile has significant variation with frequency, even for frequencies as low as 1 kHz which are far below the ion plasma frequency (about 1 MHz).

Cho, M. H.↗

Milliarcsecond radio structure of weak-lined T Tauri stars

VLBI and VLA observations of six radio-bright weak-lined T Taur (WTT) stars are reported, as well as direct measurements of the sizes of the emitting regions. VLBI measurements established that essentially all the radio emission from these premain-sequence stars originates in regions 15 stellar radii or less in size. Corresponding brightness temperatures ranged from 10 exp 7.5 to not less than 10 exp 9 K, ruling out a thermal process such as free-free bremsstrahlung radiation from a circumstellar wind. The radio luminosity and structure of several stars changed significantly between measurements separated by 1 day. HD 283447 showed intraday radio variability on time scales as short as 1 hr. Corresponding VLBI measurements show a new unresolved component appearing after an increase in flux density, possibly indicating that the driving agent for larger radio flares originates close to the star. The high conformation rate of nonthermal radio emission from this initial sample of radio-bright WTT stars show that these solar-type premain-sequence stars alter their immediate environments via magnetic processes to an extent comparable to that shown by RS CVn or Algol close binaries.

Phillips, R. B.↗

New Approaches to Parameterizing Convection

Many general circulation models (GCMs) currently use separate schemes for planetary boundary layer (PBL) processes, shallow and deep cumulus (Cu) convection, and stratiform clouds. The conventional distinctions. among these processes are somewhat arbitrary. For example, in the stratocumulus-to-cumulus transition region, stratocumulus clouds break up into a combination of shallow cumulus and broken stratocumulus. Shallow cumulus clouds may be considered to reside completely within the PBL, or they may be regarded as starting in the PBL but terminating above it. Deeper cumulus clouds often originate within the PBL with also can originate aloft. To the extent that our models separately parameterize physical processes which interact strongly on small space and time scales, the currently fashionable practice of modularization may be doing more harm than good.

Randall, David A.↗

Towards a Modern Theory of Multiphase Filtration Flow

An alternative theoretical model of joint filtration flow of immiscible incompressible fluids is presented. The model takes into account relaxation processes due to the interchange of the fluids between pores of difference sizes which is driven by capillary forces. The fluids occupy connected regions in a four-dimensional space formed by three coordinates and the pore length scale. When the fluid exchange between pores of given sizes is effected by way of successive flow through pores of all the intermediate sizes, the pressure within each region is governed by a hyperbolic equation, the role of time being played by the pore linear scale. Pressure jumps across hypersurfaces separating the regions equal corresponding values of the capillary pressure. A supplementary condition at any such hypersurface requires the speed of its displacement in the four-dimensional space to coincide with the normal velocity components of both the adjoining fluids. As a result, a principally new statement of multiphase filtration flow problems is gained with allowance for capillary relaxation in the porous space.

Buyevich, Yu A.↗

Cloud Inhomogeneity from MODIS

Two full months (July 2003 and January 2004) of MODIS Atmosphere Level-3 data from the Terra and Aqua satellites are analyzed in order to characterize the horizontal variability of cloud optical thickness and water path at global scales. Various options to derive cloud variability parameters are discussed. The climatology of cloud inhomogeneity is built by first calculating daily parameter values at spatial scales of l degree x 1 degree, and then at zonal and global scales, followed by averaging over monthly time scales. Geographical, diurnal, and seasonal changes of inhomogeneity parameters are examined separately for the two cloud phases, and separately over land and ocean. We find that cloud inhomogeneity is weaker in summer than in winter, weaker over land than ocean for liquid clouds, weaker for local morning than local afternoon, about the same for liquid and ice clouds on a global scale, but with wider probability distribution functions (PDFs) and larger latitudinal variations for ice, and relatively insensitive to whether water path or optical thickness products are used. Typical mean values at hemispheric and global scales of the inhomogeneity parameter nu (roughly the mean over the standard deviation of water path or optical thickness), range from approximately 2.5 to 3, while for the inhomogeneity parameter chi (the ratio of the logarithmic to linear mean) from approximately 0.7 to 0.8. Values of chi for zonal averages can occasionally fall below 0.6 and for individual gridpoints below 0.5. Our results demonstrate that MODIS is capable of revealing significant fluctuations in cloud horizontal inhomogenity and stress the need to model their global radiative effect in future studies.

Oreopoulos, Lazaros↗