Search NASA⌕ Search

SEARCH · Search NASA

Results for “persistence models”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

Neutron Star Spin Measurements and Dense Matter with LOFT

Observations over the last decade with RXTE have begun to reveal the X-ray binary progenitors of the fastest spinning neutron stars presently known. Detection and study of the spin rates of binary neutron stars has important implications for constraining the nature of dense matter present in neutron star interiors, as both the maximum spin rate and mass for neutron stars is set by the equation of state. Precision pulse timing of accreting neutron star binaries can enable mass constraints. Particularly promIsing is the combination of the pulse and eclipse timing, as for example, in systems like Swift 11749.4-2807. With its greater sensitivity, LOFT will enable deeper searches for the spin periods of the neutron stars, both during persistent outburst intervals and thermonuclear X-ray bursts, and enable more precise modeling of detected pulsations. I will explore the anticipated impact of LOFT on spin measurements and its potential for constraining dense matter in neutron stars

Strohmayer, Tod↗
NASA NTRS2019

Evaluating Models' Response of Tropical Low Clouds to SST Forcings Using CALIPSO Observations

Recent studies have shown that, in response to a surface warming, the marine tropical low-cloud cover (LCC) as observed by passive-sensor satellites substantially decreases, therefore generating a smaller negative value of the top-of-the-atmosphere (TOA) cloud radiative effect (CRE). Here we study the LCC and CRE interannual changes in response to sea surface temperature (SST) forcings in the GISS model E2 climate model, a developmental version of the GISS model E3 climate model, and in 12 other climate models, as a function of their ability to represent the vertical structure of the cloud response to SST change against 10 years of CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations) observations. The more realistic models (those that satisfy the observational constraint) capture the observed interannual LCC change quite well ([delta]LCC]/[delta]SST= -3.49±1.01%K [negative 1 superscript] vs. [delta]LCC/[delta]SST[subscript obs]= -3.59±0.28%K[negative 1 superscript]) while the others largely underestimate it ([delta]LCC/[delta]SST= -1.32±1.28%K[negative 1 superscript]). Consequently, the more realistic models simulate more positive shortwave (SW) feedback ([delta]CRE/[delta]SST=2.60±1.13Wm[negative 2 superscript] K[negative 1 superscript]) than the less realistic models (CRE/SST=0.87±2.63Wm2K1), in better agreement with the observations ([delta]CRE/[delta]SST[subscript obs]=3±0.26Wm[negative 2 superscript] K[negative 1 superscript] ), although slightly underestimated. The ability of the models to represent moist processes within the planetary boundary layer (PBL) and produce persistent stratocumulus (Sc) decks appears crucial to replicating the observed relationship between clouds, radiation and surface temperature. This relationship is different depending on the type of low clouds in the observations. Over stratocumulus regions, cloud-top height increases slightly with SST, accompanied by a large decrease in cloud fraction, whereas over trade cumulus (Cu) regions, cloud fraction decreases everywhere, to a smaller extent.

low clouds↗
NASA NTRS2020

Precipitation and Aridity Constraints on Early Mars from Globally-Distributed Paleolakes

The widespread occurrence of fluvio-lacustrine features on Mars support long-lived flow and accumulation of water in a warmer, wetter past. However, martian climate models have been unable to recreate the necessary conditions required to support a persistent wet climate. Orbital and in-situ data sets have revealed the existence of > 400 paleolakes on Mars, which can be subdivided into open- and closed-basin lakes. Open-basin lakes require that sufficient water accumulated to fill and overtop the basin-confining topography, providing a minimum constraint on required water volumes. Conversely, closed-basin lakes provide maximum water volumes since the absence of an outlet breach generally implies they did not overflow. Importantly, a subset of both open- and closed-basin lakes are fed by valley networks inferred to have been sourced by precipitation during the era of valley network formation > 3.7 Ga and may be used to quantitatively constrain precipitation and aridity during early Mars.

Stucky De Quay, G.↗
NASA NTRS2020

Superorbital Modulation in the High-Mass X-ray Binary 4U 1538−52, and Possible Modulation in IGR J16393−4643

Hard X-ray observations with the Neil Gehrels Swift Observatory Burst Alert Telescope (BAT) reveal superorbital modulation in the wind-accreting supergiant high-mass X-ray binary (HMXB) 4U 1538−52 at a period of 14.9130±0.0026days that is consistent with four times the 3.73 day orbital period. These periods agree with a previously suggested correlation between superorbital and orbital periods in similar HMXBs. During the∼14 years of observations the superorbital modulation changes amplitude, and since ∼MJD 57,650 it was no longer detected in the power spectrum, although a peak near the second harmonic of this was present for some time. Measurements of the spin period of the neutron star in the system with the Fermi Gamma-ray Burst Monitor show a long-term spin-down trend which halted towards the end of the lightcurve, suggesting a connection between ̇P spin and superorbital modulation, as proposed for 2S 0114+650.However, an earlier torque reversal from INTEGRAL observations was not associated with superorbital modulation changes. B and V band photometry from the Las Cumbres Observatory reveals orbital ellipsoidal photometric variability, but no superorbital optical modulation. However the photometry was obtained when the 14.9130 day period was no longer detected in the BAT power spectrum. We revisit possible superorbital modulation in BAT observations of IGR J16393−4643 but cannot conclusively determine whether this is present, although is not persistent. We consider superorbital modulation mechanisms, and suggest that the Corotation Interaction Region model, with small deviations from orbital synchronization, appears promising.

Robin H D Corbet↗
DOE OSTI2022

Post-Combat-Injury Opioid Prescription and Alcohol Use Disorder in the Military

Previous studies have identified combat exposure and combat traumatic experience as problematic drinking risk factors. Increasing evidence suggests that opioid use increases the risk of alcohol use disorder. This study investigated the association between opioid prescription use after injury and (1) alcohol use disorder and (2) severity of alcohol use disorder among deployed military servicemembers. Deidentified health records data of 9,029 deployed servicemembers from a retrospective cohort study were analyzed. Data were randomly selected from the Department of Defense Trauma Registry and included servicemembers with combat injuries during deployment in Iraq or Afghanistan (2002–2016). Pharmacy records and International Classification of Diseases, Ninth and Tenth Revision diagnosis codes were used. Three groups were identified (no opioid prescription use, nonpersistent opioid prescription use, and persistent opioid prescription use) and were compared on the basis of alcohol use disorder risk using Cox proportional hazard models. Data analyses were performed in 2021. Of the 9,029 servicemembers with combat injury, 2,262 developed alcohol use disorder (1,322 developed severe alcohol use disorder). Compared with no opioid prescription use, increased alcohol use disorder risk was associated with persistent opioid prescription use, with a hazard ratio of 1.13 (95% CI=1.02, 1.26). After covariate adjustment, increased risk remained statistically significant (hazards ratio=1.24; 95% CI=1.10, 1.39). There was no significant difference in alcohol use disorder risk between no opioid prescription use and nonpersistent opioid prescription use. The risk of severe alcohol use disorder did not vary by opioid use among servicemembers with alcohol use disorder diagnosis. Furthermore, the findings of the study suggest that the incidence of alcohol use disorder was higher among injured servicemembers with persistent opioid prescription use than among those without opioid use. If replicated in prospective studies, the findings highlight the need for clinicians to consider the current and history of alcohol use of patients in initiating treatment involving opioids.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Effect of proton irradiation temperature on persistent photoconductivity in zinc oxide metal-semiconductor-metal ultraviolet photodetectors

The electrical and structural characteristics of 50-nm-thick zinc oxide (ZnO) metal-semiconductor-metal ultraviolet (UV) photodetectors subjected to proton irradiation at different temperatures are reported and compared. The devices were irradiated with 200 keV protons to a fluence of 1016 cm−2. Examination of the x-ray diffraction (XRD) rocking curves indicates a preferred (100) orientation prior to irradiation, with decrease in crystal quality afterward. Additionally, peak shifts in XRD and Raman spectra of the control sample relative to well-known theoretical positions are indicative of tensile strain in the as-deposited ZnO films. Shifts toward theoretical unstrained positions are observed in the irradiated films, which indicates partial relaxation. Raman spectra also indicate increase in oxygen vacancies (VO) and zinc interstitial defects (Zni) compared to the control sample. Additionally, transient photocurrent measurements performed on each sample at different temperatures showed up to 2× increase in photocurrent decay time constants for irradiated samples vs the control. This persistent photoconductive behavior is linked to the activation of electron and hole traps near the surface, and to the desorption and reabsorption of O2 molecules on the ZnO surface under the influence of UV light. Using an Arrhenius model, trap activation energies were extracted and, by comparing with known energies from the literature, the dominant defects contributing to persistent photoconductivity for each irradiation condition were identified. The persistence of differences in photocurrent transients between different samples months after irradiation indicates that the defects introduced by the suppression of thermally activated dynamic annealing processes have a long-term deleterious effect on device performance.

Heuser, Thomas A. (ORCID:0000000225642400)↗
DOE OSTI2025

Evaluating mesoscale model predictions of diurnal speedup events in the Altamont Pass Wind Resource Area of California

Mesoscale model predictions of wind, turbulence, and wind energy capacity factors are evaluated in the Altamont Pass Wind Resource Area of California (APWRA), where the diurnal regional sea breeze and associated terrain-driven speedup flows drive wind energy production during the summer months. Results from the Weather Research and Forecasting model version 4.4 using a novel three-dimensional planetary boundary layer (3D PBL) scheme, which treats both vertical and horizontal turbulent mixing, are compared to those using a well-established one-dimensional (1D) scheme that treats only vertical turbulent mixing. Each configuration is evaluated over a nearly 3-month-long period during the Hill Flow Study, and due to the recurring nature of the observed speedup flows, diurnal composite averaging is used to capture robust trends in model performance. Both model configurations showed similar overall skill. The general timing and direction of the speedup flows is captured, but their magnitude is overestimated within a typical wind turbine rotor layer. Both also fail to capture a persistent observed near-surface jet-like flow, likely due to the limited grid resolution that is typical of mesoscale models. However, the 3D PBL configuration shows several minor improvements over the 1D PBL configuration, including improved wind speed and turbulence kinetic energy profiles during the accelerating phase of the speedup events, as well as reduced positive wind speed bias at surface stations across the APWRA region. Using a mesoscale wind farm parameterization, modeled capacity factors are also compared to monthly data reported to the US Energy Information Administration (EIA) during the study period. Although the monthly trend in the data is captured, both model configurations overestimate capacity factors by roughly 7 %–11 %. Through model evaluation, this study provides confidence in the 3D PBL scheme for wind energy applications in complex terrain and provides guidance for future testing.

17 WIND ENERGY↗
NASA NTRS2022

Measurement of Surface Deformation Related to the December 2018 Mt. Etna Eruption Using Time-Series Interferometry and Magma Modeling for Hazard Zone Mapping

Mount Etna has erupted several times since it was first formed. Recently, Mount Etna began erupting again over 24–27 December 2018. Because it erupts frequently, Mount Etna should be observed on a frequent basis. From June 2018 to October 2019, 34 and 56 interferometric synthetic aperture radar (InSAR) images were acquired from the ascending and descending tracks of the Sentinel-1 satellite, respectively. We employed the Stanford Method for Persistent Scatterers (StaMPS) and a refined small baseline subset (SBAS) InSAR method to produce a surface deformation time-series map. In the time-series analysis, the phase signal remained unaltered with time. The Okada model was then applied to the result to generate a modeled interferogram, and the Q-LavHA program was run to generate a lava flow prediction model. A direct comparison of the results showed that Persistent Scatterers Interferometry (PSI)-StaMPS and the refined SBAS technique were comparable in terms of the displacement pattern, with slightly different velocity values obtained for individual points. In particular, a velocity range of −25 to 21 cm/yr was obtained from PSI-StaMPS, whereas a range of −30 to 25 cm/yr was obtained from the refined SBAS method. Upon computation of the vertical and east-west displacement components based on ascending and descending track data using both methods, deformation velocities of 51.5 and 52.5 cm/yr in the westerly direction on the western flank of Mount Etna were obtained from PSI-StaMPS and the refined SBAS method, respectively, whereas on the eastern flank, deformation toward the east was estimated to occur at a velocity of 50.1 or 54.2 cm/yr, respectively. PSIStaMPS estimated a vertical deformation velocity of −5.3 to 18.3 cm/yr, whereas the refined SBAS method produced a velocity range of approximately −7 to 19 cm/yr. The interferogram obtained via Okada modeling showed two fault sources in the 2018 Mount Etna eruption and a total volume change of approximately 12.39 × 10 6 m 3 . From the modeling results, a lava flow prediction model was generated using the Q-LavHA program. The approaches described in this study can be used by government officials, authorities, and other decision-makers to monitor and assess the risk of volcanic activity in the region.

Suci Ramayanti↗
DOE OSTI2025

Quantifying precursors to void nucleation and coalescence in aluminum

Ductile rupture is a common failure mode for engineering alloys. It is generally comprised of three mechanisms: void nucleation at secondary particles, void growth, and coalescence of voids. Conventional models for ductile rupture have limited precision for predicting macroscopic failure. This is partially because they have been corroborated using ex-situ observations of these three mechanisms and calibrated by macroscopic strain or stress metrics. In this study, in-situ high-energy X-ray characterization was conducted to correlate sites of void nucleation via particle cracking and sites of void growth with grain-scale metrics. Here it is shown that particle cracking is not predicated by elevated stress metrics, which disagrees with classical models. Instead, particle cracking tended to occur for the largest, least spherical particles. This trend persisted on the aggregate-scale and within individual neighborhoods around particles. Furthermore, an Eshelby analysis illuminated a statistically significant increase in maximum principal stress within a cracked particle, compared to an uncracked particle. In-situ observations also revealed two separate examples of intragranular void growth comprised of flat, crack-like features that grew showing alignment with slip systems of the highest resolved shear stress. Post-mortem fractography revealed a secondary population of dimples on these crack-like features, implying that void sheeting may be occurring during this crack-like void growth. Furthermore, these in-situ observations imply that classical models for void growth, that assume a homogenous medium, should be extended to account for the anisotropic grain-level behavior to correctly capture distinct features of void nucleation and growth.

Al-2219↗
DOE OSTI2019

Trans-Himalayan transport of organochlorine compounds: Three- year observations and model-based flux estimation

Due to their low temperature and high precipitation, high mountains can trap semi-volatile chemicals, such as persistent organic pollutants (POPs), and hinder their dispersion. However, deep convection occurring at high elevation facilitates the upward transport of POPs, and mountain valleys provide channels for regional transport of POPs. The concerted impact of these processes on the transport of contaminants across a mountain range has not been investigated before. In this study, we conducted a three-year passive air sampling campaign along a south-north altitudinal transect (100-5200m) across the central Himalayas, the highest mountain range on Earth. A multi-compartment contaminant fate model was developed to simulate the fate and transport of POPs along this transect and an adjacent mountain valley. The results show that driven by the strong Indian monsoon, POPs emitted in the lowlands at the foot of the Himalayas can be transported northward to high altitudes and further to the inner part of the Tibetan Plateau. Modeling suggests that more than 90% of POPs are trapped along the way due to gaseous deposition to soil and foliage and rainfall scavenging; we estimate that in spite of this removal, 2×10-3 to 1×10-1 Giga-grams of POPs are transported across the Himalayas every year. This indicates that despite their height the Himalayas are not a perfect barrier to the North-bound transport of POPs. We further compared the contributions that valleys and high altitudes make to the transport of POPs. The transport flux along valleys is 2-3 times higher than that across the mountain ridge. However, due to the limited spatial coverage of mountain valleys, the amount of POPs transported through valleys only accounts for a small part of the total transport, demonstrating that high altitude transport across the mountain ridge is the dominant transport pathway. This study shows that POPs can overcome the blocking effect of the Himalayas and the transport does not depend on the ability to pass through lower-lying mountain passes.

Gong, Ping↗
NASA NTRS2023

Spatial and Temporal Characterization of Cyanobacteria Blooms in the Mississippi Sound and Their Relationship to the Bonnet Carré Spillway Openings

During the spring and summer of 2019, an unprecedented cyanobacterial harmful algal bloom (cyanoHAB) was responsible for beach advisories on 25 beaches along the Mississippi Sound for over 3 months. Due to the preceding heavy rainfall and flooding within the Mississippi River watershed, for the first time in history, the Bonnet Carré Spillway (BCS) opened twice in one year during 2019. The coastal cyanoHAB coincided with the second BCS opening. The main objectives of this study were: (1) to investigate the potential for using the National Aeronautics and Space Administration (NASA) ocean color standard Cyanobacteria Index (CIcyano) algorithm to characterize the spatial and temporal extent of the 2019 cyanoHAB; (2) to couple the CIcyano data with river discharge, salinity, and modeled-wind data to study the conditions leading to the cyanoHAB and factors aiding the advection and persistence of the bloom within the Mississippi Sound, including a possible relationship to the BCS; (3) to further investigate the relationship with the BCS by repeating the methods using data from 2018, which was a year when the BCS was opened but no evidence of cyanoHABs was reported along the Mississippi coast. Weekly means and monthly frequency CIcyano images, river discharge, salinity, and modeled-wind data from February to September of 2018 and 2019 were analyzed, which coincide with three BCS openings. In March 2018, a cyanobacteria bloom was observed within Lake Pontchartrain coinciding with the BCS opening; however, the month-long bloom was contained to the lake. Two distinct cyanoHABs were observed in 2019 and both blooms were advected into the Mississippi Sound, and likely contributed to the 3-month-long beach water advisories of 2019 along the Mississippi coastline. From March to mid-July 2019, salinity at stations within the Mississippi Sound was consistently near zero indicating high levels of freshwater. During that time, winds were predominantly northwestward, preventing the BCS waters from flushing into the Mississippi Shelf and resulting in BCS waters remaining longer within the estuarine lakes and Mississippi Sound. Although the BCS had an undeniable impact on the presence of the coastal cyanoHAB of 2019, other variables including wind direction, water flow, mixing, and persistence of freshwater within the Sound can determine the intensity and extent of the cyanoHABs. Coupling in situ phytoplankton information from freshwater water bodies to the marine continuum along with water flow, wind data, and satellite imagery could help identify cyanoHABs at early stages and forecast their trajectory and potential impacts on coastal areas.

Bonnet Carré Spillway↗
DOE OSTI2020

Concordance cosmology?

ABSTRACT We propose a new intuitive metric for evaluating the tension between two experiments, and apply it to several data sets. While our metric is non-optimal, if evidence of tension is detected, this evidence is robust and easy to interpret. Assuming a flat Lambda cold dark matter (ΛCDM) cosmological model, we find that there is a modest 2.2σ tension between the Dark Energy Survey (DES) Year 1 results and the Planck measurements of the cosmic microwave background. This tension is driven by the difference between the amount of structure observed in the late-time Universe and that predicted from fitting the Planck data, and appears to be unrelated to the tension between Planck and local estimates of the Hubble rate. In particular, combining DES, baryon acoustic oscillations, big bang nucleosynthesis, and supernovae measurements recover a Hubble constant and sound horizon consistent with Planck, and in tension with local distance–ladder measurements. If the tension between these various data sets persists, it is likely that reconciling all current data will require breaking the flat ΛCDM model in at least two different ways: one involving new physics in the early Universe, and one involving new late-time Universe physics.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2005

Nebula Models of Non-Equilibrium Mineralogy: Wark-Lovering Rims

Introduction: The meteorite record contains several examples of minerals that would not persist if allowed to come to equilibrium with a cooling gas of solar composition. This includes all minerals in CAIs and AOAs. Their survival is generally ascribed to physical removal of the object from the gas (isolation into a large parent object, or ejection by a stellar wind), but could also result from outward radial diffusion into cooler regions, which we discuss here. Accretion of CAIs into planetesimals has also been relied on to preserve them against loss into the sun. However, this suggestion faces several objections. Simple outward diffusion in turbulence has recently been modeled in some detail, and can preserve CAIs against loss into the sun [2]. Naturally, outward radial diffusion in turbulence is slower than immediate ejection by a stellar wind, which occurs on an orbital timescale. Here we ask whether these different transport mechanisms can be distinguished by nonequilibrium mineralogy, which provides a sort of clock. Our application here is to one aspect of CAI mineralogy - the Wark-Lovering rims (WLR); even more specifically, to alteration of one layer in the WLR sequence from melilite (Mel) to anorthite (An).

Cuzzi, J. N.↗
DOE OSTI2019

On Bridging A Modeling Scale Gap: Mesoscale to Microscale Coupling for Wind Energy

Accurately representing flow across the mesoscale to the microscale is a persistent roadblock for completing realistic microscale simulations. The science challenges that must be addressed to coupling at these scales include the following: 1) What is necessary to capture the variability of the mesoscale flow, and how do we avoid generating spurious rolls within the terra incognita between the scales? 2) Which methods effectively couple the mesoscale to the microscale and capture the correct nonstationary features at the microscale? 3) What are the best methods to initialize turbulence at the microscale? 4) What is the best way to handle the surface-layer parameterizations consistently at the mesoscale and the microscale? 5) How do we assess the impact of improvements in each of these aspects and quantify the uncertainty in the simulations? The U.S. Department of Energy Mesoscale-to-Microscale-Coupling project seeks to develop, verify, and validate physical models and modeling techniques that bridge the most important atmospheric scales determining wind plant performance and reliability, which impacts many meteorological applications. The approach begins with choosing case days that are interesting for wind energy for which there are observational data for validation. The team has focused on modeling nonstationary conditions for both flat and complex terrain. This paper describes the approaches taken to answer the science challenges, culminating in recommendations for best approaches for coupled modeling.

17 WIND ENERGY↗
DOE OSTI2019

Magnetic Reconnection in Three Dimensions: Modeling and Analysis of Electromagnetic Drift Waves in the Adjacent Current Sheet

Magnetic reconnection at the subsolar magnetopause is persistently accompanied by strong fluctuations of the magnetic field (B), plasma density (n), and all components of the electric field (E) and current (J). The strongest fluctuations are at frequencies below the lower hybrid frequency and observed in a thin, intense current sheet adjacent to the electron diffusion region. In this current sheet, the background magnitudes of B and n are changing considerably, creating an inhomogeneous plasma environment. In this paper, we show that the fluctuations in B and n are consistent with an oscillatory displacement of the current sheet in the surface normal direction. The displacement is propagating parallel to the magnetic reconnection X-line. Wavelengths are on the order of or longer than the thickness of the current sheet to which they are confined, so we label these waves electromagnetic drift waves. E and J fluctuations are more complex than a simple displacement. They have significant variations in the component along B, which suggest that the drift waves also may be confined along B. The current sheet is supported by an electron drift driven by normal electric field, which, in turn, is balanced by an ion pressure gradient. We suggest that wave growth comes from an instability related to the drift between the electrons and ions. We discuss the possibility that drift waves can displace or penetrate into the electron diffusion region giving magnetic reconnection three-dimensional structure. Drift waves may corrugate the X-line, possibly breaking the X-line and generating turbulence.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

Evaluating WRF-Chem aerosol indirect effects in Southeast Pacific marine stratocumulus during VOCALS-REx

We evaluate a regional-scale simulation with the WRF-Chem model for the VAMOS (Variability of the American Monsoon Systems) Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx), which sampled the Southeast Pacific's persistent stratocumulus deck. Evaluation of VOCALS-REx ship-based and aircraft observations focuses on analyzing how aerosol loading affects marine boundary layer (MBL) dynamics and cloud microphysics. We compare local time series and campaign averaged longitudinal gradients, and highlight differences in model simulations with (W) and without wet (NW) deposition processes. The higher aerosol loadings in the NW case produce considerable changes in MBL dynamics and cloud microphysics, in accordance with the established conceptual model of aerosol indirect effects. These include increase in cloud albedo, increase in MBL and cloud heights, drizzle suppression, increase in liquid water content, and increase in cloud lifetime. Moreover, better statistical representation of aerosol mass and number concentration improves model fidelity in reproducing observed spatial and temporal variability in cloud properties, including top and base height, droplet concentration, water content, rain rate, optical depth (COD) and liquid water path (LWP). Together, these help to quantify confidence in WRF-Chem's modeled aerosol-cloud interactions, while identifying structural and parametric uncertainties including: irreversibility in rain wet removal; overestimation of marine DMS and sea salt emissions and accelerated aqueous sulfate conversion. Our findings suggest that WRF-Chem simulates marine cloud-aerosol interactions at a level sufficient for applications in forecasting weather and air quality and studying aerosol climate forcing, including the reliability required for policy analysis and geo-engineering applications.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Reactive cluster model of metallic glasses

Though discovered more than a half century ago metallic glasses remain a scientific enigma. Unlike crystalline metals, characterized by short, medium, and long-range order, in metallic glasses short and medium-range order persist, though long-range order is absent. This fact has prompted research to develop structural descriptions of metallic glasses. Among these are cluster-based models that attribute amorphous structure to the existence of clusters that are incommensurate with crystalline periodicity. Not addressed, however, are the chemical factors stabilizing these clusters and promoting their interconnections. We have found that glass formers are characterized by a rich cluster chemistry that above the glass transformation temperature promotes exchange as well as static and vibronic sharing of atoms between clusters. The vibronic mechanism induces correlated motions between neighboring clusters and we hypothesize that the distance over which these motions are correlated mediates metallic glass stability and influences critical cooling rates.

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

Electronic coupling through natural amino acids

Myriad scientific domains concern themselves with biological electron transfer (ET) events that span across vast scales of rate and efficiency through a remarkably fine-tuned integration of amino acid (AA) sequences, electronic structure, dynamics, and environment interactions. Within this intricate scheme, many questions persist as to how proteins modulate electron-tunneling properties. To help elucidate these principles, we develop a model set of peptides representing the common α-helix and β-strand motifs including all natural AAs within implicit protein-environment solvation. Using an effective Hamiltonian strategy with density functional theory, we characterize the electronic coupling through these peptides, furthermore considering side-chain dynamics. For both motifs, predictions consistently show that backbone-mediated electronic coupling is distinctly sensitive to AA type (aliphatic, polar, aromatic, negatively charged and positively charged), and to side-chain orientation. The unique properties of these residues may be employed to design activated, deactivated, or switch-like superexchange pathways. Electronic structure calculations and Green’s function analyses indicate that localized shifts in the electron density along the peptide play a role in modulating these pathways, and further substantiate the experimentally observed behavior of proline residues as superbridges. The distinct sensitivities of tunneling pathways to sequence and conformation revealed in this electronic coupling database help improve our fundamental understanding of the broad diversity of ET reactivity and provide guiding principles for peptide design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗