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Results for “Local vibrational mode spectroscopy”

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At least 19 records

Defect-induced phonon-resonant scattering and its influence on thermal transport of irradiated thorium-dioxide

Thermal transport in proton irradiated thorium-dioxide (ThO 2 ) is investigated. Using a combination of experiments and first-principles computational framework, the role of lattice defects on thermal conductivity is analyzed. A resonant-phonon scattering mechanism beyond the traditionally considered Rayleigh scattering is found to significantly influence low-temperature thermal transport in the presence of irradiation-induced point defects. The existence of localized phonon modes associated with irradiation-induced defects is suggested by the inability of the first-principles based thermal conductivity model—which considers only three-phonon interactions and phonon-defects scattering using the Tamura formalism—to predict the experimental results, unless a resonant scattering mechanism is included. The emergence of additional peaks in the Raman spectra in the proximity of phonon-resonant frequency provides further evidence for the existence of localized modes. Coupled with a microstructure evolution model, this analysis enables more accurate analysis for contrasting the contributions of different phonon scattering mechanisms across all irradiation doses and temperatures.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Compensation mechanism in liquid encapsulated Czochralski GaAs Importance of melt stoichiometry

It is shown that the key to reproducible growth of undoped semi-insulating GaAs by the liquid encapsulated Czochralski (LEC) technique is the control over the melt stoichiometry. Twelve crystals were grown from stoichiometric and nonstoichiometric melts. The material was characterized by secondary ion mass spectrometry, localized vibrational mode far infrared spectroscopy, Hall-effect measurements, optical absorption, and photoluminescence. A quantitative model for the compensation mechanism in the semi-insulating material was developed based on these measurements. The free carrier concentration is controlled by the balance between EL2 deep donors and carbon acceptors; furthermore, the incorporation of EL2 is controlled by the melt stoichiometry, increasing as the As atom fraction in the melt increases. As a result, semi-insulating material can be grown only from melts above a critical As composition. The practical significance of these results is discussed in terms of achieving high yield and reproducibility in the crystal growth process.

Holmes, D. E.

Single-Atom-Resolved Vibrational Spectroscopy of a Dislocation

Dislocations in III-nitride semiconductors impede heat transport, leading to localized overheating, which severely limits the performance and reliability of optoelectronic and power devices. Current research on phonon–dislocation interactions primarily addresses bulk materials, focusing on the average effects at specific dislocation densities. However, phonon resistance from dislocation scattering arises from both short-range core interactions and long-range strain field interactions, which remain largely unexplored. Here, in this study, electron energy-loss spectroscopy is used to investigate a GaN dislocation. Vibrational modes localized on specific core atoms are revealed, reflecting short-range interactions. Additionally, phonon energy shifts driven by strain fields surrounding the dislocation are observed, reflecting long-range interactions. Ab initio calculations support these findings and draw out additional details. This work establishes a paradigm for probing defect-induced phonon scattering at the single-atom level, revealing how dislocations affect phonon behavior through atomic reconstruction and strain engineering, thus offering insights for designing improved material functionalities.

III-nitride semiconductors

Deciphering the local structure of Prussian blue analogue cathodes with Raman spectroscopy for sodium-ion batteries

Iron-based Prussian blue analogues (PBAs) have gained attention as low-cost, relatively higher-potential cathodes for sodium-ion batteries, due to their open 3D-framework structures. However, understanding the local structural changes is critical to unveiling the intercalation pathways and degradation mechanisms. We employ here operando Raman spectroscopy to probe the changes in the cyanide vibrational modes during cycling and degradation after cycling, which are not adequately resolved by X-ray diffraction due to the low structure factor and limited X-ray sensitivity of the cyanide groups. Vibrational spectroscopy has thus proven essential for deciphering these complex materials. Additionally, we implement pre-sodiation strategies to assess the impact of sodium inventory loss by pairing PBAs with a hard carbon anode in a full-cell configuration. Operando galvanostatic electrochemical impedance spectroscopy (EIS) and ex situ X-ray photoelectron spectroscopy (XPS) further elucidate the interface evolution and the role of water molecules in forming the cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI). The insights gained advance the understanding of PBAs and enhance their practical viability.

25 ENERGY STORAGE

Mechanism of Lithium Ion Exchange Into Spinel Manganese Oxide

Lithium manganese oxide (LMO) is an effective absorbent for lithium recovery from brines, characterized by its high adsorption capacity, excellent regeneration performance, and selectivity. Here, this study investigates the mechanisms of material degradation during lithium loading and unloading in LMO, employing a combination of time‐resolved Raman spectroscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy. Key findings reveal that the A 1g vibrational mode wavenumber shifts from 635 cm −1 at the onset of lithium ion exchange to 656 cm −1 after 12 min, indicating local symmetry loss and manganese (Mn) loss during lithium intercalation. The proposed lithium exchange mechanism involves initial occupation of tetrahedral interstitial voids, followed by migration into interstitial sites between Mn octahedral sites. Computational modeling suggests that the loss of symmetry in MnO cubane‐like groups occurs as lithium migrates, significantly affecting the Raman spectra. Importantly, the study demonstrates that after 100 cycles of lithium/hydrogen loading, a 24% loss in Mn is observed, which correlates with decreased structural stability; however, the structural integrity of LMO is enhanced when subjected to multiple cycles without complete loading. Here, these insights contribute to the understanding of LMO's performance in lithium recovery applications and highlight potential strategies to optimize its use in future technologies.

15 GEOTHERMAL ENERGY

How Proton Incorporation Reshapes Lattice Dynamics In BaSnO 3 ‐Type Proton Conductors

Proton conduction in acceptor-doped perovskites is fundamentally a vibronic process: mobile H + and D + do not move independently, but dynamically co-vibrate with the surrounding oxygen–metal framework. Direct experimental evidence for this behavior is presented using in situ 119⁢ 𝑆⁢𝑛 nuclear resonance vibrational spectroscopy (NRVS) on hydrated, deuterated, and dry 𝐵⁢𝑎⁢𝑆⁢𝑛 1−𝑥⁢ 𝑌 𝑥 ⁢𝑂 3−𝛿 . Hydration induces systematic redistributions in the Sn-projected phonon density of states (PDOS), including an upshift of the first spectral moment by about 0.4 meV, indicating a stiffening of the extended Sn–O network. H/D isotopic substitution leaves the Sn-projected PDOS largely unchanged, with only subtle isotope-dependent spectral reweighting, demonstrating that protonic degrees of freedom are not localized oscillators but are embedded in collective lattice modes. These results are rationalized using a classical coupled proton–phonon oscillator model that links the observed PDOS variations to changes in effective force constants and vibrational mass terms. The model captures how H + and D + participate in cooperative lattice dynamics rather than forming isolated OH/OD entities. Overall, NRVS probes proton–lattice coupling in ceramic proton conductors and quantitatively describes how protonic defects modulate host lattice dynamics to enable phonon-assisted long-range proton transport.

36 MATERIALS SCIENCE

Ferroelastic Domain-Induced Electronic Modulation in Halide Perovskites

Lead halide perovskites have emerged as promising materials for optoelectronic applications due to their exceptional properties. In the all-inorganic CsPbBr 3 perovskites, ferroelastic domains formed during phase transitions enhance bulk transport and emissive efficiency. However, the microscopic mechanisms governing carrier dynamics remain poorly understood. In this study, we employ cathodoluminescence (CL) and micro-Raman spectroscopy to image and investigate the electronic properties of the ferroelastic domain walls in CsPbBr 3 single crystals. CL measurements reveal a reduced emissive yield and a slight redshift in emission at the domain walls. Further, micro-Raman studies provide spatially resolved mapping of vibrational modes, exhibiting second-order phonon modes localized at the domain boundaries. In conclusion, our findings suggest that electron–phonon coupling at the twin domain walls plays a critical role in facilitating efficient charge separation, thereby improving the optoelectronic performance of the CsPbBr 3 perovskites.

Carrier dynamics

X-ray dichroism as a probe of orbital quenching and unquenching induced by optically excited Jahn-Teller modes

The use of soft-X-ray spectroscopy to probe changes in the ground-state due to vibronic excitations is studied. The changes in L-edge X-ray absorption on divalent cobalt in the presence of a vibrating Jahn-Teller distortion are calculated. For linear dichroism, a strong dependence on the distortion is obtained reflecting the change in the local quadrupole moment due to the changes in the xy versus yz/zx hole densities during the oscillation. Here, in the presence of a magnetic moment, significant variations in the circular dichroic signal are obtained related to the quenching and unquenching of the orbital angular momentum.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Low-cost calculation and analysis of 2D IR spectra of model diiron trinitrosyl complexes in the NO stretch region with vibrational perturbation theory

Two-dimensional infrared spectroscopy offers unique capabilities for probing vibrational coupling in complex metal–ligand systems. In this paper, we combine two-dimensional infrared spectroscopy with vibrational perturbation theory to investigate vibrational coupling in a diiron trinitrosyl complex across three stable redox states. Although these systems are challenging for electronic structure methods, we demonstrate that key features of experimental 2D IR spectra can be accurately reproduced using reduced-dimensional anharmonic calculations with a small harmonic frequency scaling. Analysis reveals that N–O stretching modes maintain high locality across all redox states, with coupling patterns that directly reflect variations in Fe–N bond strength. Using curvilinear coordinate analysis, we demonstrate these differences result from systematic changes in cubic anharmonic force constants rather than mode delocalization. Our results establish N–O stretches as sensitive probes of metal–ligand bonding strength, expanding the toolkit for studying biologically relevant nitrosyl complexes.

Moran, Hayden A. [Texas A&M University, College St

Exploring Local Vibrational Structure in Protein-Bound Chlorophyll a: Isotope-Enrichment Experiments and Electrostatic Analysis

Local chlorophyll (Chl) vibrations play an essential role in biological photosynthesis by facilitating rapid energy transfer between pigments. In research studies, they also provide a useful spectroscopic probe of the local protein environment that surrounds each pigment. However, measuring the complete vibrational absorption spectrum of a protein-bound Chl molecule is much more difficult than, for example, Chl in neat solvent due to overlap with protein vibrations that typically drown out Chl vibrational features. Resonance Raman and fluorescence spectroscopies provide a way around this problem for Franck–Condon active vibrations, but these often rely on cryogenic measurement conditions and fail to capture vibrational signatures from, e.g., ester-group vibrations that lack coupling to a convenient electronic transition. In the present contribution, we use 13 C-enrichment of the protein backbone to shift protein background signals to lower frequency, providing a largely clean spectral window in which to study local Chl a C═O stretch modes. A room-temperature absorption spectrum for Chl a in the water-soluble chlorophyll protein (WSCP) of Lepidium virginicum is thus extracted as a difference between protein-plus-pigment and protein-only vibrational spectra. Excellent agreement in the molecular fingerprint region with the vibrational spectrum of Chl a in organic solvents confirms that the resulting spectrum represents the response of the protein-bound Chl a molecule. Furthermore, the ester group resonance is observed to shift in response to the S53P mutation that eliminates a 17 3 ester group hydrogen bond from the protein environment. Finally, we analyze these experimental results using MD-based electrostatic analysis, finding that electric-field mapping at the C atom of the ester group provides a satisfactory explanation for the observed frequency shifts between organic solvent and protein environment. MD analysis further suggests that a red-shifted ester peak observed experimentally for the S53P mutant results from solvation of the 17 3 Chl ester group due increase water penetration into the Chl-binding pocket relative to wild-type WSCP. Here, we anticipate that these results will prove useful both for benchmarking future simulation work and as a reference for interpreting Chl vibrational spectra as a probe of pigment–protein interactions.

14 SOLAR ENERGY

Imaging Bias‐Driven Domain Wall Motion With Scanning Oscillator Piezoresponse Force Microscopy

Understanding ferroelectric domain wall dynamics at the nanoscale across a broad range of timescales requires measuring domain wall position under different applied electric fields. The success of piezoresponse force microscopy (PFM) as a tool to apply local electric fields at different positions and imaging their changing position, together with the information obtained from associated switching spectroscopies has fueled numerous studies of the dynamics of ferroelectric domains to determine the impact of intrinsic parameters such as crystalline order, defects and pinning centers, as well as boundary conditions such as environment. However, the investigation of sub-coercive reversible domain wall vibrational modes requires the development of new tools that enable visualizing domain wall motion under varying applied fields with high temporal and spatial resolution while also accounting for spurious electrostatic effects. Here, scanning oscillator piezoresponse force microscopy extends the investigation of domain wall dynamics to new regimes, providing direct visualization of domain wall position as a function of an external electric field that varies in time and location. In conclusion, this enables studying the energetics of field-driven ferroelectric domain wall motion, which is shown to obey a thermally activated flow regime in the millisecond timescale.

Piezoresponse Force Microscopy

Geometric control of magnetic domain morphology in electrodeposited Ni rich NiPt mesoscopic wires

In this paper, we study the electrodeposited Ni—Pt magnetic wires, exploring the mechanisms by which changes in geometry and composition influence the local magnetic structure. The samples were prepared by electrodeposition, their elemental composition was analyzed by energy dispersive X-ray spectroscopy, and phase analysis was carried out by an X-ray diffraction measurement. Magnetic force microscopy measurements, and magnetic force microscopy measurements in magnetic field were carried out to study the domain morphology of the prepared samples. Magnetization characteristics were measured via vibrating sample magnetometry mode of a superconducting quantum interference device. Here, the results were analyzed and compared with micromagnetic simulations. It is shown that a strong perpendicular magnetic anisotropy is responsible for the characteristic checkerboard-like surface magnetization patterns, which can be tuned by geometrical constriction and Ni content. Understanding these relationships provides insights into the design of magnetic materials with tailored properties for advanced applications, like magnetic sensors.

Binary alloy

Trapping light in air with membrane metasurfaces for vibrational strong coupling

Optical metasurfaces can manipulate electromagnetic waves in unprecedented ways at ultra-thin engineered interfaces. Specifically, in the mid-infrared (mid-IR) region, metasurfaces have enabled numerous biochemical sensing, spectroscopy, and vibrational strong coupling (VSC) applications via enhanced light-matter interactions in resonant cavities. However, mid-IR metasurfaces are usually fabricated on solid supporting substrates, which degrade resonance quality factors (Q) and hinder efficient sample access to the near-field electromagnetic hotspots. Besides, typical IR-transparent substrate materials with low refractive indices, such as CaF 2 , NaCl, KBr, and ZnSe, are usually either water-soluble, expensive, or not compatible with low-cost mass manufacturing processes. Here, we present novel free-standing Si-membrane mid-IR metasurfaces with strong light-trapping capabilities in accessible air voids. We employ the Brillouin zone folding technique to excite tunable, high-Q quasi-bound states in the continuum (qBIC) resonances with our highest measured Q-factor of 722. Leveraging the strong field localizations in accessible air cavities, we demonstrate VSC with multiple quantities of PMMA molecules and the qBIC modes at various detuning frequencies. Our new approach of fabricating mid-IR metasurfaces into semiconductor membranes enables scalable manufacturing of mid-IR photonic devices and provides exciting opportunities for quantum-coherent light-matter interactions, biochemical sensing, and polaritonic chemistry. The authors introduce a mid-IR metasurface fabricated by decorating a free-standing Si-membrane with air holes. The enhanced light-matter interactions in such air cavities enable vibrational strong coupling and advanced biochemical sensing.

infrared spectroscopy

Coherent anti-Stokes Raman scattering with squeezed light: CARS for quantum-enhanced spectroscopy and imaging

We theoretically investigate quantum-enhanced coherent anti-Stokes Raman scattering (CARS) using squeezed light to amplify vibrational transition rates at low photon flux. Quantum sensing approaches are needed for nondestructive nanometrology such as in bioimaging where reduced photodamage is desired while retaining resolution and sensitivity. We analyze both single-mode squeezing applied to the pump field and two-mode squeezing between the pump and Stokes fields. We also show that the ordering of displacement and squeezing operations—whether displacement precedes squeezing or squeezing precedes displacement—has an impact on the resulting CARS transition amplitudes due to a difference in the photon number and the quantum-enhancement coefficients, with the latter offering a stronger enhancement in the case of two modes squeezing of the pump and Stokes under experimentally accessible conditions. Furthermore, our calculations capture these quantum enhancements through the intrinsic photon-number correlations of squeezed light, eliminating the need for interferometric detection or higher pump powers that are otherwise required to reach comparable sensitivities in classical CARS. Finally, we outline a quantum plasmonic extension of our model in which local field enhancements caused by surface plasmon excitation in metallic nanoparticles can be incorporated via mode-selective field amplification factors, offering a pathway toward combining squeezed-light quantum optics with surface-enhanced nanoscale spectroscopy and imaging.

Atomic & molecular structure

Substrate matters: Coupled phonon modes of a spherical particle on a substrate probed with EELS

Using vibrational electron energy loss spectroscopy (vib-EELS) combined with numerical modeling, we investigate the physical mechanisms governing the phonon coupling between a spherical particle sustaining multipolar surface phonon modes and an underlying thin film. Depending upon their dielectric composition, a variety of hybrid phonon modes arise in the EEL spectrum due to the interaction between polarization charges in the particle and film. Mirror charge effects and phonon mode hybridization are the active mechanisms acting on dielectric and metallic-type films, respectively. Furthermore, processes beyond dipole-dipole interactions are required to describe the sphere-film coupling.

Localized surface phonon response

NASA Tech Briefs, November 2008

Topics covered include: Digital Phase Meter for a Laser Heterodyne Interferometer; Vision System Measures Motions of Robot and External Objects; Advanced Precipitation Radar Antenna to Measure Rainfall From Space; Wide-Band Radar for Measuring Thickness of Sea Ice; Vertical Isolation for Photodiodes in CMOS Imagers; Wide-Band Microwave Receivers Using Photonic Processing; L-Band Transmit/Receive Module for Phase-Stable Array Antennas; Microwave Power Combiner/Switch Utilizing a Faraday Rotator; Compact Low-Loss Planar Magic-T; Using Pipelined XNOR Logic to Reduce SEU Risks in State Machines; Quasi-Optical Transmission Line for 94-GHz Radar; Next Generation Flight Controller Trainer System; Converting from DDOR SASF to APF; Converting from CVF to AAF; Documenting AUTOGEN and APGEN Model Files; Sequence History Update Tool; Extraction and Analysis of Display Data; MRO DKF Post-Processing Tool; Rig Diagnostic Tools; MRO Sequence Checking Tool; Science Activity Planner for the MER Mission; UAVSAR Flight-Planning System; Templates for Deposition of Microscopic Pointed Structures; Adjustable Membrane Mirrors Incorporating G-Elastomers; Hall-Effect Thruster Utilizing Bismuth as Propellant; High-Temperature Crystal-Growth Cartridge Tubes Made by VPS; Quench Crucibles Reinforced with Metal; Deep-Sea Hydrothermal-Vent Sampler; Mars Rocket Propulsion System; Two-Stage Passive Vibration Isolator; Improved Thermal Design of a Compression Mold; Enhanced Pseudo-Waypoint Guidance for Spacecraft Maneuvers; Altimetry Using GPS-Reflection/Occultation Interferometry; Thermally Driven Josephson Effect; Perturbation Effects on a Supercritical C7H16/N2 Mixing Layer; Gold Nanoparticle Labels Amplify Ellipsometric Signals; Phase Matching of Diverse Modes in a WGM Resonator; WGM Resonators for Terahertz-to-Optical Frequency Conversion; Determining Concentration of Nanoparticles from Ellipsometry; Microwave-to-Optical Conversion in WGM Resonators; Four-Pass Coupler for Laser-Diode-Pumped Solid-State Laser; Low-Resolution Raman-Spectroscopy Combustion Thermometry; Temperature Sensors Based on WGM Optical Resonators; Varying the Divergence of Multiple Parallel Laser Beams; Efficient Algorithm for Rectangular Spiral Search; Algorithm-Based Fault Tolerance Integrated with Replication; Targeting and Localization for Mars Rover Operations; Terrain-Adaptive Navigation Architecture; Self-Adjusting Hash Tables for Embedded Flight Applications; Schema for Spacecraft-Command Dictionary; Combined GMSK Communications and PN Ranging; System-Level Integration of Mass Memory; Network-Attached Solid-State Recorder Architecture; Method of Cross-Linking Aerogels Using a One-Pot Reaction Scheme; An Efficient Reachability Analysis Algorithm.

Source record

Libration of hydroxyl groups in layered aluminum (oxy)hydroxides and other material analogs: insights from inelastic neutron scattering and theory

We analyzed the hydroxyl librational signatures of five structurally related aluminum (oxy)hydroxides, using inelastic neutron scattering (INS) and plane-wave lattice dynamics simulations. A clear trend across these aluminum-containing phases illustrates the relationship between hydrogen bonding, local atomic structure, and the spectral location and profile of the librational bands. The INS spectra have been compared to previous optical spectroscopy and computational studies, highlighting the complementary nature of the INS technique. Taking into account other structurally or chemically related material analogs, we have identified a correlation between a blueshift (to higher energy) of the upper librational band edge and the geometry of the hydrogen bond interactions, mirroring (with opposite correlation) the well-known redshift in the intramolecular O–H stretching energy with increasing hydrogen bond strength. For hydroxyl groups that do not participate in hydrogen bonding effectively, the bending librations occur at lower energies and hybridize with metal–oxygen lattice modes. Standard density functional theory approximations, including dispersion corrections, struggle to correctly predict vibrational frequencies of motions dominated by H but perform well for metal–oxygen modes, allowing us to make detailed mode assignments in several cases, including a demonstration of how layer-to-layer disorder in boehmite hydrogen bond orientations is reflected in the sharp but minor low energy peaks (at ∼70–80 meV) of the INS spectrum.

Wang, Hsiu-Wen [Oak Ridge National Laboratory (ORN

Quantitative Species Measurements in Microgravity Combustion Flames using Near-Infrared Diode Lasers

Understanding the physical phenomena controlling the ignition and spread of flames in microgravity has importance for space safety as well as for characterizing dynamical and chemical combustion processes which are normally masked by buoyancy and other gravity-related effects. Unfortunately, combustion is highly complicated by fluid mechanical and chemical kinetic processes, requiring the use of numerical modeling to compare with carefully designed experiments. More sophisticated diagnostic methods are needed to provide the kind of quantitative data necessary to characterize the properties of microgravity combustion as well as provide accurate feedback to improve the predictive capabilities of the models. Diode lasers are a natural choice for use under the severe conditions of low gravity experiments. Reliable, simple solid state operation at low power satisfies the operational restrictions imposed by drop towers, aircraft and space-based studies. Modulation wavelength absorption spectroscopy (WMS) provides a means to make highly sensitive and quantitative measurements of local gas concentration and, in certain cases, temperature. With near-infrared diode lasers, detection of virtually all major combustion species with extremely rapid response time is possible in an inexpensive package. Advancements in near-infrared diode laser fabrication technology and concurrent development of optical fibers for these lasers led to their use in drop towers. Since near-infrared absorption line strengths for overtone and combination vibrational transitions are weaker than the mid-infrared fundamental bands, WMS techniques are applied to increase detection sensitivity and allow measurement of the major combustion gases. In the first microgravity species measurement, Silver et al. mounted a fiber-coupled laser at the top of the NASA 2.2-sec drop tower and piped the light through a single-mode fiber to the drop rig. A fiber splitter divided the light into eight channels that directed the laser beam across a methane or propane diffusion jet flame. The light beams were recaptured by a set of gradient index lenses, coupled back into separate fiber optic lines, and transmitted back to detectors and electronics in the instrument package. In these experiments a 6-mm od fiber cable (containing the nine optical fibers) fell with the drop rig. Using separate detection and demodulation channels, spatial and temporal (up to 20 Hz) maps of water vapor and methane concentrations were obtained at differing heights in the flames. While this apparatus was useful from a demonstration standpoint, several drawbacks needed attention before useful scientific measurements could be obtained. First, eight lines of sight are somewhat insufficient for detailing the spatial profiles of the gas. Second, multiple detection channels operating in parallel are both expensive and present a challenge for accurate calibration. As a result, a newer scanning system was developed in our first contract under this program. The primary characteristic of this system is that it contains a single detection channel and achieves "continuous" spatial resolution by scanning the laser beam across the flame region, then directing this beam onto a single detector. Thus spatial measurements are converted to a temporal series of data. The true spatial resolution is limited only by the beam diameter and width of the sweep. In these experiments the beam is focused to about 1-mm diameter and scans across a region up to 4-cm wide.

Silver, Joel A.