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Detection and Bulk Properties of the HR 8799 Planets with High-resolution Spectroscopy

Using the Keck Planet Imager and Characterizer, we obtained high-resolution (R ~ 35,000) K-band spectra of the four planets orbiting HR 8799. We clearly detected H{sub 2}O and CO in the atmospheres of HR 8799 c, d, and e, and tentatively detected a combination of CO and H{sub 2}O in b. These are the most challenging directly imaged exoplanets that have been observed at high spectral resolution to date when considering both their angular separations and flux ratios. We developed a forward-modeling framework that allows us to jointly fit the spectra of the planets and the diffracted starlight simultaneously in a likelihood-based approach and obtained posterior probabilities on their effective temperatures, surface gravities, radial velocities, and spins. We measured vsin (i) values of 10.1{sub -2.7}{sup +2.8} km s{sup -1} for HR 8799 d and 15.0{sub -2.6}{sup +2.3} km s{sup -1} for HR 8799 e, and placed an upper limit of <14 km s{sup -1} of HR 8799 c. Under two different assumptions of their obliquities, we found tentative evidence that rotation velocity is anticorrelated with companion mass, which could indicate that magnetic braking with a circumplanetary disk at early times is less efficient at spinning down lower-mass planets.

74 ATOMIC AND MOLECULAR PHYSICS↗

Abundance and distribution of ultramafic microbreccia in Moses Rock dike - Quantitative application of mapping spectroscopy

Data from the Airborne Imaging Spectrometer were used to map the distribution and abundance of the serpentized ultramafic microbreccia (SUM) component in the Moses Rock dike, which is a Tertiary diatreme located on the Colorado Plateau in Utah. The geologic setting and composition of Moses Rock dike are discussed together with its texture and the relationship to the bedrock of surface materials. These observations along with laboratory spectroscopic data are used to interpret surface mineralogy of the dike and the surrounding regions from the imaging spectometer data. The spatial distribution and the abundance of the primary surface components were calculated using a nonlinear model for the mixing of spectra from multicomponent surfaces. The derived SUM distribution and abundance data support McGetchin's (1968) model for the emplacement of Moses Rock dike as a fluidized system.

Mustard, John F.↗

ASCA observations of supernova remnants

The combined spectral and imaging capabilities of the Advanced Satellite for Cosmology and Astrophysics (ASCA) provides new possibilities for studying supernova remnants. The most powerful of these are spatially resolved, moderate resolution spectroscopy and narrowband spectral imaging. The use of these techniques yielded a number of results that challenge the currently held views on X-ray emission processes in supernova remnants. Evidence was found for the plasmas in which a different ionization timescale must be used to characterize each metal. Some recent findings from supernova remnant surveys conducted using ASCA are presented.

Petre, R.↗

Imaging and speciation of intracellular metallic implant debris using synchrotron-based X-ray fluorescence micro-spectroscopy: a study of two cases

Debris generated from total hip arthroplasty (THA) components made from metal alloys can cause, in some cases, inflammatory cell (e.g., macrophages) responses that lead to adverse local tissue reactions (ALTR) and implant failure. The lack of information on intracellular chemical alterations of metal debris has hindered the understanding of the pathogenesis of ALTR. The goal of this study was to characterize intracellular debris within macrophages using Synchrotron imaging and spectroscopy. We studied periprosthetic tissues of two retrieved THAs with (1) a metal-on-metal (MoM) articulation and (2) a metal-on-polyethylene (MoP) articulation exhibiting corrosion of the metal femoral head. The MoM-THA exhibited different valence states of chromium- and cobalt-containing debris, suggesting three different moieties: Cr 2 O 3 , CrPO 4 , and an alloy-oxide mixture. The findings further suggest that Cr 2 O 3 formed in the tribological interfaces of the implant, while CrPO 4 is a by-product of the phagocytosis process of cobalt alloy-containing debris. Titanium debris appeared to occur in a mixed crystalline/amorphous oxide state. It remains unclear if this chemical state results from the tribochemical processes at the implant surface or intracellular alterations. The MoP-THA specimen exhibited no intracellular particulate debris associated with macrohpages, indicating that the ALTR may be entirely triggered by metal ionic species in this case. A better understanding of in vivo chemical alteration of implant debris will aid in assessing the risk for ALTR during implant design and material choice. However, various techniques are needed to accurately determine the interaction between metal particles and the inta- and extra-cellular environment.

60 APPLIED LIFE SCIENCES↗

Bioverse: A Simulation Framework to Assess the Statistical Power of Future Biosignature Surveys

Next-generation space observatories will conduct the first systematic surveys of terrestrial exoplanet atmospheres and search for evidence of life beyond Earth. While in-depth observations of the nearest habitable worlds may yield enticing results, there are fundamental questions about planetary habitability and evolution that can only be answered through population-level studies of dozens to hundreds of terrestrial planets. To determine the requirements for next-generation observatories to address these questions, we have developed Bioverse. Bioverse combines existing knowledge of exoplanet statistics with a survey simulation and hypothesis testing framework to determine whether proposed space-based direct imaging and transit-spectroscopy surveys will be capable of detecting various hypothetical statistical relationships between the properties of terrestrial exoplanets. Following a description of the code, we apply Bioverse to determine whether an ambitious direct imaging or transit survey would be able to determine the extent of the circumstellar habitable zone and study the evolution of Earth-like planets. Given recent evidence that Earth-sized habitable zone planets are likely much rarer than previously believed, we find that space missions with large search volumes will be necessary to study the population of terrestrial and habitable worlds. Moving forward, Bioverse provides a methodology for performing trade studies of future observatory concepts to maximize their ability to address population-level questions, including and beyond the specific examples explored here.

60 APPLIED LIFE SCIENCES↗

Method of Stamping Surface-Enhance Raman Spectroscopy for Label-Free, Multiplexed, Molecular Sensing and Imaging

The present disclosure relates the use of a stamping surface enhanced Raman scattering (S-SERS) technique with nanoporous gold disk (NPGD) plasmonic substrates to produce a label-free, multiplexed molecular sensing and imaging technique. A NPGD SERS substrate is stamped onto a surface containing one or more target molecules, followed by SERS measurement of the target molecules located between the surface and SERS substrate. The target molecules may be deposited on the surface, which may be a carrier substrate such as polydimethylsiloxane (PDMS).

Shih, Wei-Chuan↗

CHESS 2025: Field-collected vegetation attributes and site photos

This dataset represents field observations of vegetation samples collected as part of the Colorado Headwaters Ecological Spectroscopy Study (CHESS) during June and July of 2025. Samples were collected in the field using tablet computers and digital forms, with target data differing by sample type (individual trees, individual shrubs, or 1-meter square plots of meadow and subshrub vegetation). Field samples were collected within 72 hours of airborne data collection using the National Ecological Observatory Network’s Aerial Observation Platform (NEON AOP). The NEON AOP collected waveform LiDAR (Light Detection and Ranging) and imaging spectrometer data in 426 spectral bands from the visible to shortwave infrared. Remote sensing data for the project is available on ESS-DIVE (DOI and citation to be added upon publication). Field data collected included canopy height and per-species horizontal proportional cover for meadow plots, species identity and height information for shrubs, as well as species identity, height, diameter at breast height, and health assessment information for trees. Photos of the focal site and surrounding landscape were taken for all sampling sites and are included in this archive. Green leaves or needles were collected for plant trait and foliar chemistry analysis. This data is archived separately (DOI and citation to be added upon publication). High-precision geospatial data for each sample (crown perimeter polygons for trees and shrubs, plot boundaries for meadow plots) is available here (Henderson et al., 2026). Field and remote sensing protocols largely followed those of a previous field and airborne imaging campaign performed in 2018 (described in Chadwick et al. 2020). Field data from the 2018 campaign can be found here (Chadwick et al., 2020 doi:10.15485/1618130). Because different field measurements were taken for meadow, shrub, and tree sites, data from these three sample types are archived as separate tables (chess_meadow_site_cleaned.csv, chess_shrub_site_cleaned.csv, chess_tree_site_cleaned.csv). Meadow proportional cover data is stored in a separate table (chess_meadow_cover_cleaned.csv). Taxonomy was treated identically between sample types, and the dataset shares a common set of voucher specimens (chess_voucher_IDs_cleaned.csv), as well as a single species list (chess_species_list_cleaned.csv). All taxonomic determinations were performed to the species level, and adhere to the Global Biodiversity Information Facility (GBIF) backbone taxonomy as of January 10th, 2026 (GBIF Secretariat 2023). CHESS Project Description: The Colorado Headwaters Ecological Spectroscopy Study (CHESS) comprised a multi-week airborne remote sensing and field observation campaign in the Upper Gunnison Basin, Colorado, conducted in June and July of 2025. Airborne remote sensing was conducted by the National Ecological Observatory Network Airborne Observation Platform (NEON AOP), concurrent with a field campaign run by the Rocky Mountain Biological Laboratory (RMBL), the Lawrence Berkeley National Laboratory (LBNL) and SLAC National Accelerator Laboratory Watershed Function Science Focus Area (SFA), and NASA-JPL (Jet Propulsion Laboratory) Earth Surface Mineral Dust Source Investigation (EMIT) program. Between June 10 and July 18, 2025, the NEON AOP flight team collected high-resolution aerial imaging spectroscopy and Light Detection and Ranging (LiDAR) data over three domains: the Upper East River (CRBU), Almont Triangle (ALMO), and the Upper Taylor Basin (UPTA). In coordination with the flights, a field campaign acquired ground-truth observations, including observations of vegetation composition, foliar traits, forest demography, and subsurface properties in 18 core sampling areas within the domains. Additional surface water observations were taken at over 380 point locations. All CHESS campaign datasets can be found within the CHESS ESS-DIVE data portal: https://data.ess-dive.lbl.gov/portals/chess. Funding Acknowledgment: Field and remote-sensing data acquisition was performed under a grant from the National Aeronautics and Space Administration (80NSSC24K1005). This work was also supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231.

2018 NEON and 2025 CHESS Campaigns↗

X-ray fluorescence and XANES spectroscopy revealed diverse potassium chemistries and colocalization with phosphorus in the ectomycorrhizal fungus Paxillus ammoniavirescens

Ectomycorrhizal (ECM) fungi play a major role in forest ecosystems and managed tree plantations. Particularly, they facilitate mineral weathering and nutrient transfer towards colonized roots. Among nutrients provided by these fungi, potassium (K) has been understudied compared to phosphorus (P) or nitrogen (N). The ECM fungus Paxillus ammoniavirescens is a generalist species that interacts with the root of many trees and can directly transfer K to them, including loblolly pine. However, the forms of K that ECM fungi can store is still unknown. Here, we used synchrotron potassium X-ray fluorescence (XRF) and K-edge X-ray Absorption Near Edge Structure (XANES) spectroscopy on P. ammoniavirescens growing in axenic conditions to investigate the K chemistries accumulating in the center and the edge of the mycelium. We observed that various K forms accumulated in different part of the mycelium, including K-nitrate (KNO 3 ), K-C-O compounds (such as K-tartrate K 2 (C 4 H 4 O 6 ) and K-oxalate (K 2 C 2 O 4 )), K-S and K-P compounds. Saprotrophic fungi have been shown to excrete carboxylic acids, which in turn play a role in soil mineral weathering. Our finding of several K counter-ions to carboxylic acids may suggest that, besides their direct transfer to colonized roots, K ions can also be involved in the production of compounds necessary for sourcing nutrients from their surrounding environment by ECM fungi. Additionally, this work reveals that XANES spectroscopy can be used to identify the various forms of K accumulating in biological systems.

Ectomycorrhizal symbiosis↗

Large-Eddy / Reynolds-Averaged Navier-Stokes Simulations of a Dual-Mode Scramjet Combustor

Numerical simulations of reacting and non-reacting flows within a scramjet combustor configuration experimentally mapped at the University of Virginia s Scramjet Combustion Facility (operating with Configuration A ) are described in this paper. Reynolds-Averaged Navier-Stokes (RANS) and hybrid Large Eddy Simulation / Reynolds-Averaged Navier-Stokes (LES / RANS) methods are utilized, with the intent of comparing essentially blind predictions with results from non-intrusive flow-field measurement methods including coherent anti-Stokes Raman spectroscopy (CARS), hydroxyl radical planar laser-induced fluorescence (OH-PLIF), stereoscopic particle image velocimetry (SPIV), wavelength modulation spectroscopy (WMS), and focusing Schlieren. NC State's REACTMB solver was used both for RANS and LES / RANS, along with a 9-species, 19- reaction H2-air kinetics mechanism by Jachimowski. Inviscid fluxes were evaluated using Edwards LDFSS flux-splitting scheme, and the Menter BSL turbulence model was utilized in both full-domain RANS simulations and as the unsteady RANS portion of the LES / RANS closure. Simulations were executed and compared with experiment at two equivalence ratios, PHI = 0.17 and PHI = 0.34. Results show that the PHI = 0.17 flame is hotter near the injector while the PHI = 0.34 flame is displaced further downstream in the combustor, though it is still anchored to the injector. Reactant mixing was predicted to be much better at the lower equivalence ratio. The LES / RANS model appears to predict lower overall heat release compared to RANS (at least for PHI = 0.17), and its capability to capture the direct effects of larger turbulent eddies leads to much better predictions of reactant mixing and combustion in the flame stabilization region downstream of the fuel injector. Numerical results from the LES/RANS model also show very good agreement with OH-PLIF and SPIV measurements. An un-damped long-wave oscillation of the pre-combustion shock train, which caused convergence problems in some RANS simulations, was also captured in LES / RANS simulations, which were able to accommodate its effects accurately.

Fulton, Jesse A.↗

Field Geology/Processes

The field geology/process group examined the basic operations of a terrestrial field geologist and the manner in which these operations could be transferred to a planetary lander. Four basic requirements for robotic field geology were determined: geologic content; surface vision; mobility; and manipulation. Geologic content requires a combination of orbital and descent imaging. Surface vision requirements include range, resolution, stereo, and multispectral imaging. The minimum mobility for useful field geology depends on the scale of orbital imagery. Manipulation requirements include exposing unweathered surfaces, screening samples, and bringing samples in contact with analytical instruments. To support these requirements, several advanced capabilities for future development are recommended. Capabilities include near-infrared reflectance spectroscopy, hyper-spectral imaging, multispectral microscopy, artificial intelligence in support of imaging, x ray diffraction, x ray fluorescence, and rock chipping.

Allen, Carlton↗

New application of hyperspectral imaging to steady-state plasma observations

A new application of hyperspectral imaging (HSI) to steady-state plasma emission observations is proposed because of its prominent feature: an HSI camera records a two-dimensional image, and each spatial pixel contains spectral data typically with more than a hundred bands, while conventional digital cameras have only three bands. The characterization of an HSI camera (Specim IQ) has been performed during steady-state plasma–material interaction experiments using the linear plasma device PISCES-A. By easily subtracting the background/continuum emission in contrast to conventional filter cameras, two-dimensional images of multiple emission lines at different wavelengths are simultaneously obtained during a single measurement, demonstrating the advantage in plasma emission observations.

47 OTHER INSTRUMENTATION↗

Field-resolved space–time characterization of few-cycle structured light pulses

Accompanied by the rapid development of ultrafast laser platforms in recent decades, the spatiotemporal manipulation of ultrashort laser pulses has attracted much attention due to the potential for cutting-edge applications of structured light, including optical tweezers, optical communications, super-resolution imaging, time-resolved spectroscopy in molecules and quantum materials, and strong-field physics. Today, techniques capable of characterizing the full spatial, temporal, and polarization state properties of structured light are strongly desired. Here, we demonstrate a technique, termed 3D TIPTOE, for characterizing structured mid-infrared waveforms, which uses only a two-dimensional silicon-based image sensor as both the detector and the nonlinear medium. By combining the advantages of the sub-cycle time resolution afforded by nonlinear excitation and the spatial resolution inherent to the two-dimensional sensor, the 3D TIPTOE technique allows full characterization of structured electric fields, significantly reducing the complexity of detection compared to other techniques. The validity of the technique is established by measuring both few-cycle Bessel–Gaussian pulses and radially polarized femtosecond vector beams.

Liu, Yangyang (ORCID:0000000335205332)↗

CHESS 2025: Leaf Area Index (LAI) for meadow, shrub, tree, and understory vegetation

This dataset contains Leaf Area Index (LAI) measurements made as part of the Colorado Headwaters Ecological Spectroscopy Study (CHESS) during June and July of 2025. Data were collected in the Upper Gunnison Basin, Colorado, across three study domains: the Upper East River (CRBU), Almont Triangle (ALMO), and the Upper Taylor Basin (UPTA). Field observations of LAI were collected within 72 hours of airborne data collection by the National Ecological Observatory Network’s Aerial Observation Platform (NEON AOP). The NEON AOP collected waveform LiDAR (Light Detection and Ranging) and imaging spectrometer data in 426 spectral bands from the visible to shortwave infrared. LAI measurements were collected using the LICOR LAI-2200C Plant Canopy Analyzer following protocols outlined in the instrument manual (LI-COR 2019). Sampling targeted four distinct vegetation types: meadows, shrubs, trees, and aspen forest understory. We have archived data separately by site type because different field methods were used for each. At meadow sites, measurements were made at the four corners of 1m x 1m plots, with the instrument moving inward toward the center of the plot. At shrub sites, we measured the canopies of individual shrubs. At tree sites, we made measurements within a 10m x 10m subplot centered around a focal tree, with 30 observations taken on a regular grid. At aspen understory sites, we measured overstory trees following the tree protocol and understory herbaceous vegetation following the meadow protocol. All measurements included above-canopy (A) and below-canopy (B) readings, with specific protocols for scattering correction measurements in direct-sun conditions. Data were processed using the R package `rlai` (Worsham 2025). This package includes functions to calculate LAI, gap fraction, apparent clumping factor (Ω), scattering correction, and other canopy metrics. Package contents: Full file descriptions appear in ‘flmd.csv’. Files named according to the convention ‘lai_*_summary_data_cleaned.csv’ contain summary values of LAI, apparent clumping factor (Ωapp), and scattering correction factors for each site. These are the analysis-ready products that most data users will work with. Files named ‘lai_*_metadata_cleaned.csv’ contain additional site-level observations made during field collection. We have also archived intermediate and supplementary data for users who wish to check our processing approach or apply alternative methods. ‘raw_lai_2200C.zip’ contains the raw files as read from the LI-COR instrument, with no processing applied, in TXT format. The zip archive contains subdirectories by site type, which are further subdivided by sampling area. Filenames correspond to the sampling site number. ‘intermediate_results.zip’ contains detailed output from the processing routines, in JSON format. The zip archive contains subdirectories by site type; filenames correspond to the sampling site number. ‘scattering_correction_logs.zip’ contains logfiles from the implementation of Kobayashi et al.'s (2013) scattering correction algorithm. The logfiles report values of several parameters at each iteration of the algorithm, as the model converges toward a stable solution. They are intended for users who want to verify scattering correction performance. The zip archive contains subdirectories by site type; filenames correspond to the sampling site number. ‘spot_checks.csv’ reports LAI and other values for a small number of files processed with LI-COR FV2200 software (LI-COR 2013) using the same control parameters as in our R-based approach. Additional metadata are provided in a data dictionary describing column names and definitions (dd.csv), and in a file-level metadata file (flmd.csv). All zip files can be expanded with common archive utilities. TXT, CSV, and JSON files can be ingested into R or Python computing environments or read in common text editor utilities. Geospatial information: Geospatial data for mapping measurement site locations are in the files CHESS_polygons_lai_UTM.geojson, CHESS_polygons_shrub_UTM.geojson, and CHESS_polygons_meadow_UTM.geojson in the companion geospatial package for the 2025 CHESS campaign, ‘CHESS 2025: Location data for field observations and sampling’ (Henderson et al., 2026). CHESS Project Description: The Colorado Headwaters Ecological Spectroscopy Study (CHESS) comprised a multi-week airborne remote sensing and field observation campaign in the Upper Gunnison Basin, Colorado, conducted in June and July of 2025. Airborne remote sensing was conducted by the National Ecological Observatory Network Airborne Observation Platform (NEON AOP), concurrent with a field campaign run by the Rocky Mountain Biological Laboratory (RMBL), the Lawrence Berkeley National Laboratory (LBNL) and SLAC National Accelerator Laboratory Watershed Function Science Focus Area (SFA), and NASA-JPL (Jet Propulsion Laboratory) Earth Surface Mineral Dust Source Investigation (EMIT) program. Between June 10 and July 18, 2025, the NEON AOP flight team collected high-resolution aerial imaging spectroscopy and Light Detection and Ranging (LiDAR) data over three domains: the Upper East River (CRBU), Almont Triangle (ALMO), and the Upper Taylor Basin (UPTA). In coordination with the flights, a field campaign acquired ground-truth observations, including observations of vegetation composition, foliar traits, forest demography, and subsurface properties in 18 core sampling areas within the domains. Additional surface water observations were taken at over 380 point locations. All CHESS campaign datasets can be found within the CHESS ESS-DIVE data portal: https://data.ess-dive.lbl.gov/portals/chess. Funding Acknowledgement: Field and remote-sensing data acquisition was performed under a grant from the National Aeronautics and Space Administration (80NSSC24K1005). This work was also supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231. * Todorov and Worsham are co–first authors.

2018 NEON and 2025 CHESS Campaigns↗

High-resolution study of luminous infrared galaxies. I - The composite nature of the Seyfert 1 galaxy IRAS 20044-6114 (NGC 6860)

The physical conditions in the ionized gas, the stellar population, and the kinematics of the Seyfert 1 galaxy IRAS 20044-6114 (NGC 6860) are studied by high spatial resolution optical imaging and optical and near-IR spectroscopy of this luminous IR source. The broadband images show a compact nucleus, two weak spiral arms, a bar, a bulge, an inner ring, and a possible outer ring. The I-alpha image reveals bright emission-line regions associated with the Seyfert nucleus and an inner ring of intense star formation. The forbidden O III 5007-A image shows that the high-excitation gas is elongated perpendicularly to the direction of the bar, and reveals a bright compact object at about 40 arcsec NE of the nucleus which is undetectable in the broadband images. This object is interpreted as a dwarf young H II galaxy. The optical, near-IR, and FIR results show clear evidence that the nuclear and circumnuclear regions have composite and complex structure: a variable Seyfert 1 nucleus embedded in an intense and dusty star formation. environment.

Lipari, Sebastian↗

Ultrasonication-assisted trace amount solvent synthesis of Cs 4 PbBr 6 crystal with ultra-bright green light emission

Cs 4 PbBr 6 crystals have been synthesized by an ultrasonication-assisted trace amount polar solvent method. The prepared green Cs 4 PbBr 6 material was found to have high photoluminescence (PL) brightness and 10 ns PL lifetime. The prepared green light emitting device can achieve the maximum brightness of 3.8 × 10 9 cd/m 2 , which is nearly 100 times higher than a wick. The white light emitting device based on Cs 4 PbBr 6 crystals has better performance than commercial products, which can cover 32.3% of the color gamut and achieves 107.3% coverage for International Commission on Illumination (CIE)1931 and 84.8% coverage for CIE1976.

36 MATERIALS SCIENCE↗

Possible Ancient Anthrosols Near Lost City of Ubar Site in Oman

During mapping for the Wadi al Jubal Archaeological Project in Yemen, USGS Geologists Overstreet and Grolier mapped "anthrosols of pre-Islaniic age" east of the Marib dam site (15D 24M N, 45D 18M E). These soils were the result of agriculture supported by irrigation enabled by water impounded by the dam, areas which were abandoned after dam failure. During analysis of Landsat Thematic Mapper satellite images of Yemen and Oman for the Mahra Archaeological Project, we noted that these anthrosols had a distinctive image expression. Based on other remote sensing research and laboratory spectroscopy, we think that the distinctive image signature is due to low reflectivity in Landsat band 7 resulting from relatively high concentrations of gypsum in the anthrosols. Many anthrosol sites were noted, most, but not all, of them previously documented. Undocumented possible anthrosol sites include an area east of Shisr in Oman, the archaeological site discovered by us to be responsible for some features of the "Lost City of Ubar" legends. Included in legendary accounts of the Ubar region are reports of fertile oases, and "areas that have known the plow". Based on demonstrated reliability of aspects of carefully interpreted legendary accounts, we postulate that we may have located the area of desert agriculture that may have existed to support the frankincense caravansary of Ubar. The possible anthrosol area is located at approximately 18D 10M N, 53D 54M E, and will be the subject of study in a future expedition.

Blom, Ronald G.↗

Spatially Resolved Mapping of Three-Dimensional Molecular Orientations with ~2 nm Spatial Resolution through Tip-Enhanced Raman Scattering

We record local optical field images of silver nanocubes (75 nm) using tip-enhanced Raman (TER) spectral imaging. The images that we observe are consistent with several recent reports from our group, but here, we demonstrate sub-2 nm spatial resolution in local optical field nanoimaging under ambient laboratory conditions. This is achieved by scanning the substrate (nanocube on Si) relative to a 4-thiobenzonitrile (TBN)-functionalized Ag-coated TER probe. The spatial resolution that we obtain necessitates that only a few molecules govern the recorded optical response; molecular orientation becomes an important consideration in such measurements. We model the orientation through geometry optimization of a TBN molecule chemisorbed onto an Ag79 cluster (sphere with a ~1 nm diameter). Using the computed orientation of the cluster-bound molecule, we then model the optical response using formalism that accounts for the orientation of the molecule relative to vector components of the local optical fields. We find optimal agreement between experiment and theory. In effect, this work reveals the parallels between single-molecule Raman scattering and high-spatial-resolution TER spectroscopy, even when the images themselves cannot be used to visualize a single molecule in real space.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗