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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.

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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
NASA NTRS2021

Detection of Anomalies in the UV/Vis Reflectances from the Ozone Monitoring Instrument

Various instrumental or geophysical artifacts, such as saturation, stray light, or obstruction of light (either coming from the instrument or related to solar eclipses), negatively impact satellite measured ultraviolet and visible Earthshine radiance spectra and downstream retrievals of atmospheric and surface properties derived from these spectra. In addition, excessive noise such as from cosmic ray impacts, prevalent within the South Atlantic Anomaly, can also degrade satellite radiance measurements. Saturation specifically pertains to observations of very bright surfaces such as sun glint over open water or thick clouds. When saturation occurs, additional photoelectric charge generated at the saturated pixel may overflow to pixels adjacent to a saturated area and be reflected as a distorted image in the final sensor output.When these effects cannot be corrected to an acceptable level for science quality retrievals, flagging of the affected pixels is indicated. Here, we introduce a straightforward detection method that is based on the correlation, r, between the observed Earthshine radiance and solar irradiance spectraover a 10 nm-spectral range; our Decorrelation Index (DI for brevity) is simply defined as DI=1-r. DI increases with anomalous additive effects or excessive noise in either radiances, the most likely cause indata from theOzone Monitoring Instrument (OMI),or irradiances. DI is relatively straight-forward to use and interpret and can be 20computed for different wavelength intervals. We developed a set of DIs for two spectral channelsof the OMI, a hyperspectral pushbroom imaging spectrometer. For each OMI spatial measurement, we define 14 wavelength-dependent DIs within the OMI visible channel (350-498 nm) and 6 DIs in its ultraviolet 2 (UV2) channel (310-370 nm). As defined, DIs reflect a continuous range of deviations of observed spectra from the reference irradiance spectrum that are complementary to the binary Saturation Possibility Warning (SPW) flags currently provided for each individual spectral/spatial pixel in the OMI radiance data set. Smaller values of DI are also caused by a number of geophysical factors; this allows one to obtain interesting physical results on the global distribution of spectral variations.

Space sensor↗
NASA NTRS2003

Palagonitic (Not Andesitic) Mars: Evidence from Thermal Emission and VNIR Spectra of Palgonitic Alteration Rinds on Basaltic Rock

Visible and near-IR (VNIR) spectra of both Martian bright and dark regions are characterized by a ferric absorption edge extending from approx. 400 to 750 nm, with bright regions having about twice the reflectivity at 750 nm as dark regions. Between 750 nm to beyond 2000 nm, bright and dark regions have nearly constant and slightly negative spectral slopes, respectively. Depending on location, bright regions have shallow reflectivity minima in the range 850-910 nm that are attributed to ferric oxides. Similarly, dark regions have shallow reflectivity minima near approx. 950 and 1700-2000 nm that are attributed to ferrous silicate minerals (pyroxene). Among terrestrial geologic materials, the best spectral analogues for Martian bright regions are certain palagonitic tephras from Mauna Kea Volcano (Hawaii). By definition, palagonite is a "yellow or orange isotropic mineraloid formed by hydration and devitrification of basaltic glass". The ferric pigment in palagonite is nanometer-sized ferric oxide particles (np-Ox) dispersed throughout the hydrated basaltic glass matrix. The hydration state of the np-Ox particles is not known, but the best Martian spectral analogues contain allophane-like materials and not crystalline phyllosilicates.

R V Morris↗
DOE OSTI2016

A TRIP TO THE CATACLYSMIC BINARY ZOO: DETAILED FOLLOW-UP OF 35 RECENTLY DISCOVERED SYSTEMS

We report follow-up studies of 35 recently discovered cataclysmic variables (CVs), 32 of which were found in large, automated synoptic sky surveys. The objects were selected for observational tractability. For 34 of the objects, we present mean spectra and spectroscopic orbital periods, and for one more we give an eclipse-based period. Thirty-two of the period determinations are new, and three of these refine published estimates based on superhump periods. The remaining three of our determinations confirm previously published periods. Twenty of the stars are confirmed or suspected dwarf novae with periods shorter than 3 hr, but we also find three apparent polars (AM Her stars) and six systems with P>5 hr. Five of these systems have secondary stars visible in their spectra, from which we estimate distances when possible. The orbital period distribution of this sample is very similar to that of previously discovered CVs.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRSDate not supplied

Microbial Pigments and Their Degradation Products as Biosignatures

Carotenoids are a class of vibrant biological pigments that have a characteristic chemical structure centered around a polyene core (Lu et al. 2018). Carotenoids and their derivatives are candidate biosignatures because they can persist in the terrestrial geologic record for up to 1.73 billion years (Vinnichenko et al. 2020), have specific structures that are likely the result of complex pathways, mediate the survival of many microorganisms in Mars and Ocean Worlds analog environments, and are detectable with multiple techniques, including Raman spectroscopy. In this project, we aim to investigate the detectability of carotenoid pigments with different spectroscopic methods to inform future instrument selection. We compare the spectra of five unaltered carotenoids, two model compounds, and carotenoid-forming archaeon with visible and deep UV Raman spectroscopy and UVVis absorption spectrophotometry. We then use one model pigment, beta-carotene, to evaluate the likelihood that unique spectral properties of carotenoids, or their refractory byproducts, would be preserved and detectable on a remote planetary surface by exposing it to simulated conditions for Mars. Sample Acquisition. Pigments betacarotene, lutein, zeaxanthin, astaxanthin, and lycopene were purchased from Sigma Aldrich. Halobacterium salinarum NRC-1 was acquired from Carlina Biological and grown in Halobacterium media. Mineral salts including sodium sulfate, sodium carbonate, and halite were used to form matrices in which the beta-carotene was embedded before exposure. Pigment-mineral mixes were at a 1:10 ratio in water. Analytical Techniques. Deep UV Raman data were collected on a custom laboratory mapping spectrometer called MOBIUS (Mineral and Organic Based Investigations using Ultraviolet Spectroscopy), which is an analog to the SHERLOC instrument on the Mars 2020 Perseverance rover (Bhartia et al. 2021). It features a 248.56 nm NeCu pulsed laser, liquid nitrogen-cooled detector, and tunable optical setup. Visible Raman data were collected using a Horiba Jobin Yvon LabRam HR spectrometer with a frequencydoubled Nd:YAG laser (532 nm) and a HeNe laser (633 nm). A VWR 6300 PC UV/Visible Spectrophotometer was used to collect absorption data for carotenoid solutions, model compounds, and solvents in UVpermissible capped cuvettes. Data were collected from 190-1100 nm at 1 nm increments. All spectral data were analyzed using Igor Pro 9 (Wavemetrics). Irradiation. We used a vacuum chamber equipped with a cryostat and a flood electron gun to simulate Martian surface temperatures, low pressures, and ionizing radiation (10keV, 10μA for 6h at 200K for our initial tests). The samples were prepared by drying the pigment-mineral mix onto polished metal tabs, then mounted on the cryostat for processing. Samples were then analyzed directly on the tabs after exposure. Results: In comparing the visible and deep UV Raman spectra of unaltered pigments, we found that they differed drastically. Carotenoids are often studied with visible Raman and typically have peaks at 1525 cm-1 and 1157 cm-1, due to the stretching of the C=C and C-C bonds in the polyene structure. However, in deep UV, the strongest feature is at ~1630 cm-1 and is broad, possibly indicating that multiple peaks are forming this feature. This stark difference is likely due to different preresonant enhancement effects. The UV-Vis results show that there is an absorption band in the deep UV <300 nm, which supports the hypothesis that the 248.6 nm excitation is interrogating another aspect of carotenoids than visible Raman. Our preliminary exposure tests indicated that pigments – even without minerals present - were largely unaltered in the applied conditions, with only a slight broadening in the primary polyene peaks apparent in the visible Raman data. Figure 1. A) Visible vs. deep UV Raman spectra of unaltered beta carotene. B) Schematic of exposure. Conclusions: Our results to date indicate that deep UV and visible Raman spectroscopy, both techniques with planetary mission heritage from Mars 2020 (Wiens et al. 2021, Bhartia et al. 2021), may be used in a complementary manner to observe carotenoids. In addition, we find that beta-carotene is largely resistant to our current exposure conditions, though there may be some amount of amorphization of the material which could cause the broadening of the peaks at 1525 and 1157 cm-1. As a next step, we aim to increase the dosage and duration of exposure to observe degradation of the parent pigment, possibly add UV as a factor via an Ar mini-arc UV lamp and use GC-MS to characterize possible degradation products.

pigments↗
DOE OSTI2017

Hubble Space Telescope Ultraviolet Light Curves Reveal Interesting Properties of CC Sculptoris and RZ Leonis

Time-tag ultraviolet data obtained on the Hubble Space Telescope in 2013 reveal interesting variability related to the white dwarf spin in the two cataclysmic variables RZ Leo and CC Scl. RZ Leo shows a period at 220 s and its harmonic at 110 s, thus identifying it as a likely Intermediate Polar (IP). The spin signal is not visible in a short single night of ground-based data in 2016, but the shorter exposures in that data set indicate a possible partial eclipse. The much larger UV amplitude of the spin signal in the known IP CC Scl allows the spin of 389 s, previously only seen at outburst, to be visible at quiescence. Spectra created from the peaks and troughs of the spin times indicate a hotter temperature of several thousand degrees during the peak phases, with multiple components contributing to the UV light.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1972

New laser technique for the identification of molecular transitions.

A laser technique is proposed which may be useful for the assignment of molecular spectra in the visible and infrared regions. The method is based on the resonant interaction of two monochromatic fields with a Doppler-broadened three-level system. Under the appropriate conditions the absorption line shape of one of the transitions shows a complex structure over a narrow section of the Doppler profile, and for sufficiently high laser power the line shape splits into a number of narrow peaks. Analysis of the resulting intensity pattern leads to unambiguous assignment of the angular momentum quantum numbers of the three levels involved. A simple set of rules is given to facilitate interpretation of spectra. The line shapes discussed are also relevant to monochromatic optical pumping of gases and unidirectional laser amplifiers.

Skribanowitz, N.↗
NASA NTRS1998

Spatially Resolved Spectra of 3C Galaxy Nuclei

We present and discuss visible-wavelength long-slit spectra of four low-redshift 3C galaxies obtained with the Space Telescope Imaging Spectrograph on the Hubble Space Telescope (HST). The slit was aligned with near-nuclear jet-like structure seen in HST images of the galaxies, to give unprecedented spatial resolution of their inner regions. In 3C 135 and 3C 171, the spectra reveal clumpy emission-line structures that indicate outward motions of a few hundred kilometers per second within a centrally illuminated and ionized biconical region. There may also be some low-ionization, high-velocity material associated with 3C 135. In 3C 264 and 3C 78, the jets have blue featureless spectra consistent with their proposed synchrotron origin. There is weak associated line emission in the innermost part of the jets with mild outflow velocity. These jets are bright and highly collimated only within a circumnuclear region of lower galaxy luminosity, which is not dusty. We discuss the origins of these central regions and their connection with relativistic jets.

Hutchings, J. B.↗
DOE OSTI2018

Tailoring the Structural, Optical and Magnetic Properties of NiFe{sub 2}O{sub 4} by Varying Annealing Temperature

Magnetic nanocrystalline NiFe{sub 2}O{sub 4} nanoparticles of size ranging between 13 and 19 nm were synthesized by the hydrothermal method using polyethylene glycol (PEG) as surfactant. The role of annealing on phase, crystallite size, and morphology was determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Energy-dispersive X-ray spectroscopy (EDX) was used for qualitative analysis. X-ray diffraction confirmed the single phase of as-obtained particles. TEM revealed a spherical morphology having an average particle size of 13.73 nm at 523 K and rises to 14.89, 16.42, and 21.14 nm at 623, 723, and 823 K respectively, which is approximately the same as the crystallite size determined from XRD. EDX results confirmed that elemental ratios were in stoichiometry. Fourier transform infrared (FTIR) spectral analysis demonstrates the formation of M-O bond in NiFe{sub 2}O{sub 4} nanoparticles. The optical spectra obtained from UV-visible spectroscopy revealed that nanoparticles have direct allowed energy band gap of 2.34, 2.47, 2.70, and 2.20 eV at 523, 623, 723, and 823 K respectively. A vibrating sample magnetometer (VSM) was used at room temperature for magnetic measurements which further showed ferromagnetic behavior of as-synthesized material. In addition, it was found that saturation magnetization increases with an increase of annealing temperature while coercivity decreases with temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS2010

Mineralogy and Thermal Properties of V-Type Asteroid 956 Elisa: Evidence for Diogenitic Material from the Spitzer IRS (5-35 Micrometers) Spectrum

We present the thermal infrared (5-35 micrometer) spectrum of 956 Elisa as measured by the Spitzer Infrared Spectrograph ("IRS"; Houck,1.R. et .11. [20041. Astrophys, 1. SuppL 154, 18-24) together with new ground-based lightcurve data and near-IR spectra. From the visible lightcurve photometry, we determine a rotation period of 16.494 +/- 0.001 h, identify the rotational phase of the Spitzer observations, and estimate the visible absolute magnitude (Hv) at that rotational phase to be 12.58 +/- 0.04. From radiometric analysis of the thermal flux spectrum, we find that at the time of observation 956 Elisa had a projected radius of 5.3 +/- 0.4 km with a visible albedo pv = 0.142+/- 0.022, significantly lower than that of the prototype V-type asteroid, 4 Vesta. (This corresponds to a radius of 5.2 +/- 0.4 km at lightcurve mean.) Analysis with the standard thermal model (STM) results in a sub-solar temperature of 292.3 +/- 2.8 K and beaming parameter eta = 1.16 +/- 0.05. Thermophysical modeling places a lower limit of 20 J m(exp -2)K(exp -1)s(exp -1/2) on the thermal inertia of the asteroid's surface layer (if the surface is very smooth) but more likely values fall between 30 and 150 J m(exp -2)K(exp -1)s(exp -1/2) depending on the sense of rotation. The emissivity spectrum, calculated by dividing the measured thermal flux spectrum by the modeled thermal continuum, exhibits mineralogically interpretable spectral features within the 9-12 micrometer reststrahlen band, the 15-16.5 micrometer Si-O-Si stretching region, and the 16-25 micrometer reststrahlen region that are consistent with pyroxene of diogenitic composition: extant diogenitic pyroxenes fall within the narrow compositional range W0(sub 2+/-1)En(sub 74+/-2)Fs(sub 24+/-1). Spectral deconvolution of the 9-12 micrometer reststrahlen features indicates that up to approximately 20% olivine may also be present, suggesting an olivine-diogenite-like mineralogy. The mid-IR spectrum is inconsistent with non-cumulate eucrite as the major component on the surface of 956 Elisa, although cumulate eucrite material may be present at abundances lower than that of the diogenite component. Analysis of new near-IR spectra of 956 Elisa with the Modified Gaussian Model (MGM; Sunshine, J,M., Pieters, C.M., Pratt, S.F.[1990]. J. Geophys. Res, 95 (May), 6955-6966) results in two pyroxene compositions: 75% magnesian low-Ca pyroxene and 25% high-Ca pyroxene. High-Ca pyroxene is not evident in the mid-IR data, but may belong to a component that is underrepresented in the mid-IR spectrum either because of its spatial distribution on the asteroid or because of its particle size. High-Ca pyroxenes that occur as exsolution lamellae may also be more evident spectrally in the NIR than in the mid-IR. In any case, we find that the mid-IR spectrum of 956 Elisa is dominated by emission from material of diogenite- like composition, which has very rarely been observed among asteroids.

Lim, Lucy F.↗
DOE OSTI2016

Synthesis and characterization of natural red dye from Caesalpinia sappan linn

The study reports the synthesis and characterization of natural red dye. The dyes were extracted from woods of Caesalpiniasappanlinn at varied temperatures of 70, 80, 90, and 100°C for three hours. The dry wood chips and water at a ratio of 6:1 were immersed in the reactor of 150 liters. The absorbance spectra of the natural red dyes were measured by ultra-violet-visible spectroscopy. Meanwhile, Fourier transform infrared spectroscopy was used to investigate the functional groups of the natural red dyes. In addition, the basic production cost was calculated and the fastness property towards cotton fabrics was investigated according to the Indonesia national standard of 105-C06:2010, 105-B01:2010, and 0288-2008. The results showed that the functional groups found the extracted red dyes indicated the complex bond of brazilein with peak absorbance at a wavelength of 538-540 nm. The extraction temperature also changed the functional group of brazilein. From the color, the absorbance peak, the functional groups, and the main production cost, the best parameter to synthesize the natural red dyes from Caesalpiniasappanlinn was at a temperature of 80°C for two hours. Moreover, the natural red dyes has the fastness to wash resistance, light resistance, and scrub resistance by 4-5, 4, and 3-4, respectively. However, further studies for synthesis the natural red dyes by using a continuous reactor are required to identify the naturally complex compounds in brazilein for improving the fastness properties and for reducing the cost.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Ultrathin Visible-Light-Driven Mo Incorporating In 2 O 3 -ZnIn 2 Se 4 Z-Scheme Nanosheet Photocatalysts

Inspired by natural photosynthesis, the design of new Z-scheme photocatalytic systems is very promising for boosting the photocatalytic performance of H 2 production and CO 2 reduction, however, till now the direct synthesis of efficient Z-scheme photocatalysts remains a grand challenge. Herein, we demonstrate an interesting Z-scheme photocatalyst can be constructed by coupling In 2 O 3 and ZnIn 2 Se 4 semiconductors based on the theoretical calculations. Experimentally, we make a class of ultrathin In 2 O 3 -ZnIn 2 Se 4 (donated as In 2 O 3 -ZISe) spontaneous Z-scheme nanosheet photocatalysts for greatly enhancing the photocatalytic H 2 production. Furthermore, we incorporate Mo atoms to the Z-scheme In 2 O 3 -ZISe nanosheet photocatalyst by forming Mo-Se bond, confirmed by X-Ray photoelectron spectroscopy, in which the formed MoSe 2 works as co-catalyst of Z-scheme photocatalyst. As a consequence, such unique structure of In 2 O 3 -ZISe-Mo makes it exhibit 21.7 and 232.6 times higher photocatalytic H 2 evolution activity than those of In 2 O 3 -ZnIn 2 Se 4 nanosheet and In 2 O 3 nanosheets, respectively. And In 2 O 3 -ZISe-Mo is also very stable for photocatalytic H 2 production by showing almost no activity decay for 16 h test. Here, the ultraviolet-visible diffuse reflectance spectra, photoluminescence spectroscopy, transient photocurrent spectra and electrochemical impedance spectroscopy reveal that the enhanced photocatalytic performance of In 2 O 3 -ZISe-Mo is mainly attributed to its widened photoresponse range and effective carrier separation because of its special structure.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2018

Examination of lutetium(III)-DOTA and copper(II)-NOTA solution structures using EXAFS

Targeted radionuclide therapy generally relies on the chelation of select short-lived isotopes such as 177 Lu and 67 Cu. The majority of Lu(III) and Cu(II) chelate structural information is derived from solid state diffraction data. Herein, the complexes Lu(DOTA) - , Cu(NOTA) - were examined in solution using EXAFS for the first time. Both ligands were fully deprotonated and coordinated to the metal with four and three carboxylic sites for Lu(DOTA) - and Cu(NOTA) - , respectively. Near-neighbor correlations from nitrogen atoms on the macrocyclic cages were also visible in the spectra in addition to the adjacent carbon backbones. Coordination numbers, bond distances, and Debye-Waller factors are reported and discussed alongside differences with known crystal structures.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2017

Design of a novel dual Z-scheme photocatalytic system composited of Ag{sub 2}O modified Ti{sup 3+} self doped TiO{sub 2} nanocrystals with individual exposed (001) and (101) facets

A novel dual Z-scheme photocatalytic system composited of Ag{sub 2}O nanocrystals modified Ti{sup 3+} self doped TiO{sub 2} nanocrystals with individual exposed (001) and (101) facets were successfully fabricated. In which, the Ti{sup 3+} self doped TiO{sub 2} nanocrystals with individual exposed (001) and (101) facets have been firstly prepared by a simple hydrothermal method, subsequently the as-prepared products were modified with Ag{sub 2}O nanocrystals through a sonochemical depositing process in order to build a novel dual Z-scheme photocatalytic system. The samples were carefully characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–visible diffuse reflectance spectra (UV–vis DRS), and Brunauer-Emmett-Teller (BET). The photocatalytic activity toward degradation of Rhodamine B (Rh B) aqueous solution under stimulated solar light was investigated. The experimental results showed this new dual Z-scheme photocatalytic system possess an enhanced photocatalytic degradation activity compared to that similar surface heterojunction photocatalysts composed of Ti{sup 3+} self doped TiO{sub 2} nanocrystals with individual exposed (001) and (101) facets. This novel photocatalytic system presents a high charge-separation efficiency and strong redox ability. This study will help us to better understand the photocatalytic mechanism of semiconductor photocatalysts with exposed different facets, and provide a new insight into the design and fabrication of advanced photocatalytic materials. - Highlights: •A novel dual Z-scheme system was built by Ag{sub 2}O and facet exposed TiO{sub 2} nanocrystals. •The individual TiO{sub 2} nanocrystals exposed (001) and (101) facets respectively. •Ag{sub 2}O coupled with Ti{sup 3+} self doped TiO{sub 2} nanocrystals through a sonochemical process. •The as-prepared sample possesses a super photocatalytic activity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Growth and Characterization of Epitaxial FeWO 4 Thin Films with Controlled Oxygen Stoichiometry

Here, we report the growth of single-phase epitaxial FeWO 4 thin films, using plasma-assisted molecular beam epitaxy, and investigate structural, optical, and electronic properties. The FeWO 4 films grow in (100) orientation on c-plane sapphire (0001) substrates and exhibit 3 rotational twin variants where FeWO 4 [001] is aligned to sapphire [100] equivalent in-plane directions. X-ray diffraction measurements indicate that the epitaxial FeWO 4 (100) structure is optimized when 80-100 W of rf power is applied to an atomic oxygen source during growth, yielding films with minimal strain and impurity phases or other orientations. In films grown with 120 W of rf power, FeWO 4 crystallites develop inhomogeneous and homogeneous strains and are potentially contaminated with Fe 3+ oxide phase impurities. In films grown with 60 W of rf power, FeWO 4 crystallites do not form fully epitaxial layers. X-ray photoelectron spectroscopy indicates that the structural changes are correlated with the Fe 3+ /Fe 2+ oxidation state ratio increasing from 0.6-1.4 with rf power from 60-120 W. X-ray fluorescence spectroscopy indicates that the Fe/W composition ratio is also increasing from 1.1-1.8 with rf power from 60-120 W. Ultraviolet and visible optical absorption spectra indicate a 1.8 ± 0.1 eV band gap with an additional interband absorption feature at 3.1 ± 0.1 eV in the 80-100 W films, with similar onsets observed in the 60 W films. In the 120 W films, the higher lying transition is shifted to 2.7 ± 0.1 eV due to the Fe 3+ enrichment. Electrical resistivity decreases over 2 orders of magnitude with oxidation from 10 4 -10 5 Ω cm in 60 W films to 120 ± 10 Ω cm in 120 W films. Thermopower measurements show p-type to n-type conductivity conversion when oxidation states shift from Fe 2+ majority in the 100 W films to Fe 3+ majority in the 120 W films. We conclude that electron polaron hopping driven by Fe 3+ is a dominant transport mechanism and a source of n-type conductivity in overoxidized FeWO 4 films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Metal-to-Ligand Charge-Transfer Spectrum of a Ru-Bipyridine-Sensitized TiO 2 Cluster from Embedded Multiconfigurational Excited-State Theory

Understanding optical properties of the dye molecule in dye-sensitized solar cells (DSSCs) from first-principles quantum mechanics can contribute to improving the efficiency of such devices. While density functional theory (DFT) and time-dependent DFT have been pivotal in simulating optoelectronic properties of photoanodes used in DSSCs at the atomic scale, questions remain regarding DFT’s adequacy and accuracy to furnish critical information needed to understand the various excited-state processes involved. In this work, we simulate the absorption spectra of a dye-sensitized solar cell analogue, comprised of a Ru-bipyridine (Ru-bpy) dye molecule and a small TiO2 cluster via DFT and via an accurate embedded correlated wavefunction (CW) theory. We generated CW spectra for the adsorbed Ru-bpy dye via a recently introduced capped density functional embedding theory or capped-DFET (to generate the embedding potential that accounts for the interaction of the molecule and the TiO 2 cluster). We then combined capped-DFET with the accurate but expensive multiconfigurational complete active space second-order perturbation theory (CASPT2)—embedded CASPT2. Because the CW theory is conducted on only a portion of the total system in the presence of an embedding potential that describes that portion’s interaction with its environment, we efficiently obtain CW-quality predictions that reflect local properties of the entire system. Specifically, for example, with capped-DFET and embedded CW theory, we can simulate accurately a plethora of metal-to-ligand charge-transfer excited properties at a manageable computational cost. Here, we predict detailed electronic spectra within the visible region, featuring the lowest three singlet and triplet excited states, along with predictions of the singlets’ lifetimes. We illustrated these results using a Jablonski diagram that show the relative energy position of the singlet and longer-lived triplet excited states and analyzed and proposed relaxation paths for the excited state corresponding to the most intense but short-lived absorption (interconversion, intersystem crossing, fluorescence, and phosphorescence) that may lead to longer-lived excited states necessary for efficient charge separation required to generate current in solar cells.

14 SOLAR ENERGY↗
DOE OSTI2017

Tunable UV-Emitters through Graphene Plasmonics

Control over the spontaneous emission of light through tailored optical environments remains a fundamental paradigm in nanophotonics. The use of highly confined plasmons in materials such as graphene provides a promising platform to enhance transition rates in the IR-THz by many orders of magnitude. However, such enhancements involve near-field plasmon modes or other kinds of near-field coupling like quenching, and it is challenging to use these highly confined modes to harness light in the far-field due to the difficulty of plasmonic outcoupling. Here in this paper, we propose that through the use of radiative cascade chains in multilevel emitters, IR plasmons can be used to enhance far field spectra in the visible and UV range, even at energies greater than 10 eV. Combining Purcell-enhancement engineering, graphene plasmonics, and radiative cascade can result in a new type of UV emitter whose properties can be tuned by electrically doping graphene. Varying the distance between the emitter and the graphene surface can change the strength of the far-field emission lines by 2 orders of magnitude. We also find that the dependence of the far-field emission on the Fermi energy is potentially extremely sharp at the onset of interband transitions, allowing the Fermi energy to effectively serve as a “switch” for turning on and off certain plasmonic and far-field emissions.

42 ENGINEERING↗
DOE OSTI2026

Photovoltage behaviour of p-Sb 2 S 3 photocathodes for hydrogen evolution: effect of n-In 2 S 3 passivation layers

The 1.76 eV band gap of antimony(iii) sulphide (Sb 2 S 3 ) makes this semiconductor material a promising light absorber for photoelectrochemical water splitting, but scalable fabrication approaches to efficient devices are still lacking. Here we show that compact Sb 2 S 3 films on FTO can be obtained by electrochemical growth from aqueous colloidal sulphur and antimony trichloride solutions, followed by mild annealing. These films can be converted into hydrogen evolution photocathodes after coating with In 2 S 3 passivation layers and the addition of Pt proton reduction co-catalysts. For the first time, vibrating Kelvin probe surface photovoltage (VKP-SPV) spectroscopy is used to observe the carrier dynamics in such photoelectrodes. While the bare Sb 2 S 3 films suffer from high surface recombination rates and poor electron extraction, the In 2 S 3 overlayer is found to raise the photovoltage and cathodic photocurrent density, due to passivation of surface defects and formation of a p–n heterojunction. In thick In 2 S 3 films, these benefits are offset by shading and slow electron transfer. Also, we find that O 2 strongly affects the band bending in the Sb 2 S 3 –air and In 2 S 3 –air junctions and their photovoltage. The optimised devices evolve H 2 at 77.5% Faradaic efficiency and with 0.084% applied bias photon-to-current efficiency (ABPE) at 0.12 V vs. RHE. The low ABPE value is attributed to Sb 2 S 3 sub-bandgap defects visible in SPV spectra, the random orientation of Sb 2 S 3 crystallites in the films, which inhibits charge transport, the absence of crystal facets of Sb 2 S 3 , and a detrimental Schottky junction at the FTO|Sb 2 S 3 interface.

de Araújo, Moisés A. [University of California, Da↗
DOE OSTI2016

Energy band gap and spectroscopic studies in Mn{sub 1-x}Cu{sub x}WO{sub 4} (0 ≤ x ≤ 0.125)

A study on the effect of nonmagnetic Cu{sup 2+} substitution at Mn{sup 2+} site on the structural and energy band gap of the MnWO{sub 4} is reported. Convenient solid state reaction route has been adopted for the synthesis of Mn{sub 1-x}Cu{sub x}WO{sub 4}. X-ray diffraction (XRD) pattern showed high crystalline quality of the prepared samples. Raman spectroscopic studies were carried out to understand the structural aspects of the doping. 15 Raman active modes were identified out of 18, predicted for wolframite type monoclinic structure of MnWO{sub 4}. UV-visible diffuse reflectance spectra were recorded and analyzed to get energy band gap of the studied system and are found in the range of 2.5 eV to 2.04 eV with a systematic decrease with the increase in Cu{sup 2+} concentration. Energy band gap values are verified by Density Functional Theory calculations based on projector augmented wave (PAW) method. The calculated values are in good agreement with the experimental data.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗