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At least 73 records · Page 4

Further investigation of CsI-coated microchannel plate quantum efficiencies

Previously, pulse-counting detection efficiencies measured for CsI-coated microchannel plate (MCP) detectors (two-stage chevron configuration with a single collecting anode) have been reported to be 15-20 percent near Lyman-alpha (1216 A), compared to typical 65 percent quantum yields of opaque CsI photocathodes. To investigate the possibility that an improvement in quantum yield could result from use of MCPs with a bias angle of about 25 deg instead of 8 deg as used previously, the previous measurements were reported with new MCPs having the larger bias angle. No significant improvement in detection efficiency was achieved; the new detector tests still yielded maximum efficiencies of the order of 20 percent near 1216 A.

Carruthers, George R.

OCS photolysis and absorption in the 200- to 300-nm region

A continuum source with three different interference filters and two different monochromatic sources were used to photolyze OCS in the region from 200 nm to 300 nm. The total quantum yield for the production of CO was measured, and the results indicate a primary quantum yield of 0.72 + or - 0.08. Absorption cross sections for OCS measured at 0.5-nm intervals are reported as well as the percent change in absorption upon cooling to 195 K. The structured features in the absorption are reinvestigated and discussed.

Rudolph, R. N.

The source of stratospheric NO and N2O

The photodissociation of O3 was investigated as a possible sources of N2O production in the stratosphere. Photolysis was conducted at 1576 A to generate the excited O2 states that react with N2 to form N2O. At this wavelength, there is a quantum yield of two for prompt production of oygen atoms, which is a consequence of the existence of two photodissociative channels giving comparable yields. One of these channels gives O(D1) and O2(b1sigma(+)subg), with a quantum yield of 0.6, whereas the other results in fragmentation of the O3, with production of three ground state oxygen atoms. The O2(b) is generated with vibrational excitation, and there are comparable populations in levels O to 3. These observations are the first to show O2(b) production from any photodissociative process, and were made under conditions in which the kinetics of vibrationally excited O2(b) can be studied. It appears that O3 photodissociation at 1576 A is not a good system for generating the higher electronic states of O2; it is likely that better results will be obtained at 1930 A.

Slanger, T. G.

Keldysh tuning of photoluminescence in a lead halide perovskite crystal

In 1964, Keldysh laid the groundwork for strong-field physics in atomic, molecular, and solid-state systems by delineating a ubiquitous transition from multiphoton absorption to quantum electron tunneling under intense AC driving forces. While both processes in semiconductors can generate carriers and result in photon emission through electron-hole recombination, the low quantum yields in most materials have hindered direct observation of the Keldysh crossover. Leveraging the large quantum yields of photoluminescence in lead halide perovskites, we show that we can not only induce bright light emission from extreme sub-bandgap light excitation but also distinguish between photon-induced and electric-field-induced processes. Our results are rationalized by the Landau-Dykhne formalism, providing insights into the non-equilibrium dynamics of strong-field light-matter interactions. These findings open new avenues for light upconversion and sub-bandgap photon detection, highlighting the potential of lead halide perovskites in advanced optoelectronic applications.

FOS: Physical sciences

Radiative Transfer Modeling of Phytoplankton Fluorescence Quenching Processes

We report the first radiative transfer model that is able to simulate phytoplankton fluorescence with both photo chemical and non-photo chemical quenching included. The fluorescence source term in the inelastic radiative transfer equation is proportional to both the quantum yield and scalar irradiance at excitation wavelengths. The photo chemical and non photo chemical quenching processes change the quantum yield based on the photosynthetic active radiation. A sensitivity study was performed to demonstrate the dependence of the fluorescence signal on chlorophyll a concentration, aerosol optical depths and solar zenith angles. This work enables us to better model the phytoplankton fluorescence, which can be used in the design of new space-based sensors that can provide sufficient sensitivity to detect the phytoplankton fluorescence signal. It could also lead to more accurate remote sensing algorithms for the study of phytoplankton physiology.

Inelastic scattering

Photodissociation of CO2 and quenching of metastables

Investigations in four different areas were carried out to further our understanding of the chemistry of the atmospheres of Mars and Venus. CO2 photodissociation quantum yields were determined in the 1300-1500 A spectral region by measuring both CO and oxygen atoms. The O(1S) quantum yield was determined for CO2 photodissociation in the 1060-1175 A spectral region. The measurement resolves the differences between two earlier experiments, and demonstrates that the O(1S) yield is unity throughout most of the measured region. The pathways for the quenching of O(1S) by N2O, CO2, H2O and NO were investigated and the source of the Venus nightglow, detected by Venera 9 and 10, was investigated. What appears to be a new O2 band system, was detected although the identity of the transition is not yet evident.

Slanger, T. G.

Quantitative absorption and fluorescence studies of NO between 1060 and 2000 A

Synchrotron radiation in the 1060 to 2000 A region was used to measure the average absorption and fluorescence cross sections of NO and to determine approximate photodissociation quantum yields. Several vibrational levels of the D(2) sigma(+), E(2) sigma(+), and B(2) delta states have high fluorescence quantum yields. The C(2) and B(2) states do not fluoresce when the excitation energies are above the first dissociation limit, in accord with previous experiments. In general, the fluorescence yields decrease with increasing photon energy. The quantitative measurements are compared with spectroscopic observations and are found to be reasonably consistent.

Guest, J. A.

Photodissociation of cyanoacetylene: Application to the atmospheric chemistry of Titan

The quantum yield and reaction threshold for the photochemical dissociation of cyanoacetylene into a hydrogen atom and the cyanoethynyl radical have been determined. The quantum yield at 185 nm is approximately 0.09. The threshold is approximately 240 nm. Combination of this data with literature values shows that production of excited-state cyanoacetylene is the major primary process resulting from irradiation between 185 and 254 nm. Also determined are the relative rate constants for the abstraction of a hydrogen atom from hydrogen, methane, and ethane by the cyanoethynyl radical (k(H2):k(CH4):k(C2H6) = 1:9.3:63). Implications of these results for the proposal that hydrogen abstraction plays an important role in the conversion of methane to ethane and in the protection of unsaturated compounds from photoconsumption in the atmosphere of Titan are discussed.

Clarke, David W.

Elucidating the role of oxidation in two-dimensional silicon nanosheets

We report a synthetic protocol that yields hydrogen-terminated 2D silicon nanosheets with greatly reduced siloxane (e.g., Si–O–Si, O x Si) content. These nanosheets displayed weak, broad photoluminescence centered near 610 nm with a low absolute photoluminescence quantum yield (as low as 0.2%). By intentionally oxidizing the nanosheets, the photoluminescence peak emission wavelength blueshifted to 510 nm, and the quantum yield increased by more than an order of magnitude to 8.5%. These results demonstrate that oxidation of 2D silicon nanosheets modulates the material's bandgap and suggests that previously reported photoluminescence properties for this material resulted, in part, from oxidation.

Essner, Jeremy B. [Iowa State Univ., Ames, IA (Uni

Oxygen interaction with space-power materials

Data from the space shuttle flights have established that many materials experience relatively rapid degradation when exposed to the low Earth orbit ambient atmosphere, which is predominately atomic oxygen. While much was learned from samples flown on the shuttle, laboratory simulations of the shuttle environment are necessary for a detailed understanding of the various interactions which contribute to the observed degradations. These laboratory experiments are particularly important for predicting the deterioration to be expected for materials aboard orbiting power systems, which will be exposed for long periods of time and could have components operating at very high temperatures. By using a mass spectrometer to synchronously detect molecules emitted from the surface as a result of amplitude modulated oxygen ion bombardment, quantum yields were obtained as a function of ion energy. A technique was developed to obtain preliminary yield data by slowly scanning the mass setting of the mass spectrometer; measurements were extended down to zero modulation frequency; yield data was obtained for the insulating materials (Nomex, Kevlar, and Teflon) used in the construction of electrodynamic tethers; a heated sample holder was constructed to investigate the effect of sample temperature on quantum yields; and the instrumentation was developed to observe the mass spectrometer signal as a function of time during and following bombardment of the sample by a brief (approximately 1 millisecond) pulse of ions.

Eck, T. G.

Quantitative absorption and fluorescence study of CO from 1060 to 1550 A

Measurement of the photoabsorption cross section of CO in the 1060-1550 A region using synchrotron radiation is described. The oscillator strengths for the transitions from CO (Chi1Sigma+ to various excited states are obtained from these data. Fluorescence from excited CO was observed in the 1150 to 3000 A and 3000 to 8000 A regions. The quantum yields for the production of fluroescence from the Alpha(1)P and B(1)Sigma(+) states are unity because their excitation energies are below the dissociation limit. The C(1)Sigma(+) , v = O level has significant fluorescence quantum yields both in the UV and visible region, but the yields for the E(1)Pi, v = O and C(1)Sigma(+), v = 1 levels are very small. The C(1)Sigma(+), v = 1 level is presumably predissociated. The cross sections for the production of fluroescence from the a'(3)Sigma(+), d(3)Delta sub 1, e(3)Sigma(-) yields a(3)Pi, and B(1)Sigma(+), C(1)Sigma(+) yields A(1)Pi transitions upon excitation from the X(1)Sigma(+) were measured.

Lee, L. C.

Single-Step Nonthermal Plasma Synthesis of Water-Soluble and Near-Infrared-Emitting Si Quantum Dots for Bioimaging Applications

Here, we present a single-step nonthermal plasma method for the synthesis of near-infrared (NIR)-emitting and water-soluble Si quantum dots (QDs) for bioimaging applications. Oxygen gas and water vapor were introduced together with acrylic acid (AA) into the afterglow region of the synthesis plasma leading to the surface functionalization of the upstream synthesized Si QDs. The simultaneous surface oxidation and ligand grafting enabled solubility and colloidal stability of the Si QDs in water, as evidenced by strongly reduced hydrodynamic diameters. Aged Si QDs in water emitted NIR photoluminescence (PL) at around 830 nm. The PL quantum yield of the Si QDs in water increased over time from initially undetectable to ~30% after 8 days. Cell viability tests showed that >70% of 3T3 cells survived for 24 h at a concentration of 200 μg/mL of oxidized AA grafted Si QDs. The water solubility, NIR emission with a high quantum yield, and cell viability make the Si QDs promising for bioimaging applications.

36 MATERIALS SCIENCE

Production of NO2 from Photolysis of Peroxyacetyl Nitrate

Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248 nm, and the NO2 photoproduct was detected by laser-induced fluorescence. The quantum yield for the production of NO2 from PAN photolysis was determined by comparison to HNO3 photolysis data taken under identical experimental conditions. The average of data collected over a range of total pressures, precursor concentrations, and buffer gases was 0.83 +/- 0.09 for the NO2 quantum yield, where the statistical uncertainty is 2 standard deviations.

Mazely, Troy L.

Revisions to Photochemical Data for Use in Atmospheric Modeling

Solar and stellar flux incident on an atmosphere can cause molecules to dissociate into highly reactive species and allows for photochemical processes to play a fundamental role in atmospheric chemistry. While models have tried to simulate such processes, they are extremely sensitive to photoabsorption cross-sections and quantum yields: two parameters that are important in determining the photodissociation rate, and hence the lifetime, of atmospheric compounds. Obtaining high-resolution and current data for these parameters is therefore highly desirable. Due to this, database and literature searches for high-quality cross-sections and quantum yields were performed and compiled for KINETICS, a Caltech/JPL Chemical Transport Model that can be used in modeling planetary atmospheres. Furthermore, photodissociation rates determined by running a Titan 1-D model were used to verify the completeness of these latest revisions.

Chemical Transport Model (CTM)

Third-order photon correlations extract single-nanocrystal multiexciton properties in solution

Colloidal semiconductor nanocrystals are considered promising materials for high-flux optical applications, including lasing, light-emitting diodes, biological imaging, and quantum optics. In high-flux applications, multiexcitons can significantly contribute to emission, influencing its brightness, spectral purity, and kinetics. As a result, understanding and controlling multiexciton emission in colloidal nanocrystal materials is of the utmost importance. In the past, single-nanocrystal photon correlation methods have been applied to understand biexciton and triexciton efficiencies, lifetimes, and spectra. While powerful, such methods suffer from user selection bias and require stable emission from single nanocrystals. To compensate for this shortcoming, second-order correlation methods were developed to extract sample-averaged biexciton properties from a solution of nanocrystals. Until now, however, the analogous third-order solution photon correlation methods remained unexplored. In this work, we present a pair of third-order photon correlation techniques to obtain the sample-averaged single-nanocrystal triexciton quantum yield and lifetime in a solution-phase experiment. These techniques derive from the relationship between the Poisson probability of nanocrystal photon absorption and the intrinsic probability of nanocrystal photon emission. We validate the theoretical background of these techniques by creating a numerical model to simulate the diffusion and emission of many nanocrystals in solution. Our simulations confirm that the average triexciton quantum yield and triexciton lifetime can be extracted from a solution of nanocrystals. These techniques will enable researchers to gain a better understanding of the fundamental multiexciton properties of colloidal nanocrystals.

Horowitz, Jonah R. [Massachusetts Institute of Tec

N2O5 photolysis products investigated by fluorescence and optoacoustic techniques

Pulsed laser photolysis of N2O5 near 290 nm, coupled with fluorescence detection (calibrated by NO2 photoloysis), showed that the O(P-3) quantum yield is not more than 0.1. A pulsed laser optoacoustic technique in a flow tube was tested by photolysis of NO2 and then applied to N2O5. Nitric oxide was added to react with NO3 free radicals; the resulting increase in the optoacoustic signal confirmed the presence of NO3 free radicals. Based on the relative optoacoustic signals observed for NO2 and N2O5, the quantum yield for NO3 production is 0.8 + or - 0.2.

Barker, J. R.

Biosynthetic Porphyrins and the Origin of Photosynthesis

Since the prebiotic atmosphere was anaerobic, if not reducing, a useful function of primordial photosynthesis would have been to photooxidize reduced substrates such as Fe(+2), S(-2) or reduced organic molecules and to emit hydrogen. Experiments have shown that the early biogenic pigments uroporphyrin and coproporphyrin do photooxidize organic compounds and emit hydrogen in the presence of a platinum catalyst. These experiments were carried out in dilute aqueous solution near neutral pH under anaerobic atmosphere, and quantum yields near 10-2 were obtained. Thus relevant prebiotic conditions were maintained. Rather then to further optimize conditions, attempts were made to replace the platinum catalyst by a more prebiotically suitable catalyst. Trials with an Fe4S4(SR)4 cluster, in analogy to the present hydrogenase and nitrogenase, were not successful. However, experiments using cobalt complexes to catalyze the formation of hydrogen are promising. In analogy with biological photosynthetic systems which group pigments, electron transfer molecules and enzymes in clusters for efficiency, it was found that binding the biogenic porphyrins to the polyvinyl alcohol used to support the platinum catalyst did increase the quantum yield of the reaction. It was also found that ultraviolet light can serve to photo-oxidize porphyrinogens to porphyrins under anaerobic conditions. Thus the formation of the colorless porphyriogens by the extraordinarily simple biosynthetic pathway would not be a problem because of the prevalence of UV light in the prebiotic, anoxic atmosphere.

David Mauzerall

Relationship between the Fluorescence Lifetime of Chlorophyll 'a' and Primary Productivity within the Mississippi River Plume and Adjacent Shelf Region

In situ measurements of chlorophyll fluorescence intensity have been widely used to estimate phytoplankton biomass. However, because the fluorescence quantum yield of chlorophyll a in vivo can be highly variable, measurements of chlorophyll fluorescence intensity cannot be directly correlated with phytoplankton biomass and do not provide information on the physiological state of the phytoplankton under study. Conversely, lifetime-based measurements of chlorophyll fluorescence provide a framework in which photosynthetic rates of phytoplankton can be analyzed according to phytoplankton physiology. Along with the measurement of primary production and ambient nutrient concentrations within the Mississippi River plume in the northern Gulf of Mexico, phytoplankton fluorescence lifetimes were measured using a Fluorescence Lifetime Phytoplankton Analyzer (developed under a NASA Small Business Innovative Research contract to Ciencia, Inc.). Variability of fluorescence lifetimes within the plume can be used as a background from which to interpret variations in the maximum quantum yield of photochemistry. The extent to which nutrient and effluent loading in this dynamic coastal area affect the photosynthetic performance of phytoplankton will be presented as a function of phytoplankton fluorescence lifetimes.

Hall, Callie