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At least 217 records · Page 12

Digital Architecture for a Trace Gas Sensor Platform

A digital architecture has been implemented for a trace gas sensor platform, as a companion to standard analog control electronics, which accommodates optical absorption whose fractional absorbance equivalent would result in excess error if assumed to be linear. In cases where the absorption (1-transmission) is not equivalent to the fractional absorbance within a few percent error, it is necessary to accommodate the actual measured absorption while reporting the measured concentration of a target analyte with reasonable accuracy. This requires incorporation of programmable intelligence into the sensor platform so that flexible interpretation of the acquired data may be accomplished. Several different digital component architectures were tested and implemented. Commercial off-the-shelf digital electronics including data acquisition cards (DAQs), complex programmable logic devices (CPLDs), field-programmable gate arrays (FPGAs), and microcontrollers have been used to achieve the desired outcome. The most completely integrated architecture achieved during the project used the CPLD along with a microcontroller. The CPLD provides the initial digital demodulation of the raw sensor signal, and then communicates over a parallel communications interface with a microcontroller. The microcontroller analyzes the digital signal from the CPLD, and applies a non-linear correction obtained through extensive data analysis at the various relevant EVA operating pressures. The microcontroller then presents the quantitatively accurate carbon dioxide partial pressure regardless of optical density. This technique could extend the linear dynamic range of typical absorption spectrometers, particularly those whose low end noise equivalent absorbance is below one-part-in-100,000. In the EVA application, it allows introduction of a path-length-enhancing architecture whose optical interference effects are well understood and quantified without sacrificing the dynamic range that allows quantitative detection at the higher carbon dioxide partial pressures. The digital components are compact and allow reasonably complete integration with separately developed analog control electronics without sacrificing size, mass, or power draw.

Gonzales, Paula↗

Polymer nanoparticle photocatalysts realized in non-aqueous solvents

Colloidal organic nanoparticles (oNPs) have emerged as a promising category of photocatalyst, thanks to their long-lived surface-bound charges, electronic tunability, and strong absorption in the visible spectrum. Our previous research has established a direct correlation between charge generation in oNPs and their photocatalytic activity, highlighting their effectiveness as a framework for stable, long-lived free carriers. However, oNPs have been restricted to use only in aqueous environments as a result of being synthesized via either nano-emulsion or nano-precipitation procedures. Herein, we present a method for transferring oNP photocatalysts from water into polar non-aqueous solvents while retaining their long-term colloidal stability. We observed that the polymer chains in the solvent-transferred oNPs rearrange from a predominantly H-aggregate structure in water to a combination of H- and J-aggregate characteristics in N,N-dimethylformamide, suggesting a dynamic rearrangement in response to the new solvent environment. Importantly, transient absorption and time-resolved microwave conductivity measurements confirm that the solvent-transferred oNPs maintain their ability to generate free charges at an internal heterojunction. This development opens unique opportunities for eventually leveraging light-generated, long-lived electrons and holes in synthetic redox chemistry across diverse solvent environments, a direction that will be explored in future studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron tail suppression and effective collisionality due to synchrotron emission and absorption in mildly relativistic plasmas

Synchrotron radiation losses are a significant cause of concern for high-temperature aneutronic fusion reactions such as proton–Boron 11. The fact that radiation losses occur primarily in the high-energy tail, where the radiation itself has a substantial impact on the electron distribution, necessitates a self-consistent approach to modeling the diffusion and drag induced by synchrotron absorption and emission. Furthermore, an accurate model must account for the fact that the radiation emission spectrum is momentum-dependent, and the plasma opacity is frequency-dependent. Here, we present a simple Fokker–Planck operator, built on a newly solved-for blackbody synchrotron diffusion operator, which captures all relevant features of the synchrotron radiation. Focusing on magnetic mirror fusion plasmas, we show that significant suppression of the electron distribution occurs for relativistic values of the perpendicular electron momentum, which therefore emit much less radiation than predicted under the assumption of a Maxwell–Jüttner distribution.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Comparison of measured and theoretical inverse bremsstrahlung and photoionization absorption of infrared radiation in a H-He plasma.

The absorption coefficients of 1.15- and 3.39-micrometer radiation for a homogeneous H-He plasma have been measured in a temperature and electron density range where the major absorption mechanisms are electron-ion inverse bremsstrahlung and neutral-atom photoionization. Measurements were made behind both the incident and reflected shock waves in a driven tube by recording the laser intensity transmitted along the tube diameter as a function of time. The measured values compare well with those obtained from theoretical calculations for a gas in thermodynamic equilibrium.

Billman, K. W.↗

Quenching of the fluorescence of NO2

The fluorescence yield of NO2 was monitored at 25 C with incident wavelengths of 4047, 4358, and 4800A at fluorescence wavelengths of 4860, 5577, and 6300A. The NO2 pressure was varied between 0.004 and 0.080 torr. Measurements were taken both in the absence of foreign gases and in the presence of up to 30 torr. He, N2, and O2 at each NO2 pressure. In the absence of foreign gases, the self quenching follows a Stern-Volmer quenching mechanism, but foreign-gas quenching shows marked deviations from this mechanism. Both from lifetime and kinetic considerations, it is argued that the electronic state formed by absorption of the radiation cannot be the emitting state. Emission occurs from several vibrational levels of the emitting state, the various vibrational levels being formed by collisional cascade reactions. The appropriate quenching rate constant ratios were measured and tabulated. Even the two electronic state mechanism is insufficient to explain all the observations.

Braslavsky, S.↗

Interstellar grains in elliptical galaxies

We consider the evolution and heating of dust embedded in the hot interstellar medium of isolated elliptical galaxies. We first construct a new set of galaxy models spanning a decade in luminosity which we use to study the evolution of dust as it is ejected by stellar sources, merges and flows with the interstellar gas, and is sputtered away due to the presence of the hot gas. We find that although grains can flow a considerable distance from the parent star in some cases before being sputtering away, the grain size distribution at a given location is accurately determined by assuming in situ sputtering of dust grains as they are ejected by the parent star. We find that dust heating is dominated by absorption of ambient starlight. Heating due to collisions with energetic electrons in the hot gas and absorption of thermal X-rays is smaller by orders of magnitude. We also find that for the largest galaxy considered (L(sub B) approximately 10 (exp 11) solar luminosity) the energy lost from the hot gas due to electronic collisions with the dust is about an order of magnitude less than that lost due to thermal emission in X-rays. The gas in smaller galaxies loses even less of its energy via heating of grains. In deriving this result, we find that the inclusion of grain sputtering is a crucial ingredient of the calculation. The presence of dust grains is therefore energetically unimportant for elliptical galaxy cooling flow models.

Tsai, John C.↗

Physics of compact nonthermal sources. III - Energetic considerations

The energy content of the compact incoherent electron-synchrotron sources 3C 84, 3C 120, 3C 273, 3C 279, 3C 454.3, CTA 102, 3C 446, PKS 2134+004, VRO 42.22.01 and OJ 287 is calculated on the assumption that the low-frequency turnovers in the radio spectrum are due to self-absorption and that the electron distribution is isotropic. The dependence of the source parameters on various modifications of the standard assumptions is determined. These involve relativistic motions, alternate explanations for the low-frequency turnover, proton-synchrotron radiation, and distance to the source. The canonical interpretation is found to be accurate in many respects; some of the difficulties and ways of dealing with them are discussed in detail.

Burbidge, G. R.↗

Interstellar medium model

A model of the ionized part of the interstellar medium was developed, based on the low frequency observations by the Radio Astronomy Explorer Satellite with a background of nonthermal radiation. This nonthermal background radiation is caused by synchrotron emission from cosmic ray electrons, and at low frequencies this emission is heavily absorbed by free-free absorption from the residual thermal electrons in the interstellar medium. By an appropriate model, parameters relevant to both the thermal and nonthermal components of the interstellar medium are shown. The observations were taken with the 100 deg dipole antenna and separated into galactic and extragalactic components. This model was developed using only the separated galactic component.

Novaco, J. C.↗

Direct observation of entangled electronic-nuclear wave packets

We present momentum resolved covariance measurements of entangled electronic-nuclear wave packets created and probed with octave spanning phaselocked ultrafast pulses. We launch vibrational wave packets on multiple electronic states via multiphoton absorption, and probe these wave packets via strong field double ionization using a second phaselocked pulse. Momentum resolved covariance mapping of the fragment ions highlights the nuclear motion, while measurements of the yield as a function of the relative phase between pump and probe pulses highlight the electronic coherence. The combined measurements allow us to directly visualize the entanglement between the electronic and nuclear degrees of freedom and follow the evolution of the complete wavefunction. Published by the American Physical Society 2024

Moğol, Gönenç↗

Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. Furthermore, a detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-N amido complexes using a high-spin ground-state analogue as a spectral model for the 5 T 2 excited state.

14 SOLAR ENERGY↗

Nanoscale and Element-Specific Lattice Temperature Measurements Using Core-Loss Electron Energy-Loss Spectroscopy

Measuring nanoscale local temperatures, particularly in vertically integrated and multicomponent systems, remains challenging. Spectroscopic techniques like X-ray absorption and core-loss electron energy-loss spectroscopy (EELS) are sensitive to lattice temperature, but understanding thermal effects is nontrivial. This work explores the potential for nanoscale and element-specific core-loss thermometry by comparing the Si L2,3 edge’s temperature- dependent redshift against plasmon energy expansion thermometry (PEET) in a scanning TEM. Using density functional theory (DFT), time-dependent DFT, and the Bethe−Salpeter equation, we ab initio model both the Si L 2,3 and plasmon redshift. We find that the core-loss redshift occurs due to bandgap reduction from electron−phonon renormalization. Our results indicate that despite lower core-loss signal intensity compared to plasmon features, core-loss thermometry has key advantages and can be more accurate through standard spectral denoising. Specifically, we show that the Varshni equation easily interprets the core-loss redshift for semiconductors, which avoids plasmon spectral convolution for PEET in complex junctions and interfaces. We also find that core-loss thermometry is more accurate than PEET at modeling thermal lattice expansion in semiconductors, unless the specimen’s temperature-dependent dielectric properties are fully characterized. Furthermore, core-loss thermometry has the potential to measure nanoscale heating in multicomponent materials and stacked interfaces with elemental specificity at length scales smaller than the plasmon’s wave function.

Bethe–Salpeter equation↗

Direct Observation of the ππ* to nπ* Transition in 2-Thiouracil via Time-Resolved NEXAFS Spectroscopy

The photophysics of nucleobases has been the subject of both theoretical and experimental studies over the past decades due to the challenges posed by resolving the steps of their radiationless relaxation dynamics, which cannot be described in the framework of the Born–Oppenheimer approximation (BOA). In this context, the ultrafast dynamics of 2-thiouracil has been investigated with a time-resolved NEXAFS study at the Free Electron Laser FLASH. Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS) can be used to observe electronic transitions in ultrafast molecular relaxation. We performed time-resolved UV-pump/X-ray probe absorption measurements at the sulfur 2s (L1) and 2p (L2/3) edges. We are able to identify absorption features corresponding to the S2 (ππ*) and S1 (nπ*) electronic states. We observe a delay of 102 ± 11 fs in the population of the nπ* state with respect to the initial optical excitation and interpret the delay as the time scale for the S2 → S1 internal conversion. We furthermore identify oscillations in the absorption signal that match a similar observation in our previous X-ray photoelectron spectroscopy study on the same molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron-impact excitation of UF6 at an electron energy of 20 eV in the energy-loss range of 0-10 eV

A technique combining electron impact excitation and optical absorption spectroscopy was applied to UF6. The crucial features of the experiment were that: (1) the electron optics was differentially pumped relative to the scattering chamber and (2) the target UF6 beam was condensed on a liquid nitrogen cold trap placed immediately above the scattering center. Energy loss spectra are presented at an incident electron energy of 20 eV and at scattering angles between 20 and 135 degrees. It is shown that no transitions are found below the first-detected feature at 3.0 eV and an optically forbidden excitation is found at 4.2 eV. A fairly strong optical absorption at 4.8 eV is observed to 'fill-in' at a scattering angle of 20 degrees but is practically absent at higher angles.

Chutjian, A.↗

A Study of the Non-Thermal X-ray Emission of Shell-Type Supernova Remnants

The term of the forth year of the award is the period from March 15, 2003 to March 14, 2004. During this year, Dr. Thomas Pannuti, who had been performing most of the analyses, made a transition to a new position at Caltech. As of September 2003, Dr. Michael Stage began performing most of the analyses. Dr. Stage has begun constructing a detailed catalog of the spatial and spectral properties of young supernova remnants as described in sections 1 and 4 of the proposal. Specifically, he has focused on the analysis of Chandra ACIS data. The exquisite spatial resolution of the Chandra telescope and the modest spectral resolution of the CCDs make these data ideal. Dr. Stage has developed a standard set of procedures to reduce the data, generate telescope and detector response libraries and handle instrumental and celestial background subtraction. He has also adapted some existing code to automate spectral extraction and fitting. This code enables us to analyze the spectra of tens of thousands of small subregions of supernova remnants. Dr. Stage has recently applied this process to ACIS data for the supernova remnants Cas A and Kepler. The results include maps of the fitted parameters, such as individual line intensities and centroids (i.e. Doppler shifts), the electron temperature, and the absorption column density. These maps are more accurate than simple energy-cut images because it is difficult (and sometimes impossible) to cleanly separate the line emission from the underlying continuum (especially at low energies). It is now possible to identify the locations at which emission from each element is produced. Some of the elements are seen to be layered. The electron temperature maps demonstrate that the outer edges of Cas A and Kepler are very hot with weak lines. This emission is almost certainly synchrotron dominated. Therefore, not only are the maps interesting in and of themselves, but they also provide an unbiased means of easily identifying features in the remnants that can be studied in more detail using, for example, synchrotron models. Over the next year, Dr. Stage will refine the analysis procedures, expand the analyses to include several other remnants, present the results at major scientific conferences and publish a catalog of the results. Since this work is producing impressive results, we have applied for very long Chandra observations of Kepler and Tycho to obtain enough counts to take lull advantage of the technique. A i Ms observation of Cas A is already scheduled. Over the past year, I completed a joint, spectra,l analysis of some X-ray, radio, and gamma-ray data for the supernova remnant SN 1006. The results of this analysis show that the synchrotron and, hence, electron spectrum of the remnant is curved. The amount of curvature in the electron spectrum is quantitatively consistent with predictions of the amount of curvature in the proton spectrum of the remnant. A paper describing this work is nearly complete. When Dr. Pannuti left, he was analyzing X-ray data for the young supernova remnant G266.2-1.2. Dr. Pannuti found the first evidence of thermal X-ray emission from this remnant. Furthermore, like SN 1006, the cutoff frequency varies with azimuth along the bright northeastern rim. This work will be published during the coming year.

Allen, Glenn E.↗

Simultaneous satellite and riometer measurements of particles during solar cosmic ray events.

The expected 30 and 50 MHz riometer absorptions have been calculated for three events in 1969 using data from the MDAC-W charged particle experiment on OGO 6. Several times during each event, the satellite passed over the MDAC-W Arctic and Antarctic Geophysical Observatories. The calculated total absorption (using 2 minute averages of the data) agrees well with the measured absorption for the overpasses. The alpha particle and electron contributions usually amount to less than a few percent of the proton absorption. During the large November 2, 1969 event, however, the electrons produced the major part of the absorption up to the peak and a significant contribution during virtually its entire duration. With the two frequencies for which simultaneous riometer data were taken, it is possible to detect the softening of the particle spectra during the events, and the relative hardness differences between events.

Baker, M. B.↗

Hierarchical Hybrid Multifunctional Materials through Interface Engineering

This project focuses on the development of stimuli-responsive hybrid multifunctional materials. We place emphasis on the design, synthesis, structural characterization, evaluation of functional properties (electronic, thermal and optical) of several (1-x)Cu 2 Se/(x)WBGS hierarchical bulk composites between Cu 2 Se, a narrow band gap semiconductor (NBGS), with a range of wider band gap semiconductors (WBGS) such as CuMSe 2 (M = Al, Ga, In, Fe, Cr) and Cu 4 TiSe 4 . Cu2Se is a well-studied NBGS with excellent thermoelectric properties (high electrical conductivity, large thermopower, etc.) while CuMSe 2 and Cu 4 TiSe 4 are high performance solar absorber materials (large band gap, large absorption coefficient, etc.). Our primary objectives are (i) to demonstrate the ability to integrate dissimilar functional properties such as large optical absorption coefficient and high electronic conductivity, within (1-x)Cu 2 Se/(x)WBGS composite; and (ii) to establish the correlation between the hierarchical structural entanglement of Cu 2 Se with WBGS (CuMSe 2 or Cu 4 TiSe 4 ) phase, the interactions between native electronic defects within the coexisting phases in the resulting (1-x)Cu 2 Se/(x)WBGS bulk composites , and the impacts on their electronic conductivity, thermal transport and optical properties.

36 MATERIALS SCIENCE↗