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At least 1,711 records · Page 95

Laser Induced Fluorescence Spectroscopy of Neutral and Ionized Polycyclic Aromatic Hydrocarbons in the Cosmic Simulation Chamber

Polycyclic aromatic hydrocarbon (PAH) molecules are considered the best carriers to account for the ubiquitous infrared emission bands. PAHs have also been proposed as candidates to explain the diffuse interstellar bands (DIBs), a series of absorption features seen on the interstellar extinction curve and are plausible carriers for the extended red emission (ERE), a photoluminescent process associated with a wide variety of interstellar environments. Extensive efforts have been devoted over the past two decades to characterize the physical and chemical properties of PAH molecules and ions in space. Absorption spectra of PAH molecules and ions trapped in solid matrices have been compared to the DIBs. Absorption spectra of several cold, isolated gas-phase PAHs have also been measured under experimental conditions that mimic the interstellar conditions. The purpose of this study is to provide a new dimension to the existing spectroscopic database of neutral and single ionized PAHs that is largely based on absorption spectra by adding emission spectroscopy data. The measurements are based on the laser induced fluorescence (LIF) technique and are performed with the Pulsed Discharge Nozzle (PDN) of the COSmIC laboratory facility at NASA Ames laboratory. The PDN generates a plasma in a free supersonic jet expansion to simulate the physical and the chemical conditions in interstellar environments. We focus, here, on the fluorescence spectra of large neutral PAHs and their cations where there is a lack of fluorescence spectroscopy data. The astronomical implications of the data (e.g., ERE) are examined.

Laboratory↗

Extracting Olivine (Fo-Fa) Compositions from Raman Spectral Peak Positions

Olivine and pyroxene are two major basaltic minerals that have been identified at Gusev Crater and Meridiani Planum by the Mars Exploration Rovers. Full petrologic characterization of a sample (rock or soil), however, requires determining the range of mineral compositions, extent of zoning, range of grain sizes, mineral associations, presence of xenocrysts, etc. Information of this sort will aid the interpretation of sample crystallization and differentiation histories and help discriminate between lithologies. In Raman spectroscopic experiments, minerals are identified by their spectral patterns and mineral compositions can be inferred from the peak positions. Instruments currently in use or slated for impending surface exploration missions provide only average elemental compositions for relatively large rock or soil targets or bulk mineral analysis. No techniques currently in use or scheduled for flight can characterize both structure and composition of individual mineral grains, in-situ, like the Mars Microbeam Raman Spectrometer (MMRS). The MMRS is designed to take 100 spectra along a 1 cm linear traverse on the surface of a sample, with contributions from one or a few mineral phases per spectrum. We presented a method to extract structural and compositional information from the Raman spectra of quadrilateral pyroxenes. The pyroxene calibration was applied to a Raman spectroscopic study of Martian meteorite EETA79001 along with a preliminary olivine calibration, where we demonstrated the capability to discriminate related lithologies using Raman point counts. This paper presents an improved olivine calibration that will further aid sample characterization and the study of alteration processes.

Kuebler, K.↗

Spectroscopic properties of (PVA+ZnO):Mn{sup 2+} polymer films

Electron Paramagnetic Resonance (EPR), optical absorption and infrared spectral studies have been carried out on Mn{sup 2+} ions doped in poly(vinyl alcohol) complexed with zinc oxide polymer films prepared by solution cast technique. The EPR spectra of 1 mol% Mn{sup 2+} ions doped polymer complex (PVA+ZnO) at room temperature exhibit sextet hyperfine structure (hfs), centered at 2.01. The spin-Hamiltonian parameter values indicate that the ground state of Mn{sup 2+} ion in d{sup 5} and the site symmetry around Mn{sup 2+} ions in tetragonally distorted octa hedral site. The optical absorption spectra exhibits two bands centered at 275nm at 437nm. The FTIR spectrum exhibits bands characteristic of stretching and banding vibrations of O-H, C-H and C=C groups.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Synthesis and Characterization of Poly-3,4-ethylenedioxythiophene/2,5-Dimercapto-1,3,4-thiadiazole (PEDOT-DMcT) Hybrids

Organosulfur Compounds (OSCs) represent an attractive alternative as organic cathode materials for electrochemical energy storage (EES) applications. They intrinsically have high gravimetric capacity (although low volumetric) and are typically inexpensive, since they are composed of abundant elements (i.e. C, N, O, and S). However, OSCs, specifically thiolate-containing OSCs generally suffer from slow charge transfer kinetics. To mitigate the charge transfer limitations, conducting polymers (CPs) such as poly-3,4-ethylenedioxythiophene (PEDOT) have been employed as electrocatalysts. In this manuscript, we have covalently modified a PEDOT film with an OSC (i.e. 2,5-dimercapto-1,3,4-thiadiazole di-lithium salt (Li2DMcT)). We have developed a synthetic strategy that employs, for the first time, a post-polymerization modification reaction as a tractable and viable technique to modify organic materials for EES electrodes. Electrochemical characterization, via cyclic voltammetry showed the expected pseudocapacitive response of PEDOT with the superimposed faradaic processes of the covalently bound DMcT. Moreover, spectroscopic characterization using Raman spectroscopy provided mechanistic insights into the electrochemical reactions. Furthermore, we electropolymerized films onto coin-cell electrodes and tested them in half-cell configurations and found that the capacity retention of the films was significantly enhanced, when compared with the PEDOT/DMcT composites (mixed but not covalently bound).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First fringes with an integrated-optics beam combiner at 10 µm A new step towards instrument miniaturization for mid-infrared interferometry

Context. Observations of milliarcsecond-resolution scales and high dynamic range hold a central place in the exploration of distant planetary systems in order to achieve, for instance, the spectroscopic characterization of exo-Earths or the detailed mapping of their protoplanetary disc birthplace. Multi-aperture infrared interferometry, either from the ground or from space, is a very powerful technique to tackle these goals. However, significant technical

79 ASTRONOMY AND ASTROPHYSICS↗

Accurate gravities of F, G, and K stars from high resolution spectra without external constraints

We demonstrate a new procedure to derive accurate and precise surface gravities from high resolution spectra without the use of external constraints. Our analysis utilizes Spectroscopy Made Easy with robust spectral line constraints and uses an iterative process to mitigate degeneracies in the fitting process. We adopt an updated radiative transfer code, a new treatment for neutral perturber broadening, a line list with multiple gravity constraints and separate fitting for global stellar properties and abundance determinations. To investigate the sources of temperature dependent trends in determining log g noted in previous studies, we obtained Keck HIRES spectra of 42 Kepler asteroseismic stars. In comparison to asteroseismically determined log g our spectroscopic analysis has a constant offset of 0.01 dex with a rms scatter of 0.05 dex. We also analyzed 30 spectra which had published surface gravities determined using the a/R{sub ∗} technique from planetary transits and found a constant offset of 0.06 dex and rms scatter of 0.07 dex. The two samples covered effective temperatures between 5000 and 6700 K with log g between 3.7 and 4.6.

79 ASTRONOMY AND ASTROPHYSICS↗

Maximizing the impact of the Vera Rubin Observatory LSST, and DESI and CMB-S4 experiments in constraining gravity and dark sector physics

The work in this award has addressed our objectives on a number of fronts: Current graduate student Chris Wilson and Bean are determining how cosmic voids can be used to test the properties of gravity, leveraging simulations from DESI collaborator Baojiu Li and refining theoretical Gaussian Streaming Model approaches to predict galaxy dynamics in voids when the cosmology is not GR. This work is still underway, including analyses of the efficacy of void quadrupole correlation statistics and void size functions when studying dark matter halo statistics or the expected galaxy distributions from upcoming galaxy surveys; Current graduate student Yulin Gong, Bean with collaborators are refining techniques to extract out the kinetic Sunyaev Zel’dovich effect from galaxy cluster survey data and CMB temperature anisotropies, with the intent to further ready this pipeline development in readiness for spectroscopic data from DESI and LSST along with CMB-S4 measurements.

79 ASTRONOMY AND ASTROPHYSICS↗

Design, fabrication and performance of two grazing incidence telescopes for celestial extreme ultraviolet astronomy

The design and performance of grazing incidence telescopes for celestial extreme ultraviolet (EUV) astronomy are described. The telescopes basically consist of a star tracker, collimator, grazing incidence mirror, vacuum box lid, vacuum housing, filters, a ranicon detector, an electronics box, and an aspect camera. For the survey mirror a Wolter-Schwarzschild type II configuration was selected. Diamond-turning was used for mirror fabrication, a technique which machines surfaces to the order of 10 microns over the required dimensions. The design of the EUV spectrometer is discussed with particular reference to the optics for a primarily spectroscopic application and the fabrication of the f/10 optics.

Lampton, M.↗

0.Measurements of H216O Linestrengths and Air-Induced Broadenings and Shifts in the 815-nm Spectral Region

The linestrengths for 40 absorption lines of H2 16-O water vapor that were located between 813 and 820 nm were measured; most of these lines were selected for their potential usefulness in laser remote measurements of atmospheric humidity using the differential absorption lidar technique. The air-induced pressure-broadening coefficients were also measured for 32 of these lines and the air-induced pressure shift coefficients were measured for 29 lines. These spectroscopic parameters were derived from spectra obtained with an AlGaAs diode laser and two long-path absorption cells. Collisional narrowing effects were observed and were accurately described by a Galatry profile. Comparisons were made with previous experimental work or theoretical calculations as available.

Ponsardin, Patrick L.↗

Remote Sensing of the Haughton Impact Structure (HIS): A Terrestrial Proof of Concept for Using the Remote Sensing of Martian Craters as a Probe of Subsurface Composition

Impact cratering is the most widespread geological process in the Solar System. Impact craters can provide 'windows' into the subsurfaces of planetary bodies through excavation and uplift. By utilizing remote methods in the visible and near infrared (VNIR; 0.4-1.4 micron), short-wavelength infrared (SWIR; 1.4-2.5 micron) and thermal infrared (TIR 7-14 micron), subsurface mineral compositions may be identified and mapped via impact craters. Complex craters in particular, expose minerals from both the shallow and deep-seated subsurface, which may be identified spectroscopically. Complex craters have morphological features such as central peaks or peak rings, which are composed of relatively coherent lithologies tapped from deep-seated crustal components. While near-surface crustal components can be observed as coherent rocks uplifted and exposed in the rim and the crater walls, and from the ejecta deposits. Only two previously published studies using this approach have been successful on large planetary bodies. Tompkins and Pieters utilized ultraviolet and VNIR from Clementine to characterize near- and deep-subsurface materials in and around lunar craters. The work of Ramsey and Wright was the first remote spectroscopic study to successfully identify near-subsurface materials in the ejecta and crater wall of a terrestrial impact structure, namely Meteor Crater. Here we present early results of a third such study, a remote spectroscopy evaluation of the Haughton impact structure (HIS). The purpose of this study is to serve as terrestrial proof of concept that remote visible/infrared spectroscopic methods in this case, analysis of LANDSAT 7 ETM+ and ASTER data of the well-preserved HIS can be utilized in deciphering the subsurface composition of planetary crusts. This technique is particularly promising for Mars were limited tectonic uplift and ubiquitous dust-mantling offer few opportunities to access subsurface information.

Tornabene, L. L.↗

Growth, defect structure, and THz application of stoichiometric lithium niobate

Owing to the extraordinary richness of its physical properties, congruent lithium niobate has attracted multidecade-long interest both for fundamental science and applications. The combination of ferro-, pyro-, and piezoelectric properties with large electro-optic, acousto-optic, and photoelastic coefficients as well as the strong photorefractive and photovoltaic effects offers a great potential for applications in modern optics. To provide powerful optical components in high energy laser applications, tailoring of key material parameters, especially stoichiometry, is required. This paper reviews the state of the art of growing large stoichiometric LiNbO{sub 3} (sLN) crystals, in particular, the defect engineering of pure and doped sLN with emphasis on optical damage resistant (ODR) dopants (e.g., Mg, Zn, In, Sc, Hf, Zr, Sn). The discussion is focused on crystals grown by the high temperature top seeded solution growth (HTTSSG) technique using alkali oxide fluxing agents. Based on high-temperature phase equilibria studies of the Li{sub 2}O–Nb{sub 2}O{sub 5}–X{sub 2}O ternary systems (X = Na, K, Rb, Cs), the impact of alkali homologue additives on the stoichiometry of the lithium niobate phase will be analyzed, together with a summary of the ultraviolet, infrared, and far-infrared absorption spectroscopic methods developed to characterize the composition of the crystals. It will be shown that using HTTSSG from K{sub 2}O containing flux, crystals closest to the stoichiometric composition can be grown characterized by a UV-edge position of at about 302 nm and a single narrow hydroxyl band in the IR with a linewidth of less than 3 cm{sup −1} at 300 K. The threshold concentrations for ODR dopants depend on crystal stoichiometry and the valence of the dopants; Raman spectra, hydroxyl vibration spectra, and Z-scan measurements prove to be useful to distinguish crystals below and above the photorefractive threshold. Crystals just above the threshold are preferred for most nonlinear optical applications apart holography and have the additional advantage to minimize the absorption even in the far-infrared (THz) range. The review also provides a discussion on the progress made in the characterization of non-stoichiometry related intrinsic and extrinsic defect structures in doped LN crystals, with emphasis on ODR-ion-doped and/or closely stoichiometric systems, based on both spectroscopic measurements and theoretical modelling, including the results of first principles quantum mechanical calculations on hydroxyl defects. It will also be shown that new perspective applications, e.g., the generation of high energy THz pulses with energies on the tens-of-mJ scale, are feasible with ODR-doped sLN crystals if optimal conditions, including the contact grating technique, are applied.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Nuclear Resonance Vibrational Spectroscopic Definition of Peroxy Intermediates in Nonheme Iron Sites

Fe III -(hydro)peroxy intermediates have been isolated in two classes of mononuclear nonheme Fe enzymes that are important in bioremediation: the Rieske dioxygenases and the extradiol dioxygenases. The binding mode and protonation state of the peroxide moieties in these intermediates are not well-defined, due to a lack of vibrational structural data. Nuclear resonance vibrational spectroscopy (NRVS) is an important technique for obtaining vibrational information on these and other intermediates, as it is sensitive to all normal modes with Fe displacement. Here in this paper, we present the NRVS spectra of side-on Fe III -peroxy and end-on Fe III -hydroperoxy model complexes and assign these spectra using calibrated DFT calculations. We then use DFT calculations to define and understand the changes in the NRVS spectra that arise from protonation and from opening the Fe–O–O angle. This study identifies four spectroscopic handles that will enable definition of the binding mode and protonation state of Fe III -peroxy intermediates in mononuclear nonheme Fe enzymes. These structural differences are important in determining the frontier molecular orbitals available for reactivity.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Study of charge transfer interaction modes in the mixed Donor-Acceptor cocrystals of pyrene derivatives and TCNQ: A combined structural, thermal, spectroscopic, and hirshfeld surfaces analysis

Highlights: • Three pyrene derivatives were synthesized as donors. • Co-crystallization of donor and acceptor resulted in mixed CT cocrystals. • The crystal structures and packing of the CT mixed assemblies are studied. • CT state has been affirmed by spectroscopic measurements. • The three cocrystals exhibited strong absorptions extend to near infrared. - Abstract: The role of charge-transfer (CT) interactions in the synthesis of charge-transfer (CT) complexes is of great significance, which has led to promising materials for a range of applications. Herein, we report the synthesis of three new binary mixed stack CT systems I, II, and III, grown by solvent evaporation technique involving, 1-(naphthalene-2-yl)− 3-(pyrene-1-yl)prop-2-en-1-one (NPPO), 3-(pyrene-1-yl)− 1-(thiophene-2-yl)prop-2-en-1-one (PTPO) and 2-phenyl-3-(pyrene-2-yl)acrylonitrile (PPA) as the donors and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as an acceptor material. X-ray diffraction, thermal behavior, and spectroscopic analysis affirm the formation of CT complex and material purity. Based on the structural analysis the three CT complexes exhibit mixed stack arrangement (DAD-DAD) directed by the CT π–π interactions while the auxiliary hydrogen bonds (C-H-O, and C-H-N) stabilize and contribute to the overall packing of CT complexes. Remarkably, the complexes exhibit strong CT absorptions spreading to near infrared, making the crystals appear black. Not to mention, Hirshfeld surface analysis was employed to study the different intermolecular interactions and crystal packing in these materials. These results indicate that such a cocrystal design helps to explore new D-A systems, particularly with a mixed stack, that might have potential research values for applications in materials science.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectroscopic Chemical Sensing and Imaging: From Plants to Animals and Humans

Chemical sensing and imaging technologies are of great importance in medical diagnostics and environmental sensing due to their ability to detect and localize chemical targets and provide valuable information in real-time. Biophotonic techniques are the most promising for in vivo applications due to their minimal invasivity. Our laboratory has introduced various biophotonics-based technologies for chemical sensing and imaging for biochemical sensing, medical diagnostics, and fundamental research. Over the years, we have developed a wide variety of fluorescence and surface-enhanced Raman scattering (SERS)-based technologies for the detection of biomarkers for cancer and other diseases. This paper provides an overview of the research on chemical and biological sensors developed in our laboratory, highlighting our work on in vivo imaging and sensing, including minimally invasive detection of endogenous fluorophores associated with malignant tissue, SERS-tag localization of cancer cells and tissues, and SERS-based detection of nucleic acid biotargets and its feasibility for in vivo applications. This manuscript also presents new development on the use of Raman imaging of SERS-labeled nanoprobes incubated in leaves for use in biofuel research, laying the foundation for studies on functional imaging of nucleic acid biomarkers in plants.

Strobbia, Pietro (ORCID:0000000308846185)↗

Morin-like spin canting in the magnetic CaFe{sub 5}O{sub 7} ferrite: A combined neutron and Mössbauer study

Magnetic structure of CaFe{sub 5}O{sub 7} ferrite has been studied jointly from neutron powder diffraction data and spectroscopic Mössbauer measurements in the thermal range from 5 to 500 K. This coupled work highlights three distinct magnetic domains around two specific temperatures: T{sub M}=125 K and T{sub N}=360 K. The latter corroborates the structural monoclinic-orthorhombic transition previously reported by transmission electron microscopy techniques and X-ray thermodiffractometry. Complementary heat capacity measurements have confirmed this first order transition with a sharp peak at 360 K. Interestingly, this large study has revealed a second magnetic transition associated to a spin rotation at 125 K similar to this one reported by Morin in α-Fe{sub 2}O{sub 3} hematite at T{sub M}=260 K. - Graphical abstract: Magnetic structure of CaFe{sub 5}O{sub 7} ferrite has been studied jointly from neutron powder diffraction data and spectroscopic Mössbauer measurements in the thermal range from 5 to 500 K. This coupled work highlights three distinct magnetic domains around two specific temperatures: T{sub M}=125 K and T{sub N}=360 K. Interestingly, this large study has revealed a magnetic transition associated to a spin rotation at 125 K similar to this one reported by Morin in α-Fe{sub 2}O{sub 3} hematite at T{sub M}=260 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Spectroscopic Studies of Phenanthroimidazole-Imine Derivatives and Evaluation of Their Antioxidant Activity

The phenanthroimidazole derivatives are used in the drug industry in large scale. In this study four new phenanthroimidazole-imine derivatives were synthesized and their spectroscopic studies as well as their antioxidant behaviors were examined. Structural analyses were made by FT-IR, {sup 1}H-NMR, {sup 13}C-NMR, LC-MS spectroscopy techniques. UV–vis absorption and emission spectroscopy techniques have been used to determine the photophysical characteristics of four newly synthesized phenanthroimidazoles. The maximum absorption and emission wavelengths, molar extinction coefficients (ε), singlet energy levels (Es), Stokes’ shift values (Δλ) of phenanthroimidazole-imine derivatives are given. Additionally, the antioxidant behavior of all compounds were investigated which the ascorbic acid used as standard molecule in present study.

74 ATOMIC AND MOLECULAR PHYSICS↗

Reduced dimension discrete variable representation study of cis–trans isomerization in the S 1 state of C 2 H 2

Isomerization between the cis and trans conformers of the S 1 state of acetylene is studied using a reduced dimension discrete variable representation (DVR) calculation. Existing DVR techniques are combined with a high accuracy potential energy surface and a kinetic energy operator derived from FG theory to yield an effective but simple Hamiltonian for treating large amplitude motions. The spectroscopic signatures of the S 1 isomerization are discussed, with emphasis on the vibrational aspects. The presence of a low barrier to isomerization causes distortion of the trans vibrational level structure and the appearance of nominally electronically forbidden $\tilde{A}$ 1 A 2 ← $\tilde{X}$ 1 Σ$^+_g$ transitions to vibrational levels of the cis conformer. Both of these effects are modeled in agreement with experimental results, and the underlying mechanisms of tunneling and state mixing are elucidated by use of the calculated vibrational wavefunctions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thickness controlled sol-gel silica films for plasmonic bio-sensing devices

Plasmonics has recently received considerable interest due to its potentiality in many fields as well as in nanobio-technology applications. In this regard, various strategies are required for modifying the surfaces of plasmonic nanostructures and to control their optical properties in view of interesting application such as bio-sensing, We report a simple method for depositing silica layers of controlled thickness on planar plasmonic structures. Tetraethoxysilane (TEOS) was used as silica precursor. The control of the silica layer thickness was obtained by optimizing the sol-gel method and dip-coating technique, in particular by properly tuning different parameters such as pH, solvent concentration, and withdrawal speed. The resulting films were characterized via atomic force microscopy (AFM), Fourier-transform (FT) spectroscopy, and spectroscopic ellipsometry (SE). Furthermore, by performing the analysis of surface plasmon resonances before and after the coating of the nanostructures, it was observed that the position of the resonance structures could be properly shifted by finely controlling the silica layer thickness. The effect of silica coating was assessed also in view of sensing applications, due to important advantages, such as surface protection of the plasmonic structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗