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41 records · Page 3

CF2 and CFCl fluorescence from VUV excitation of C2F3Cl

The photoexcitation process of C2F3Cl molecule was investigated in the 106 to 230 nm region using synchrotron radiation as a light source. Photoabsorption and fluorescence cross sections were measured and used to determine the fluorescence quantum yield. Fluorescence yield starts to appear at 170 nm and increases to about 2% at 155 nm. The fluorescence spectra were dispersed to identify the emitting species. At the excitation wavelength of 155 nm, the emission system is CFCl (Hermitian conjugate of A - Hermitian conjugate of X), and at 123.9 nm, both the CF2 (Hermitian conjugate of A - Hermitian conjugate of X) and CFCl (Hermitian conjugate of A - Hermitian conjugate of X) systems are observed. The dissociation processes that produced these excited species are discussed.

Nee, J. B.↗

Influence of gap states on the nonresonant second hyperpolarizabilities of conjugated organic polymers

The presence of conjugation and substitution defects introduces gap states in finite polyenes that are shown to influence the size and sign of the second molecular hyperpolarizability (SMH). Using a one-electron tight-binding model, the dependence of SMH on the defect-state occupancy and energy in finite polyenes is calculated. Defects can cause a significant decrease or enhancement of SMH by impeding charge delocalization or by creating partly filled bands (mimicking the one-band limit), respectively. Concomitant sign changes in SMH are predicted. Calculation results suggest strategies for designing molecules that can be either photochemically or electrochemically switched between states with considerably different SMHs.

Beratan, David N.↗

Prediction of nonlinear optical properties of organic materials. General theoretical considerations

The prediction of nonlinear optical properties of organic materials is geared to assist materials scientists in the selection of good candidate molecules. A brief summary of the quantum mechanical methods used for estimating hyperpolarizabilities will be presented. The advantages and limitations of each technique will be discussed. Particular attention will be given to the finite-field method for calculating first and second order hyperpolarizabilities, since this method is better suited for large molecules. Corrections for dynamic fields and bulk effects will be discussed in detail, focusing on solvent effects, conformational isomerization, core effects, dispersion, and hydrogen bonding. Several results will be compared with data obtained from third-harmonic-generation (THG) and dc-induced second harmonic generation (EFISH) measurements. These comparisons will demonstrate the qualitative ability of the method to predict the relative strengths of hyperpolarizabilities of a class of compounds. The future application of molecular mechanics, as well as other techniques, in the study of bulk properties and solid state defects will be addressed. The relationship between large values for nonlinear optical properties and large conjugation lengths is well known, and is particularly important for third-order processes. For this reason, the materials with the largest observed nonresonant third-order properties are conjugated polymers. An example of this type of polymer is polydiacetylene. One of the problems in dealing with polydiacetylene is that substituents which may enhance its nonlinear properties may ultimately prevent it from polymerizing. A model which attempts to predict the likelihood of solid-state polymerization is considered, along with the implications of the assumptions that are used. Calculations of the third-order optical properties and their relationship to first-order properties and energy gaps will be discussed. The relationship between monomeric and polymeric third-order optical properties will also be considered.

Cardelino, B.↗

Tholins as Coloring Agents on Solar System Bodies

Pre-biotic organic materials appear to be common on many small bodies in the outer Solar System, as evidenced by the color properties of these objects. We report on our continuing study of color properties in connection with the presence of complex organic solids (tholins) among the planets and their satellites, the asteroids, and the trans- Neptunian objects (Kuiper Belt objects). Most small, icy bodies in the Solar System, whether they have high or low surface reflectance (albedo), show a pronounced downward slope in reflectance at wavelengths shorter than approx. 1 micron. This increasing absorption of sunlight toward shorter wavelengths is characteristic of pi-bonds in hydrocarbons having chains or rings of conjugated C atoms. Tholins, which contain polycyclic aromatic and aliphatic hydrocarbons, exhibit these color properties. Using the complex refractive indices of tholins in models of the reflectance spectra of icy bodies in the Solar System, we find that these complex organic materials satisfactorily account for the coloration so widely observed. The new results presented here show that the wide variety of colors of Kuiper Belt objects can be fit very well with tholins, as can the colors of Pluto and Triton. The implications of these fits of Kuiper Belt objects is that complex organic material is created on their surfaces by energetic particle bombardment of native ices, and also may be accreted from external sources. In the cases of Pluto and Triton, photochemistry of their weak N2 + CH4 + CO atmospheres produces complex organic molecules that precipitate to the surface, providing local color.

Cruikshank, D. P.↗

On the Hunt for Detectable Biosignatures in Jezero Crater: What to Look for and Where

Introduction: The Perseverance rover, which is currently exploring Jezero crater on Mars, is equipped with seven instruments that allow for observation of textures, minerals, color, structure, and chemistry of rocks and sediments in order to search for signs of ancient life, understand the geologic history of the crater, and identify candidates for sample return (Farley et al. 2020). The first of these aims includes the direct detection of potential biosignatures, including textures, organic molecules, minerals, and elemental chemistries that are of biogenic origin (Mustard et al. 2013). The presence of these biosignatures will be constrained by the habitability of the local region, the preservation potential of the host rocks, and the sensitivity of the instrument suite, and their biogenicity will be investigated after return to Earth as part of the Mars Sample Return campaign. Here, we examine key targets on the three planned campaigns, potential biosignatures that may be present, and the capabilities of key rover instruments. High Potential Biosignature Sites in Jezero: To date, measurements have been made on multiple sites that both contain minerals known in terrestrial settings to preserve biosignatures and likely were habitable settings (Williford et al. 2021). Two examples include the fine-grained rocks at the base of the delta fan and the NW inner margin of the crater. Fine-grained Rocks at Base of Delta Fan. Fine-grained, clay-bearing rocks may have been deposited as muddy lake sediments that could have hosted life and preserved biosignatures settling out of the water column. The report of organic molecules by the Curiosity rover in the Sheepbed mudstone and Murray formation has highlighted this site in particular. Potential biosignatures in mudstones, especially those rich in silica (McMahon et al. 2018), microbialites and complex organics. NW Inner Margin of Crater. This unit, located along the inner margin of the crater, contains strong carbonate signatures and may have been the littoral zone of a lake (Horgan et al. 2020). The potential biosignatures here include microfossils, microbialites, biominerals, and complex organics. Detectability of Biosignatures by the Mars 2020 Instrument Suite: The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument comprises a Deep UV spectrometer, context imager, and color camera to generate spatially resolved chemical maps (Bhartia et al. 2020). It is sensitive to trace organics as well as a range of minerals and can detect native fluorescence from aromatic organics; the WATSON and ACI cameras can be used to observe morphologies such as stromatolitic laminations or filaments ranging from the tens of micron to millimeter scale. SHERLOC can detect organics that may be present in either of the high potential biosignature targets, as well as detect carbonates in the latter. However, the presence of high amounts of iron, such as in iron-rich clays, would cause attenuation of spectral response through UV absorption. The Planetary Instrument for X-ray Lithochemistry (PIXL) comprises an X-ray fluorescence spectrometer and camera that can scan rock surfaces to generate elemental maps (Allwood et al. 2020). PIXL can detect chemical biosignatures such as spatial variations of elemental abundances that may have resulted from biological activity. PIXL would be particularly useful in detecting fine textures and elemental chemistries in either high potential biosignature target, but cannot directly detect minerals such as carbonate. The SuperCam instrument performs three types of spectroscopy, color imaging, and acoustic recording to remotely examine elemental composition, minerals, organics, and textures (Maurice et al. 2021). Using laser induced breakdown spectroscopy and time resolved luminescence spectroscopy, SuperCam can detect major elemental building blocks of organics (i.e., C, H, N, O, P, S) and conjugated organic structures, respectively, which may be found in either site. While in other contexts, luminescence is a useful tool for biosignature identification, luminescence generated by the 532 nm laser may obscure the Raman signal. Conclusion: The three instruments discussed can be used collaboratively to establish the presence of potential biosignatures in samples. These high-priority samples may then be returned to Earth for detailed laboratory analysis.

S. Sharma↗