SEARCH · Engineering Papers

Results for “VISIBLE SPECTRA”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 757 records · Page 42

All sources NASA NTRS DOE OSTI

NASA NTRS1993

Reflectance and Mossbauer spectroscopy of ferrihydrite-montmorillonite assemblages as Mars soil analog materials

Spectroscopic analyses show that Fe(3+)-doped smectites prepared in the laboratory exhibit important similarities to the soils on Mars. Ferrihydrite has been identified as the interlayer ferric component in Fe(3+)-doped smectites by a low quadrupole splitting and magnetic field strength of approximately 48 tesla in Mossbauer spectra measured at 4.2 K, as well as a crystal field transition at 0.92 micrometer. Ferrihydrite in these smectites explains features in the visible-near infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. Clay silicates have met resistance in the past as Mars soil analogs because terrestrial clay silicates exhibit prominent hydrous spectral features at 1.4, 1.9, and 2.2 micrometers; and these are observed weakly, if at all, in reflectance spectra of Mars. However, several mechanisms can weaken or compress these features, including desiccation under low-humidity conditions. The hydration properties of the interlayer cations also effect band strengths, such that a ferrihydrite-bearing smectite in the Martian environment would exhibit a 1.9 micrometers H2O absorption that is even weaker than the 2.2 micrometers structural OH absorption. Mixing experiments demonstrate that infrared spectral features of clays can be significantly suppressed and that the reflectance can be significantly darkened by mixing with only a few percent of a strongly absorbing opaque material. Therefore, the absolute reflectance of a soil on Mars may be disproportionately sensitive to a minor component. For this reason, the shape and position of spectral features and the chemical composition of potential analogs are of utmost importance in assessing the composition of the soil on Mars. Given the remarkable similarity between visible-infrared reflectance spectra of soils in bright regions on Mars and Fe(3+)-doped montmorillonites, coupled with recent observations of smectites in SNC meteorites and a weak 2.2 micrometers absorption in some Mars soils, ferrihydrite-bearing smectites warrant serious consideration as a Mars soil analog.

NASA Discipline Exobiology↗

DOE OSTI2017

Oxo Crater on (1) Ceres: Geological History and the Role of Water-ice

Dwarf planet Ceres (∅ ∼ 940 km) is the largest object in the main asteroid belt. Investigations suggest that Ceres is a thermally evolved, volatile-rich body with potential geological activity, a body that was never completely molten, but one that possibly partially differentiated into a rocky core and an ice-rich mantle, and may contain remnant internal liquid water. Thermal alteration and the infall of exogenic material contribute to producing a (dark) carbonaceous chondritic-like surface containing ammoniated phyllosilicates. Here we report imaging and spectroscopic analyses of data on the bright Oxo crater derived from the Framing Camera and the Visible and Infrared Spectrometer on board the Dawn spacecraft. We confirm that the transitional complex crater Oxo (∅ ∼ 9 km) exhibits exposed surface water-ice. We show that this water-ice-rich material is associated exclusively with two lobate deposits at pole-facing scarps, deposits that also contain carbonates and admixed phyllosilicates. Due to Oxo’s location at −4802 m below the cerean reference ellipsoid and its very young age of only 190 ka (1 σ : +100 ka, −70 ka), Oxo is predestined for ongoing water-ice sublimation.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2015

Facile synthesis of efficient visible active C-doped TiO{sub 2} nanomaterials with high surface area for the simultaneous removal of phenol and Cr(VI)

Highlights: • Facile synthesis of C-doped TiO{sub 2} nanomaterials with high surface area. • Utilization of citric acid and ascorbic acid as fuels based on evolution of gases. • Enhanced visible activity for the oxidation of phenol and reduction of Cr(VI). • Study of simultaneous oxidation of phenol and reduction of Cr(VI) for the first time. • Proposed plausible mechanism for the simultaneous removal of phenol and Cr(VI). - Abstract: A single step synthesis of carbon doped TiO{sub 2} (anatase) nanomaterials have been reported by using combustion synthesis using ascorbic acid and citric acid fuels. X-ray diffraction studies indicated the formation of nanosized anatase titania, whereas, transmission electron microscopy confirmed the formation of nanosized TiO{sub 2} anatase. The carbon doping into TiO{sub 2} matrix was identified by X-ray photoelectron spectroscopy, whereas, thermogravimetric study quantified the carbon doping. Diffuse reflectance UV–vis spectra indicated the band gap of less than 3 eV, a prerequisite for the photocatalytic activity under visible light irradiation. The N{sub 2} adsorption studies revealed the high surface area (upto 290 m{sup 2}/g) of the synthesized photocatalysts. Typical photocatalytic activity data indicated that the simultaneous removal of Cr(VI) and phenol is advantageous than degradation of the individual pollutants.

36 MATERIALS SCIENCE↗

DOE OSTI2014

Photo-fragmentation spectroscopy of benzylium and 1-phenylethyl cations

The electronic spectra of cold benzylium (C{sub 6}H{sub 5}-CH{sub 2}{sup +}) and 1-phenylethyl (C{sub 6}H{sub 5}-CH-CH{sub 3}{sup +}) cations have been recorded via photofragment spectroscopy. Benzylium and 1-phenylethyl cations produced from electrosprayed benzylamine and phenylethylamine solutions, respectively, were stored in a cryogenically cooled quadrupole ion trap and photodissociated by an OPO laser, scanned in parts of the UV and visible regions (600–225 nm). The electronic states and active vibrational modes of the benzylium and 1-phenylethyl cations as well as those of their tropylium or methyl tropylium isomers have been calculated with ab initio methods for comparison with the spectra observed. Sharp vibrational progressions are observed in the visible region while the absorption features are much broader in the UV. The visible spectrum of the benzylium cation is similar to that obtained in an argon tagging experiment [V. Dryza, N. Chalyavi, J. A. Sanelli, and E. J. Bieske, J. Chem. Phys. 137, 204304 (2012)], with an additional splitting assigned to Fermi resonances. The visible spectrum of the 1-phenylethyl cation also shows vibrational progressions. For both cations, the second electronic transition is observed in the UV, around 33 000 cm{sup −1} (4.1 eV) and shows a broadened vibrational progression. In both cases the S{sub 2} optimized geometry is non-planar. The third electronic transition observed around 40 000 cm{sup −1} (5.0 eV) is even broader with no apparent vibrational structures, which is indicative of either a fast non-radiative process or a very large change in geometry between the excited and the ground states. The oscillator strengths calculated for tropylium and methyl tropylium are weak. Therefore, these isomeric structures are most likely not responsible for these absorption features. Finally, the fragmentation pattern changes in the second and third electronic states: C{sub 2}H{sub 2} loss becomes predominant at higher excitation energies, for both cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

Ferromagnetic resonance spectra of H2-reduced minerals and glasses

In an earlier paper, we reported that H2 reduction of basaltic glass, olivine, pyroxene, and plagioclase resulted in the formation of metallic iron, in the darkening and reddening of the reflectance spectra, and the masking of individual spectral features in the visible and near-IR. In this work, we report FMR spectra for H2-reduced minerals and glasses that include the samples studied in the earlier paper. The FMR spectra were reduced at room temperature at a nominal frequency of 9.5 GHz. Sample saturation magnetization reported as F3(0) was measured with a vibrating sample magnetometer.

Morris, Richard V.↗

NASA NTRS1995

Low-temperature and low atmospheric pressure infrared reflectance spectroscopy of Mars soil analog materials

Infrared reflectance spectra of carefully selected Mars soil analog materials have been measured under low atmospheric pressures and temperatures. Chemically altered montmorillonites containing ferrihydrite and hydrated ferric sulfate complexes are examined, as well as synthetic ferrihydrate and a palagonitic soil from Haleakala, Maui. Reflectance spectra of these analog materials exhibit subtle visible to near-infrared features, which are indicative of nanophase ferric oxides or oxyhydroxides and are similar to features observed in the spectra of the bright regions of Mars. Infrared reflectance spectra of these analogs include hydration features due to structural OH, bound H2O and adsorbed H2O. The spectal character of these hydration features is highly dependent on the sample environment and on the nature of the H2O/OH in the analogs. The behavior of the hydration features near 1.9 micrometers, 2.2 micrometers, 2.7 micrometers, 3 micrometers, and 6 micrometers are reported here in spetra measured under Marslike atmospheric environment. In spectra of these analogs measured under dry Earth atmospheric conditions the 1.9-micrometer band depth is 8-17%; this band is much stonger under moist conditions. Under Marslike atmospheric conditions the 1.9-micrometer feature is broad and barely discernible (1-3% band depth) in spectra of the ferrihydrite and palagonitic soil samples. In comparable spectra of the ferric sulfate-bearing montmorillonite the 1.9-micrometer feature is also broad, but stronger (6% band depth). In the low atmospheric pressure and temperature spectra of the ferrihydrite-bearing montmorillonite this feature is sharper than the other analogs and relatively stronger (6% band depth). Although the intensity of the 3- micrometer band is weaker in spectra of each of the analogs when measured under Marslike conditions, the 3-micromter band remains a dominant feature and is especially broad in spectra of the ferrihydrite and palagonitic soil. The structural OH features observed in these materials at 2.2-2.3 micrometers and 2.27 micrometers remain largely unaffected by the environmental conditions. A shift in the Christiansen feature towards shorter wavelengths has also been observed with decreasing atmospheric pressure and temperature in the midinfrared spectra of these samples.

Bishop, Janice L.↗

NASA NTRS1995

Low-temperature and low atmospheric pressure infrared reflectance spectroscopy of Mars soil analog materials

Infrared reflectance spectra of carefully selected Mars soil analog materials have been measured under low atmospheric pressures and temperatures. Chemically altered montmorillonites containing ferrihydrite and hydrated ferric sulfate complexes are examined, as well as synthetic ferrihydrite and a palagonitic soil from Haleakala, Maui. Reflectance spectra of these analog materials exhibit subtle visible to near-infrared features, which are indicative of nanophase ferric oxides or oxyhydroxides and are similar to features observed in the spectra of the bright regions of Mars. Infrared reflectance spectra of these analogs include hydration features due to structural OH, bound H2O, and adsorbed H2O. The spectral character of these hydration features is highly dependent on the sample environment and on the nature of the H2O/OH in the analogs. The behavior of the hydration features near 1.9 micron, 2.2 micron, 2.7 micron, 3 micron, and 6 microns are reported here in spectra measured under a Marslike atmospheric environment. In spectra of these analogs measured under dry Earth atmospheric conditions the 1.9-micron band depth is 8-17%; this band is much stronger under moist conditions. Under Marslike atmospheric conditions the 1.9-micron feature is broad and barely discernible (1-3% band depth) in spectra of the ferrihydrite and palagonitic soil samples. In comparable spectra of the ferric sulfate-bearing montmorillonite the 1.9-micron feature is also broad, but stronger (6% band depth). In the low atmospheric pressure and temperature spectra of the ferrihydrite-bearing montmorillonite this feature is sharper than the other analogs and relatively stronger (6% band depth). Although the intensity of the 3-micron band is weaker in spectra of each of the analogs when measured under Marslike conditions, the 3-micron band remains a dominant feature and is especially broad in spectra of the ferrihydrite and palagonitic soil. The structural OH features observed in these materials at 2.2-2.3 micron and 2.75 microns remain largely unaffected by the environmental conditions. A shift in the Christiansen feature towards shorter wavelengths has also been observed with decreasing atmospheric pressure and temperature in the midinfrared spectra of these samples.

Bishop, Janice L.↗

DOE OSTI2017

Exploring the SDSS Data Set with Linked Scatter Plots. I. EMP, CEMP, and CV Stars

We present the results of a search for extremely metal-poor (EMP), carbon-enhanced metal-poor (CEMP), and cataclysmic variable (CV) stars using a new exploration tool based on linked scatter plots (LSPs). Our approach is especially designed to work with very large spectrum data sets such as the SDSS, LAMOST, RAVE, and Gaia data sets, and it can be applied to stellar, galaxy, and quasar spectra. As a demonstration, we conduct our search using the SDSS DR10 data set. We first created a 3326-dimensional phase space containing nearly 2 billion measures of the strengths of over 1600 spectral features in 569,738 SDSS stars. These measures capture essentially all the stellar atomic and molecular species visible at the resolution of SDSS spectra. We show how LSPs can be used to quickly isolate and examine interesting portions of this phase space. To illustrate, we use LSPs coupled with cuts in selected portions of phase space to extract EMP stars, CEMP stars, and CV stars. We present identifications for 59 previously unrecognized candidate EMP stars and 11 previously unrecognized candidate CEMP stars. We also call attention to 2 candidate He ii emission CV stars found by the LSP approach that have not yet been discussed in the literature.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2014

Inverted cones grating for flexible metafilter at optical and infrared frequencies

By combining the antireflective properties from gradual changes in the effective refractive index and cavity coupling from cone gratings and the efficient optical behavior of a tungsten film, a flexible filter showing very broad antireflective properties from the visible to short wavelength infrared region and, simultaneously, a mirror-like behavior in the mid-infrared wavelength region and long-infrared wavelength region has been conceived. Nanoimprint technology has permitted the replication of inverted cone patterns on a large scale on a flexible polymer, afterwards coated with a thin tungsten film. This optical metafilter is of great interest in the stealth domain where optical signature reduction from the optical to short wavelength infrared region is an important matter. As it also acts as selective thermal emitter offering a good solar-absorption/infrared-emissivity ratio, interests are found as well for solar heating applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Investigating Np(VI) Nitrate Speciation Control through Temperature and Optical Spectroscopy

Numerous areas of nuclear processing, such as radioisotope production, nuclear waste remediation, and separations, depend upon the speciation of f-elements in the solution state. However, fundamental knowledge of the actinides─particularly Np─lags behind most of the elements on the periodic table. Despite the importance of Np(VI) chemistry in separations and nuclear processing, its speciation in HNO 3 remains uncertain. This work addresses some of these gaps by investigating the effect of HNO 3 concentration and temperature on the spectra and speciation of the Np(VI) nitrate system. Six samples of Np in 1 to 10 M HNO 3 were prepared and treated with (NH 4 ) 2 [Ce(NO 3 ) 6 ] to stabilize the hexavalent oxidation state. The absorbance spectrum of the 10 M HNO 3 is drastically different from the spectra of the other samples; the 10 M spectrum indicates coordination of nitrate ligands to the Np(VI)O 2 2+ ion to form a complex with high symmetry. Additionally, absorbance spectra were recorded over the temperature range of 15 to 40 °C, and systematic increases and decreases in certain spectral features of the ultraviolet–visible (UV–vis)–near-infrared (NIR) spectra are present in the spectra. The difference in spectral features suggests that Np(VI) nitrate speciation depends on temperature. Dilution studies of this sample were monitored with UV–vis–NIR and Raman spectroscopies. Spectral data indicate the presence of multiple complexes with different symmetries, including a high-symmetry complex with an inversion center. As samples are diluted and aquo ligands replace nitrate ligands bound to the Np(VI) neptunyl cation, changes in spectroscopic signals indicate a decrease in the high-symmetry nitrate complex and an increase in the lower-symmetry aquo complex. Additionally, the Raman band associated with the Np(VI)O 2 2+ symmetric stretch broadens with dilution and is fitted with two peaks. These peaks are assigned to Np(VI) aquo and nitrato complexes, indicating that this vibrational mode is sensitive to the coordination environment of the Np(VI) neptunyl cation and that contributions from these two Np(VI) complexes can be distinguished. This unique experimental data could be used to advance computational models describing the electronic transitions of complex actinyl ions.

Absorption↗

DOE OSTI2015

Microwave-assisted synthesis and characterization of nickel ferrite nanoparticles

Nickel ferrite nanoparticles (NiFe{sub 2}O{sub 4}) were successfully prepared by microwave-assisted combustion method (MWAC) using citric Electron acid as a chelating agent. NiFe{sub 2}O{sub 4} nanoparticles were characterized by X-ray diffraction (XRD) pattern, Scanning Microscopy (SEM), Fourier transform infrared (FTIR) and UV-Visible techniques. XRD analysis revealed that NiFe{sub 2}O{sub 4} nanoparticles have spinel cubic structure with the average crystalline size of 26.38 nm. SEM analysis revealed random and porous structural morphology of particles and FTIR showed absorption bands related to octahedral and tetrahedral sites, in the range 400–600cm{sup −1} which strongly favor the formation of NiFe{sub 2}O{sub 4} nanoparticles. The optical band gap is determined by UV Visible method and found to be 5.4 eV.

36 MATERIALS SCIENCE↗

NASA NTRS1999

Validation of Airborne Visible-Infrared Imaging Spectrometer Data at Ray Mine, AZ

We validate 1997 Airborne Visible-Infrared Imaging Spectrometer (AVIRIS) reflectance spectra covering 0.4 meu - 2.4 meu from a stable, flat mineralogically characterized man-made target at Ray Mine, AZ, the site for an EPA/NASA assessment of the utility of remote sensing for monitoring acid drainage from an active open pit mine.

AVIRIS visible-infrared spectrometer imaging↗

DOE OSTI2015

Annealing-free synthesis of carbonaceous Nb{sub 2}O{sub 5} microspheres by flame thermal method and enhanced photocatalytic activity for hydrogen evolution

Graphical abstract: Carbonaceous Nb{sub 2}O{sub 5} microspheres were firstly prepared by annealing-free flame thermal approach and its enhanced photocatalytic activity was demonstrated for hydrogen production. - Highlights: • Carbonaceous Nb{sub 2}O{sub 5} microspheres were prepared by annealing-free flame thermal approach in the first time. • Hydrolysis and incomplete combustion gave rise to Nb{sub 2}O{sub 5} incorporated with carbon. • Carbon species act as surface sensitizer to enhance photocatalytic activity. • It is possible to extend the strategy to develop various other metal oxides. - Abstract: An annealing-free synthesis of carbonaceous Nb{sub 2}O{sub 5} photocatalyst via a one-step flame assisted pyrolysis approach was proposed for the first time. Nearly amorphous carbonaceous Nb{sub 2}O{sub 5} microspheres were obtained directly through the facile and waste-free method. The presence of carbonate species was confirmed by means of EDS, XPS, BET and TEM. Both FT-IR and Raman analysis further revealed the existence form of carbon residuals for the resulted sample. UV–vis diffuse reflectance spectra showed the strong absorption of visible light and narrowed band gap for the carbon modified Nb{sub 2}O{sub 5}. On account of the vital role that carbon played in efficient electron-hole separation and light absorption, the hydrogen generation rate was 2.7 times that of the annealed and commercial Nb{sub 2}O{sub 5} samples. Further calcination can foster the crystallinity and expand specific surface area but lower the photocatalytic performance of as-prepared Nb{sub 2}O{sub 5} because of the elimination of carbon species. This work provides a new strategy for the preparation of carbonaceous Nb{sub 2}O{sub 5} candidates with enhanced photocatalytic activity.

36 MATERIALS SCIENCE↗

NASA NTRS2019

Space Weathering Maps of (101955) Bennu Using a Radiative Transfer Model

Space weathering is an important process that affects the surfaces of airless bodies, such as (101955) Bennu. The consequences of this process include physical and chemical changes to materials on the surface, which in turn change spectral characteristics, especially in the visible to near infrared wavelengths. These spectral changes are not the same across airless bodies because the changes are dependent on the composition and mineralogy of the surface and even location within the Solar System. The main space weathering products responsible for these spectral changes are submicroscopic particles, which consist of two types, nanophase and microphase particles, and affect visible to near-infrared reflectance spectra differently. Nanophase particles are particles <33 nm in size and occur in agglutinates and within glassy patinas around regolith particles. In contrast, microphase particles are >33 nm in size and are present only within agglutinates. These spectral differences are best illustrated by lunar samples. In lunar soils, the nanophase and microphase particles consist of metallic iron. With increasing abundance of nanophase iron particles in a regolith, its spectrum exhibits a lower overall reflectance in the visible to near infrared, weakened absorption bands, and a reddened continuum slope. In contrast, an increasing abundance of microphase iron only causes decreases in reflectance and not reddening. Because of the spectral differences introduced by these two types of particles, it is possible to model the nanophase and microphase particle abundances of a surface through the radiative transfer technique. Beyond the Moon, the composition of the nanophase and microphase particles can include other phases because the mineralogy of the surfaces of other planetary bodies is different. For example, the nanophase and microphase particles may consist of amorphous carbon (Mercury) and sulfides (Itokawa). The mineralogy of Bennu is consistent with carbonaceous chondrites. From a number of space weathering experiments on CM chondrites, the likely nanophase and microphase mineral phases on Bennu includes iron, magnetite, and sulfides (i.e., pentlandite and troilite). The goal of this work is to input the predicted nanophase and microphase compositions for Bennu into the radiative transfer technique. Next, we use this technique to model the OSIRIS-REx Visible Infrared Spectrometer (OVIRS) so that we can model the nanophase and microphase particle abundances across the surface. This will result in space weathering maps of the surface of Bennu, which are useful for understanding the degree of space weathering across the surface and its relationship to various regions and geological features.

Trang, D.↗

NASA NTRS2020

Weak Spectral Features on (101995) Bennu from the OSIRIS-REx Visible and InfraRed Spectrometer

Context. The NASA Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission has obtained thousands of spectra of asteroid (101955) Bennu with the OSIRIS-REx Visible and InfraRed Spectrometer (OVIRS). Aims. We present a spectral search for minor absorption bands and determine compositional variations on the surface of Bennu. Methods. Reflectance spectra with low and high spatial resolutions were analyzed for evidence of weak absorption bands. Spectra were also divided by a global average spectrum to isolate unique spectral features, and variations in the strongest band depths were mapped on a surface shape model. The global visible to near-IR spectrum of Bennu shows evidence of several weak absorption bands with depths of a few percent. Results. Several observed bands are consistent with phyllosilicates, and their distribution correlates with the stronger 2.74-μm hydration band. A 0.55-μm band is consistent with iron and is deepest in the spectrally reddest areas on Bennu. The presence of hydrated phyllosilicates and iron oxides indicates substantial aqueous alteration in Bennu’s past. Conclusions. Bennu’s spectra are not identical to a limited set of carbonaceous chondrite spectra, possibly due to compositional properties and spatial scale differences; however, returned samples should contain a mixture of common chondrite materials.

OSIRIS-REx↗

DOE OSTI2026

Quantifying Temperature Dependence of Pu(IV) Absorbance Spectra for Advanced Online Monitoring of Nuclear Processes

This article presents a systematic study of Pu(IV) absorbance spectral features as a function of temperature to develop an understanding of this parameter’s effect on chemometric models that can be used as online monitoring tools to support nuclear processing. The descriptive and predictive models that provide real-time feedback of these processes are usually constructed with data collected in conditions typical of a laboratory environment, which can differ drastically from a processing environment. To assess the impact of temperature on Pu(IV) absorbance spectra, 11 samples of Pu(IV) were synthesized with varying HNO 3 concentrations ranging from 0.6 to 9.5 M and heated between 15 and 45 °C. Ultraviolet (UV)–visible (vis)–near-infrared (NIR) absorption spectra collected at different HNO 3 concentrations and temperatures revealed that features associated with Pu(IV) are sensitive to temperature at all HNO 3 concentrations and that changes in features depend on HNO 3 concentration. The contributions of temperature and HNO 3 concentration to variation in Pu(IV) spectral features were evaluated using the principal component analysis of spectra that were baseline-corrected with an asymmetric least-squares method. Furthermore, predictive modeling for HNO 3 concentration with partial least-squares regression of UV–vis–NIR spectra highlighted the importance of accounting for temperature in the calibration set to optimize model performance. This methodology constitutes a new, systematic approach to account for the effect of temperature on the absorption spectra of metal ions and is useful for process monitoring applications in many industries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1991

Effect of isotopic substitution on the visible absorption spectrum of ozone

Gas-phase spectra for (O-16)3 and (O-18)3 are examined to consider the electronic states which cause the Chappuis bands. Specifications of the spectrometer and spectra calibrations are given. The results of both a conventional description of the vibrational structure and an examination of the autocorrelation functions are discussed. Transitions to two electronically excited states are the significant features of the isotope shifts. The transitions are characterized by adiabatic energies about 750/cm apart, and the higher energy approaches 16,400/cm. The vibrational structure of the higher state accompanies a relatively simple progression, and the lower state accompanies one isolated band. The autocorrelation analysis shows that for (O-16)3, major recurrences near 31 and 41 fs are found, and longer equivalent times are found for (O-18)3. At longer times, minor recurrences are also found. The results are considered significant for the understanding of the electronic and vibrational structures of the Chappuis bands. Suggestions for future work based on these results are discussed.

Anderson, Stuart M.↗

DOE OSTI2016

Entropic screening preserves non-equilibrium nature of nematic phase while enthalpic screening destroys it

The present manuscript describes the role of entropic and enthalpic forces mediated by organic non-polar (hexane) and polar (methanol) solvents on the bulk and microscopic phase transition of a well known nematic liquid crystalline material MBBA (N-(4-methoxybenzylidene)-4-butylaniline) through Differential Scanning calorimetry (DSC), UV-Visible (UV–Vis), and Fourier Transform Infrared (FTIR) spectroscopy. DSC study indicates continuous linear decreases in both nematic-isotropic (N-I) phase transition temperature and enthalpy of MBBA in presence of hexane while both these parameters show a saturation after an initial decay in methanol. These distinct transitional behaviours were explained in terms of the “depletion force” model for entropic screening in hexane and “screening-self-screening” model for methanol. Heating rate dependent DSC studies find that non-Arrhenius behaviour, characteristic of pristine MBBA and a manifestation of non-equilibrium nature [Dan et al., J. Chem. Phys. 143, 094501 (2015)], is preserved in presence of entropic screening in the hexane solution, while it changes to Arrhenius behaviour (signifying equilibrium behaviour) in presence of enthalpic screening in methanol solution. FTIR spectra show similar dependence on the solvent induced screening in the intensities of the imine (—C = N) stretch and the out-of-plane distortion vibrations of the benzene rings of MBBA with hexane and methanol as in DSC, further establishing our entropic and enthalpic screening models. UV–Vis spectra of the electronic transitions in MBBA as a function of temperature also exhibit different dependences of intensities on the solvent induced screening, and an exponential decrease is observed in presence of hexane while methanol completely changes the nature of interaction to follow a linear dependence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗