Sample records for ultraviolet photodissociation uvpd

  1. UV-POSIT: Web-Based Tools for Rapid and Facile Structural Interpretation of Ultraviolet Photodissociation (UVPD) Mass Spectra

    NASA Astrophysics Data System (ADS)

    Rosenberg, Jake; Parker, W. Ryan; Cammarata, Michael B.; Brodbelt, Jennifer S.

    2018-04-01

    UV-POSIT (Ultraviolet Photodissociation Online Structure Interrogation Tools) is a suite of web-based tools designed to facilitate the rapid interpretation of data from native mass spectrometry experiments making use of 193 nm ultraviolet photodissociation (UVPD). The suite includes four separate utilities which assist in the calculation of fragment ion abundances as a function of backbone cleavage sites and sequence position; the localization of charge sites in intact proteins; the calculation of hydrogen elimination propensity for a-type fragment ions; and mass-offset searching of UVPD spectra to identify unknown modifications and assess false positive fragment identifications. UV-POSIT is implemented as a Python/Flask web application hosted at http://uv-posit.cm.utexas.edu. UV-POSIT is available under the MIT license, and the source code is available at https://github.com/jarosenb/UV_POSIT. [Figure not available: see fulltext.

  2. UV-POSIT: Web-Based Tools for Rapid and Facile Structural Interpretation of Ultraviolet Photodissociation (UVPD) Mass Spectra.

    PubMed

    Rosenberg, Jake; Parker, W Ryan; Cammarata, Michael B; Brodbelt, Jennifer S

    2018-06-01

    UV-POSIT (Ultraviolet Photodissociation Online Structure Interrogation Tools) is a suite of web-based tools designed to facilitate the rapid interpretation of data from native mass spectrometry experiments making use of 193 nm ultraviolet photodissociation (UVPD). The suite includes four separate utilities which assist in the calculation of fragment ion abundances as a function of backbone cleavage sites and sequence position; the localization of charge sites in intact proteins; the calculation of hydrogen elimination propensity for a-type fragment ions; and mass-offset searching of UVPD spectra to identify unknown modifications and assess false positive fragment identifications. UV-POSIT is implemented as a Python/Flask web application hosted at http://uv-posit.cm.utexas.edu . UV-POSIT is available under the MIT license, and the source code is available at https://github.com/jarosenb/UV_POSIT . Graphical Abstract.

  3. Vacuum Ultraviolet Photodissociation and Fourier Transform-Ion Cyclotron Resonance (FT-ICR) Mass Spectrometry: Revisited.

    PubMed

    Shaw, Jared B; Robinson, Errol W; Paša-Tolić, Ljiljana

    2016-03-15

    We revisited the implementation of 193 nm ultraviolet photodissociation (UVPD) within the ion cyclotron resonance (ICR) cell of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. UVPD performance characteristics were examined in the context of recent developments in the understanding of UVPD and in-cell tandem mass spectrometry. Efficient UVPD and photo-ECD of a model peptide and proteins within the ICR cell of a FT-ICR mass spectrometer are accomplished through appropriate modulation of laser pulse timing, relative to ion magnetron motion and the potential applied to an ion optical element upon which photons impinge. It is shown that UVPD yields efficient and extensive fragmentation, resulting in excellent sequence coverage for model peptide and protein cations.

  4. Ultraviolet photodissociation enhances top-down mass spectrometry as demonstrated on green fluorescent protein variants.

    PubMed

    Dang, Xibei; Young, Nicolas L

    2014-05-01

    Ultraviolet photodissociation (UVPD) is a compelling fragmentation technique with great potential to enhance proteomics generally and top-down MS specifically. In this issue, Cannon et al. (Proteomics 2014, 14, XXXX-XXXX) use UVPD to perform top-down MS on several sequence variants of green fluorescent protein and compare the results to CID, higher energy collision induced dissociation, and electron transfer dissociation. As compared to the other techniques UVPD produces a wider variety of fragment ion types that are relatively evenly distributed across the protein sequences. Overall, their results demonstrate enhanced sequence coverage and higher confidence in sequence assignment via UVPD MS. Based on these and other recent results UVPD is certain to become an increasingly widespread and valuable tool for top-down proteomics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Direct Identification of Tyrosine Sulfation by using Ultraviolet Photodissociation Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Robinson, Michelle R.; Moore, Kevin L.; Brodbelt, Jennifer S.

    2014-08-01

    Sulfation is a common post-translational modification of tyrosine residues in eukaryotes; however, detection using traditional liquid chromatography-mass spectrometry (LC-MS) methods is challenging based on poor ionization efficiency in the positive ion mode and facile neutral loss upon collisional activation. In the present study, 193 nm ultraviolet photodissociation (UVPD) is applied to sulfopeptide anions to generate diagnostic sequence ions, which do not undergo appreciable neutral loss of sulfate even using higher energy photoirradiation parameters. At the same time, neutral loss of SO3 is observed from the precursor and charge-reduced precursor ions, a spectral feature that is useful for differentiating tyrosine sulfation from the nominally isobaric tyrosine phosphorylation. LC-MS detection limits for UVPD analysis in the negative mode were determined to be around 100 fmol for three sulfated peptides, caerulein, cionin, and leu-enkephalin. The LC-UVPD-MS method was applied for analysis of bovine fibrinogen, and its key sulfated peptide was confidently identified.

  6. Direct Identification of Tyrosine Sulfation by using Ultraviolet Photodissociation Mass Spectrometry

    PubMed Central

    Robinson, Michelle R.; Moore, Kevin L.; Brodbelt, Brodbelt

    2014-01-01

    Sulfation is a common post-translational modification of tyrosine residues in eukaryotes; however, detection using traditional liquid chromatography-mass spectrometry (LC-MS) methods is challenging based on poor ionization efficiency in the positive ion mode and facile neutral loss upon collisional activation. In the present study, 193 nm ultraviolet photodissociation (UVPD) is applied to sulfopeptide anions to generate diagnostic sequence ions which do not undergo appreciable neutral loss of sulfate even using higher energy photoirradiation parameters. At the same time, neutral loss of sulfate is observed from the precursor and charge reduced precursor ions, a spectral feature that is useful for differentiating tyrosine sulfation from the nominally isobaric tyrosine phosphorylation. LC-MS detection limits for UVPD analysis in the negative mode were determined to be around 100 fmol for three sulfated peptides, caerulein, cionin, and leu-enkephalin. The LC-UVPD-MS method was applied for analysis of bovine fibrinogen, and its key sulfated peptide was confidently identified. PMID:24845354

  7. Top-Down Hydrogen-Deuterium Exchange Analysis of Protein Structures Using Ultraviolet Photodissociation.

    PubMed

    Brodie, Nicholas I; Huguet, Romain; Zhang, Terry; Viner, Rosa; Zabrouskov, Vlad; Pan, Jingxi; Petrotchenko, Evgeniy V; Borchers, Christoph H

    2018-03-06

    Top-down hydrogen-deuterium exchange (HDX) analysis using electron capture or transfer dissociation Fourier transform mass spectrometry (FTMS) is a powerful method for the analysis of secondary structure of proteins in solution. The resolution of the method is a function of the degree of fragmentation of backbone bonds in the proteins. While fragmentation is usually extensive near the N- and C-termini, electron capture (ECD) or electron transfer dissociation (ETD) fragmentation methods sometimes lack good coverage of certain regions of the protein, most often in the middle of the sequence. Ultraviolet photodissociation (UVPD) is a recently developed fast-fragmentation technique, which provides extensive backbone fragmentation that can be complementary in sequence coverage to the aforementioned electron-based fragmentation techniques. Here, we explore the application of electrospray ionization (ESI)-UVPD FTMS on an Orbitrap Fusion Lumos Tribrid mass spectrometer to top-down HDX analysis of proteins. We have incorporated UVPD-specific fragment-ion types and fragment-ion mixtures into our isotopic envelope fitting software (HDX Match) for the top-down HDX analysis. We have shown that UVPD data is complementary to ETD, thus improving the overall resolution when used as a combined approach.

  8. Radical Rearrangement Chemistry in Ultraviolet Photodissociation of Iodotyrosine Systems: Insights from Metastable Dissociation, Infrared Ion Spectroscopy, and Reaction Pathway Calculations.

    PubMed

    Ranka, Karnamohit; Zhao, Ning; Yu, Long; Stanton, John F; Polfer, Nicolas C

    2018-05-29

    We report on the ultraviolet photodissociation (UVPD) chemistry of protonated tyrosine, iodotyrosine, and diiodotyrosine. Distonic loss of the iodine creates a high-energy radical at the aromatic ring that engages in hydrogen/proton rearrangement chemistry. Based on UVPD kinetics measurements, the appearance of this radical is coincident with the UV irradiation pulse (8 ns). Conversely, sequential UVPD product ions exhibit metastable decay on ca. 100 ns timescales. Infrared ion spectroscopy is capable of confirming putative structures of the rearrangement products as proton transfers from the imine and β-carbon hydrogens. Potential energy surfaces for the various reaction pathways indicate that the rearrangement chemistry is highly complex, compatible with a cascade of rearrangements, and that there is no preferred rearrangement pathway even in small molecular systems like these. Graphical Abstract.

  9. Ultraviolet, Infrared, and High-Low Energy Photodissociation of Post-Translationally Modified Peptides

    NASA Astrophysics Data System (ADS)

    Halim, Mohammad A.; MacAleese, Luke; Lemoine, Jérôme; Antoine, Rodolphe; Dugourd, Philippe; Girod, Marion

    2018-02-01

    Mass spectrometry-based methods have made significant progress in characterizing post-translational modifications in peptides and proteins; however, certain aspects regarding fragmentation methods must still be improved. A good technique is expected to provide excellent sequence information, locate PTM sites, and retain the labile PTM groups. To address these issues, we investigate 10.6 μm IRMPD, 213 nm UVPD, and combined UV and IR photodissociation, known as HiLoPD (high-low photodissociation), for phospho-, sulfo-, and glyco-peptide cations. IRMPD shows excellent backbone fragmentation and produces equal numbers of N- and C-terminal ions. The results reveal that 213 nm UVPD and HiLoPD methods can provide diverse backbone fragmentation producing a/x, b/y, and c/z ions with excellent sequence coverage, locate PTM sites, and offer reasonable retention efficiency for phospho- and glyco-peptides. Excellent sequence coverage is achieved for sulfo-peptides and the position of the SO3 group can be pinpointed; however, widespread SO3 losses are detected irrespective of the methods used herein. Based on the overall performance achieved, we believe that 213 nm UVPD and HiLoPD can serve as alternative options to collision activation and electron transfer dissociations for phospho- and glyco-proteomics.

  10. Directed-Backbone Dissociation Following Bond-Specific Carbon-Sulfur UVPD at 213 nm

    NASA Astrophysics Data System (ADS)

    Talbert, Lance E.; Julian, Ryan R.

    2018-04-01

    Ultraviolet photodissociation or UVPD is an increasingly popular option for tandem-mass spectrometry experiments. UVPD can be carried out at many wavelengths, and it is important to understand how the results will be impacted by this choice. Here, we explore the utility of 213 nm photons for initiating bond-selective fragmentation. It is found that bonds previously determined to be labile at 266 nm, including carbon-iodine and sulfur-sulfur bonds, can also be cleaved with high selectivity at 213 nm. In addition, many carbon-sulfur bonds that are not subject to direct dissociation at 266 nm can be selectively fragmented at 213 nm. This capability can be used to site-specifically create alaninyl radicals that direct backbone dissociation at the radical site, creating diagnostic d-ions. Furthermore, the additional carbon-sulfur bond fragmentation capability leads to signature triplets for fragmentation of disulfide bonds. Absorption of amide bonds can enhance dissociation of nearby labile carbon-sulfur bonds and can be used for stochastic backbone fragmentation typical of UVPD experiments at shorter wavelengths. Several potential applications of the bond-selective fragmentation chemistry observed at 213 nm are discussed. [Figure not available: see fulltext.

  11. Photodissociation of conformer-selected ubiquitin ions reveals site-specific cis/trans isomerization of proline peptide bonds.

    PubMed

    Warnke, Stephan; Baldauf, Carsten; Bowers, Michael T; Pagel, Kevin; von Helden, Gert

    2014-07-23

    Ultraviolet photodissociation (UVPD) of gas-phase proteins has attracted increased attention in recent years. This growing interest is largely based on the fact that, in contrast to slow heating techniques such as collision induced dissociation (CID), the cleavage propensity after absorption of UV light is distributed over the entire protein sequence, which can lead to a very high sequence coverage as required in typical top-down proteomics applications. However, in the gas phase, proteins can adopt a multitude of distinct and sometimes coexisting conformations, and it is not clear how this three-dimensional structure affects the UVPD fragmentation behavior. Using ion mobility-UVPD-mass spectrometry in conjunction with molecular dynamics simulations, we provide the first experimental evidence that UVPD is sensitive to the higher order structure of gas-phase proteins. Distinct UVPD spectra were obtained for different extended conformations of 11(+) ubiquitin ions. Assignment of the fragments showed that the majority of differences arise from cis/trans isomerization of one particular proline peptide bond. Seen from a broader perspective, these data highlight the potential of UVPD to be used for the structural analysis of proteins in the gas phase.

  12. UVnovo: A De Novo Sequencing Algorithm Using Single Series of Fragment Ions via Chromophore Tagging and 351 nm Ultraviolet Photodissociation Mass Spectrometry

    PubMed Central

    Robotham, Scott A.; Horton, Andrew P.; Cannon, Joe R.; Cotham, Victoria C.; Marcotte, Edward M.; Brodbelt, Jennifer S.

    2016-01-01

    De novo peptide sequencing by mass spectrometry represents an important strategy for characterizing novel peptides and proteins, in which a peptide’s amino acid sequence is inferred directly from the precursor peptide mass and tandem mass spectrum (MS/MS or MS3) fragment ions, without comparison to a reference proteome. This method is ideal for organisms or samples lacking a complete or well-annotated reference sequence set. One of the major barriers to de novo spectral interpretation arises from confusion of N- and C-terminal ion series due to the symmetry between b and y ion pairs created by collisional activation methods (or c, z ions for electron-based activation methods). This is known as the ‘antisymmetric path problem’ and leads to inverted amino acid subsequences within a de novo reconstruction. Here, we combine several key strategies for de novo peptide sequencing into a single high-throughput pipeline: high efficiency carbamylation blocks lysine side chains, and subsequent tryptic digestion and N-terminal peptide derivatization with the ultraviolet chromophore AMCA yields peptides susceptible to 351 nm ultraviolet photodissociation (UVPD). UVPD-MS/MS of the AMCA-modified peptides then predominantly produces y ions in the MS/MS spectra, specifically addressing the antisymmetric path problem. Finally, the program UVnovo applies a random forest algorithm to automatically learn from and then interpret UVPD mass spectra, passing results to a hidden Markov model for de novo sequence prediction and scoring. We show this combined strategy provides high performance de novo peptide sequencing, enabling the de novo sequencing of thousands of peptides from an E. coli lysate at high confidence. PMID:26938041

  13. Concurrent Automated Sequencing of the Glycan and Peptide Portions of O-Linked Glycopeptide Anions by Ultraviolet Photodissociation Mass Spectrometry

    PubMed Central

    Madsen, James A.; Ko, Byoung Joon; Xu, Hua; Iwashkiw, Jeremy A.; Robotham, Scott A.; Shaw, Jared B.; Feldman, Mario F.; Brodbelt, Jennifer S.

    2013-01-01

    O -glycopeptides are often acidic owing to the frequent occurrence of acidic saccharides in the glycan, rendering traditional proteomic workflows that rely on positive mode tandem mass spectrometry (MS/MS) less effective. In this report, we demonstrate the utility of negative mode ultraviolet photodissociation (UVPD) MS for the characterization of acidic O-linked glycopeptide anions. This method was evaluated for a series of singly- and multiply-deprotonated glycopeptides from the model glycoprotein kappa casein, resulting in production of both peptide and glycan product ions that afforded 100% sequence coverage of the peptide and glycan moieties from a single MS/MS event. The most abundant and frequent peptide sequence ions were a/x-type products, which, importantly, were found to retain the labile glycan modifications. The glycan-specific ions mainly arose from glycosidic bond cleavages (B, Y, C, and Z ions) in addition to some less common cross-ring cleavages. Based on the UVPD fragmentation patterns, an automated database searching strategy (based on the MassMatrix algorithm) was designed that is specific for the analysis of glycopeptide anions by UVPD. This algorithm was used to identify glycopeptides from mixtures of glycosylated and non-glycosylated peptides, sequence both glycan and peptide moieties simultaneously, and pinpoint the correct site(s) of glycosylation. This methodology was applied to uncover novel site-specificity of the O-linked glycosylated OmpA/MotB from the “superbug” A. baumannii to help aid in the elucidation of the functional role that protein glycosylation plays in pathogenesis. PMID:24006841

  14. High-throughput Database Search and Large-scale Negative Polarity Liquid Chromatography–Tandem Mass Spectrometry with Ultraviolet Photodissociation for Complex Proteomic Samples*

    PubMed Central

    Madsen, James A.; Xu, Hua; Robinson, Michelle R.; Horton, Andrew P.; Shaw, Jared B.; Giles, David K.; Kaoud, Tamer S.; Dalby, Kevin N.; Trent, M. Stephen; Brodbelt, Jennifer S.

    2013-01-01

    The use of ultraviolet photodissociation (UVPD) for the activation and dissociation of peptide anions is evaluated for broader coverage of the proteome. To facilitate interpretation and assignment of the resulting UVPD mass spectra of peptide anions, the MassMatrix database search algorithm was modified to allow automated analysis of negative polarity MS/MS spectra. The new UVPD algorithms were developed based on the MassMatrix database search engine by adding specific fragmentation pathways for UVPD. The new UVPD fragmentation pathways in MassMatrix were rigorously and statistically optimized using two large data sets with high mass accuracy and high mass resolution for both MS1 and MS2 data acquired on an Orbitrap mass spectrometer for complex Halobacterium and HeLa proteome samples. Negative mode UVPD led to the identification of 3663 and 2350 peptides for the Halo and HeLa tryptic digests, respectively, corresponding to 655 and 645 peptides that were unique when compared with electron transfer dissociation (ETD), higher energy collision-induced dissociation, and collision-induced dissociation results for the same digests analyzed in the positive mode. In sum, 805 and 619 proteins were identified via UVPD for the Halobacterium and HeLa samples, respectively, with 49 and 50 unique proteins identified in contrast to the more conventional MS/MS methods. The algorithm also features automated charge determination for low mass accuracy data, precursor filtering (including intact charge-reduced peaks), and the ability to combine both positive and negative MS/MS spectra into a single search, and it is freely open to the public. The accuracy and specificity of the MassMatrix UVPD search algorithm was also assessed for low resolution, low mass accuracy data on a linear ion trap. Analysis of a known mixture of three mitogen-activated kinases yielded similar sequence coverage percentages for UVPD of peptide anions versus conventional collision-induced dissociation of

  15. Ultraviolet Photodissociation Spectroscopy of the Cold K⁺·Calix[4]arene Complex in the Gas Phase.

    PubMed

    Inokuchi, Yoshiya; Soga, Kazuki; Hirai, Kenta; Kida, Motoki; Morishima, Fumiya; Ebata, Takayuki

    2015-08-06

    The cooling of ionic species in the gas phase greatly simplifies the UV spectrum, which is of special importance when studying the electronic and geometric structures of large systems, such as biorelated molecules and host-guest complexes. Many efforts have been devoted to achieving ion cooling with a cold, quadrupole Paul ion trap (QIT), but one problem was the insufficient cooling of ions (up to ∼30 K) in the QIT. In this study, we construct a mass spectrometer for the ultraviolet photodissociation (UVPD) spectroscopy of gas-phase cold ions. The instrument consists of an electrospray ion source, a QIT cooled with a He cryostat, and a time-of-flight mass spectrometer. With great care given to the cooling condition, we can achieve ∼10 K for the vibrational temperature of ions in the QIT, which is estimated from UVPD spectra of the benzo-18-crown-6 (B18C6) complex with a potassium ion, K(+)·B18C6. Using this setup, we measure a UVPD spectrum of cold calix[4]arene (C4A) complex with potassium ion, K(+)·C4A. The spectrum shows a very weak band and a strong one at 36018 and 36156 cm(-1), respectively, accompanied by many sharp vibronic bands in the 36000-36600 cm(-1) region. In the geometry optimization of the K(+)·C4A complex, we obtain three stable isomers: one endo and two exo forms. On the basis of the total energy and UV spectral patterns predicted by density functional theory calculations, we attribute the structure of the K(+)·C4A complex to the endo isomer (C2 symmetry), in which the K(+) ion is located inside the cup of C4A. The vibronic bands of K(+)·C4A at 36 018 and 36 156 cm(-1) are assigned to the S1(A)-S0(A) and S2(B)-S0(A) transitions of the endo isomer, respectively.

  16. Near-UV Photodissociation of Tryptic Peptide Cation Radicals. Scope and Effects of Amino Acid Residues and Radical Sites

    NASA Astrophysics Data System (ADS)

    Nguyen, Huong T. H.; Tureček, František

    2017-07-01

    Peptide cation-radical fragment ions of the z-type, [●AXAR+], [●AXAK+], and [●XAR+], where X = A, C, D, E, F, G, H, K, L, M, N, P, Y, and W, were generated by electron transfer dissociation of peptide dications and investigated by MS3-near-ultraviolet photodissociation (UVPD) at 355 nm. Laser-pulse dependence measurements indicated that the ion populations were homogeneous for most X residues except phenylalanine. UVPD resulted in dissociations of backbone CO-NH bonds that were accompanied by hydrogen atom transfer, producing fragment ions of the [yn]+ type. Compared with collision-induced dissociation, UVPD yielded less side-chain dissociations even for residues that are sensitive to radical-induced side-chain bond cleavages. The backbone dissociations are triggered by transitions to second ( B) excited electronic states in the peptide ion R-CH●-CONH- chromophores that are resonant with the 355-nm photon energy. Electron promotion increases the polarity of the B excited states, R-CH+-C●(O-)NH-, and steers the reaction to proceed by transfer of protons from proximate acidic Cα and amide nitrogen positions.

  17. Combining UV photodissociation action spectroscopy with electron transfer dissociation for structure analysis of gas-phase peptide cation-radicals.

    PubMed

    Shaffer, Christopher J; Pepin, Robert; Tureček, František

    2015-12-01

    We report the first example of using ultraviolet (UV) photodissociation action spectroscopy for the investigation of gas-phase peptide cation-radicals produced by electron transfer dissociation. z-Type fragment ions (●) Gly-Gly-Lys(+), coordinated to 18-crown-6-ether (CE), are generated, selected by mass and photodissociated in the 200-400 nm region. The UVPD action spectra indicate the presence of valence-bond isomers differing in the position of the Cα radical defect, (α-Gly)-Gly-Lys(+) (CE), Gly-(α-Gly)-Lys(+) (CE) and Gly-Gly-(α-Lys(+))(CE). The isomers are readily distinguishable by UV absorption spectra obtained by time-dependent density functional theory (TD-DFT) calculations. In contrast, conformational isomers of these radical types are calculated to have similar UV spectra. UV photodissociation action spectroscopy represents a new tool for the investigation of transient intermediates of ion-electron reactions. Specifically, z-type cation radicals are shown to undergo spontaneous hydrogen atom migrations upon electron transfer dissociation. Copyright © 2015 John Wiley & Sons, Ltd.

  18. Detailed Structural Characterization of Sphingolipids via 193 nm Ultraviolet Photodissociation and Ultra High Resolution Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ryan, Eileen; Nguyen, Catherine Quynh Nhu; Shiea, Christopher; Reid, Gavin E.

    2017-07-01

    Sphingolipids serve not only as components of cellular membranes but also as bioactive mediators of numerous cellular functions. As the biological activities of these lipids are dependent on their structures, and due to the limitations of conventional ion activation methods employed during tandem mass spectrometry (MS/MS), there is a recognized need for the development of improved structure-specific methods for their comprehensive identification and characterization. Here, positive-ionization mode 193 nm ultraviolet photodissociation (UVPD)-MS/MS has been implemented for the detailed structural characterization of lipid species from a range of sphingolipid classes introduced to the mass spectrometer via electrospray ionization as their lithiated or protonated adducts. These include sphingosine d18:1(4E), dihydrosphingosine (sphinganine) d18:0, sphingadiene d18:2(4E,11Z), the isomeric sphingolipids ceramide d18:1(4E)/18:0 and dihydroceramide d18:0/18:1(9Z), ceramide-1-phosphate d18:1(4Z)/16:0, sphingomyelin d18:1(4E)/18:1(9Z) the glycosphingolipids galactosyl ceramide d18:1(4E)/24:1(15Z) and lactosyl ceramide d18:1(4E)/24:0, and several endogenous lipids present within a porcine brain total lipid extract. In addition to the product ions formed by higher energy collision dissociation (HCD), UVPD is shown to yield a series of novel structurally diagnostic product ions resulting from cleavage of both sphingosine carbon-carbon and acyl chain carbon-carbon double bonds for direct localization of site(s) of unsaturation, as well as via diagnostic cleavages of the sphingosine backbone and N-C amide bond linkages. With activation timescales and dissociation efficiencies similar to those found in conventional MS/MS strategies, this approach is therefore a promising new tool in the arsenal of ion activation techniques toward providing complete structural elucidation in automated, high-throughput lipid analysis workflows.

  19. High-throughput bioconjugation for enhanced 193 nm photodissociation via droplet phase initiated ion/ion chemistry using a front-end dual spray reactor.

    PubMed

    Cotham, Victoria C; Shaw, Jared B; Brodbelt, Jennifer S

    2015-09-15

    Fast online chemical derivatization of peptides with an aromatic label for enhanced 193 nm ultraviolet photodissociation (UVPD) is demonstrated using a dual electrospray reactor implemented on the front-end of a linear ion trap (LIT) mass spectrometer. The reactor facilitates the intersection of protonated peptides with a second population of chromogenic 4-formyl-1,3-benzenedisulfonic acid (FBDSA) anions to promote real-time formation of ion/ion complexes at atmospheric pressure. Subsequent collisional activation of the ion/ion intermediate results in Schiff base formation generated via reaction between a primary amine in the peptide cation and the aldehyde moiety of the FBDSA anion. Utilizing 193 nm UVPD as the subsequent activation step in the MS(3) workflow results in acquisition of greater primary sequence information relative to conventional collision induced dissociation (CID). Furthermore, Schiff-base-modified peptides exhibit on average a 20% increase in UVPD efficiency compared to their unmodified counterparts. Due to the efficiency of covalent labeling achieved with the dual spray reactor, we demonstrate that this strategy can be integrated into a high-throughput LC-MS(n) workflow for rapid derivatization of peptide mixtures.

  20. Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hansen, Christopher S., E-mail: csh297@uowmail.edu.au; Trevitt, Adam J., E-mail: adamt@uow.edu.au; Blanksby, Stephen J.

    2015-01-07

    The S{sub 1}←S{sub 0} electronic transition of the N-pyridinium ion (C{sub 5}H{sub 5}NH{sup +}) is investigated using ultraviolet photodissociation (PD) spectroscopy of the bare ion and also the N{sub 2}-tagged complex. Gas-phase N-pyridinium ions photodissociate by the loss of molecular hydrogen (H{sub 2}) in the photon energy range 37 000–45 000 cm{sup −1} with structurally diagnostic ion-molecule reactions identifying the 2-pyridinylium ion as the exclusive co-product. The photodissociation action spectra reveal vibronic details that, with the aid of electronic structure calculations, support the proposal that dissociation occurs through an intramolecular rearrangement on the ground electronic state following internal conversion. Quantum chemical calculationsmore » are used to analyze the measured spectra. Most of the vibronic features are attributed to progressions of totally symmetric ring deformation modes and out-of-plane modes active in the isomerization of the planar excited state towards the non-planar excited state global minimum.« less

  1. Vacuum Ultraviolet Photodissociation and Fourier Transform–Ion Cyclotron Resonance (FT-ICR) Mass Spectrometry: Revisited

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shaw, Jared B.; Robinson, Errol W.; Pasa-Tolic, Ljiljana

    2016-02-16

    We revisited the implementation of UVPD within the ICR cell of a FT-ICR mass spectrometer. UVPD performance characteristics were examined in the context of recent developments in the understanding of UVPD and in-cell tandem mass spectrometry. Efficient UVPD and photo-ECD of a model peptide and small protein within the ICR cell of a FT-ICR mass spectrometer are accomplished through appropriate modulation of laser pulse timing relative to ion magnetron motion and the potential applied to an ion optical element that photons impinge on. It is shown that UVPD yields efficient and extensive fragmentation resulting in excellent sequence coverage for modelmore » peptide and protein cations.« less

  2. Ultraviolet photodissociation dynamics of the benzyl radical.

    PubMed

    Song, Yu; Zheng, Xianfeng; Lucas, Michael; Zhang, Jingsong

    2011-05-14

    Ultraviolet (UV) photodissociation dynamics of jet-cooled benzyl radical via the 4(2)B(2) electronically excited state is studied in the photolysis wavelength region of 228 to 270 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance enhanced multiphoton ionization (REMPI) techniques. In this wavelength region, H-atom photofragment yield (PFY) spectra are obtained using ethylbenzene and benzyl chloride as the precursors of benzyl radical, and they have a broad peak centered around 254 nm and are in a good agreement with the previous UV absorption spectra of benzyl. The H + C(7)H(6) product translational energy distributions, P(E(T))s, are derived from the H-atom TOF spectra. The P(E(T)) distributions peak near 5.5 kcal mol(-1), and the fraction of average translational energy in the total excess energy, , is ∼0.3. The P(E(T))s indicate the production of fulvenallene + H, which was suggested by recent theoretical studies. The H-atom product angular distribution is isotropic, with the anisotropy parameter β ≈ 0. The H/D product ratios from isotope labeling studies using C(6)H(5)CD(2) and C(6)D(5)CH(2) are reasonably close to the statistical H/D ratios, suggesting that the H/D atoms are scrambled in the photodissociation of benzyl. The dissociation mechanism is consistent with internal conversion of the electronically excited benzyl followed by unimolecular decomposition of the hot benzyl radical on the ground state.

  3. Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: Wavelength, pressure and temperature dependency.

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid

    Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasingmore » synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.« less

  4. Anatomy of the Photodissociation Region in the Orion Bar

    NASA Technical Reports Server (NTRS)

    Tielens, A. G. G. M.; Meixner, M. M.; vanderWerf, P. P.; Bregman, J.; Tauber, J. A.; Stutzki, J.; Rank, D.

    1993-01-01

    Much of the interstellar gas resides in photodissociation regions whose chemistry and energy balance is controlled by the flux of far-ultraviolet radiation upon them. These photons can ionize and dissociate molecules and heat the gas through the photoelectric effect working on dust grains. These regions have been extensively modeled theoretically, but detailed observational studies are few. Mapping of the prominent Orion Bar photo-dissociation region at wavelengths corresponding to the carbon-hydrogen stretching mode of polycyclic aromatic hydrocarbons, the 1-0 S(l) line of molecular hydrogen, and the J = 1-0 rotational line of carbon monoxide allows the penetration of the far-ultraviolet radiation into the cloud to be traced. The results strongly support the theoretical models and show conclusively that the incident far-ultraviolet radiation field, not shocks as has sometimes been proposed, is responsible for the emission in the Orion Bar.

  5. Single-layer graphene/titanium oxide cubic nanorods array/FTO heterojunction for sensitive ultraviolet light detection

    NASA Astrophysics Data System (ADS)

    Liang, Feng-Xia; Wang, Jiu-Zhen; Wang, Yi; Lin, Yi; Liang, Lin; Gao, Yang; Luo, Lin-Bao

    2017-12-01

    In this study, we report on the fabrication of a sensitive ultraviolet photodetector (UVPD) by simply transferring single-layer graphene (SLG) on rutile titanium oxide cubic nanorod (TiO2NRs) array. The cubic TiO2NRs array with strong light trapping effect was grown on fluorine-doped tin oxide (FTO) glass through a hydrothermal approach. The as-assembled UVPD was very sensitive to UV light illumination, but virtually blind to white light illumination. The responsivity and specific detectivity were estimated to be 52.1 A/W and 4.3 × 1012 Jones, respectively. What is more, in order to optimize device performance of UVPD, a wet-chemistry treatment was then employed to reduce the high concentration of defects in TiO2NRs during hydrothermal growth. It was found that the UVPD after treatment showed obvious decrease in sensitivity, but the response speed (rise time: 80 ms, fall time: 160 ms) and specific detectivity were substantially increased. It is also found that the speicific detectivity was imporoved by six-fold to 3.2 × 1013 Jones, which was the best result in comparison with previously reported TiO2 nanostructures or thin film based UVPDs. This totality of this study shows that the present SLG/TiO2NR/FTO UVPD may find potential application in future optoelectronic devices and systems.

  6. Combined Infrared Multiphoton Dissociation with Ultraviolet Photodissociation for Ubiquitin Characterization

    NASA Astrophysics Data System (ADS)

    Halim, Mohammad A.; Girod, Marion; MacAleese, Luke; Lemoine, Jérôme; Antoine, Rodolphe; Dugourd, Philippe

    2016-09-01

    Herein we report the successful implementation of the consecutive and simultaneous photodissociation with high (213 nm) and low (10.6 μm) energy photons (HiLoPD, high-low photodissociation) on ubiquitin in a quadrupole-Orbitrap mass spectrometer. Absorption of high-energy UV photon is dispersed over the whole protein and stimulates extensive C-Cα backbone fragmentation, whereas low-energy IR photon gradually increases the internal energy and thus preferentially dissociates the most labile amide (C-N) bonds. We noticed that simultaneous irradiation of UV and IR lasers on intact ubiquitin in a single MS/MS experiment provides a rich and well-balanced fragmentation array of a/x, b/y, and z ions. Moreover, secondary fragmentation from a/x and z ions leads to the formation of satellite side-chain ions (d, v, and w) and can help to distinguish isomeric residues in a protein. Implementation of high-low photodissociation in a high-resolution mass spectrometer may offer considerable benefits to promote a comprehensive portrait of protein characterization.

  7. Ground and Excited-Electronic-State Dissociations of Hydrogen-Rich and Hydrogen-Deficient Tyrosine Peptide Cation Radicals

    NASA Astrophysics Data System (ADS)

    Viglino, Emilie; Lai, Cheuk Kuen; Mu, Xiaoyan; Chu, Ivan K.; Tureček, František

    2016-09-01

    We report a comprehensive study of collision-induced dissociation (CID) and near-UV photodissociation (UVPD) of a series of tyrosine-containing peptide cation radicals of the hydrogen-rich and hydrogen-deficient types. Stable, long-lived, hydrogen-rich peptide cation radicals, such as [AAAYR + 2H]+● and several of its sequence and homology variants, were generated by electron transfer dissociation (ETD) of peptide-crown-ether complexes, and their CID-MS3 dissociations were found to be dramatically different from those upon ETD of the respective peptide dications. All of the hydrogen-rich peptide cation radicals contained major (77%-94%) fractions of species having radical chromophores created by ETD that underwent photodissociation at 355 nm. Analysis of the CID and UVPD spectra pointed to arginine guanidinium radicals as the major components of the hydrogen-rich peptide cation radical population. Hydrogen-deficient peptide cation radicals were generated by intramolecular electron transfer in CuII(2,2 ':6 ',2 ″-terpyridine) complexes and shown to contain chromophores absorbing at 355 nm and undergoing photodissociation. The CID and UVPD spectra showed major differences in fragmentation for [AAAYR]+● that diminished as the Tyr residue was moved along the peptide chain. UVPD was found to be superior to CID in localizing Cα-radical positions in peptide cation radical intermediates.

  8. The Photodissociation of HCN and HNC: Effects on the HNC/HCN Abundance Ratio in the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Aguado, Alfredo; Roncero, Octavio; Zanchet, Alexandre; Agúndez, Marcelino; Cernicharo, José

    2017-03-01

    The impact of the photodissociation of HCN and HNC isomers is analyzed in different astrophysical environments. For this purpose, the individual photodissociation cross sections of HCN and HNC isomers have been calculated in the 7-13.6 eV photon energy range for a temperature of 10 K. These calculations are based on the ab initio calculation of three-dimensional adiabatic potential energy surfaces of the 21 lower electronic states. The cross sections are then obtained using a quantum wave packet calculation of the rotational transitions needed to simulate a rotational temperature of 10 K. The cross section calculated for HCN shows significant differences with respect to the experimental one, and this is attributed to the need to consider non-adiabatic transitions. Ratios between the photodissociation rates of HCN and HNC under different ultraviolet radiation fields have been computed by renormalizing the rates to the experimental value. It is found that HNC is photodissociated faster than HCN by a factor of 2.2 for the local interstellar radiation field and 9.2 for the solar radiation field, at 1 au. We conclude that to properly describe the HNC/HCN abundance ratio in astronomical environments illuminated by an intense ultraviolet radiation field, it is necessary to use different photodissociation rates for each of the two isomers, which are obtained by integrating the product of the photodissociation cross sections and ultraviolet radiation field over the relevant wavelength range.

  9. Tyrosine sulfation in a Gram-negative bacterium

    PubMed Central

    Han, Sang-Wook; Lee, Sang-Won; Bahar, Ofir; Schwessinger, Benjamin; Robinson, Michelle R.; Shaw, Jared B.; Madsen, James A.; Brodbelt, Jennifer S.; Ronald, Pamela C.

    2015-01-01

    Tyrosine sulfation, a well-characterized post-translation modification in eukaryotes, has not previously been reported in prokaryotes. Here we demonstrate that the RaxST protein from the Gram-negative bacterium, Xanthomonas oryzae pv. oryzae, is a tyrosine sulfotransferase. We used a newly developed sulfotransferase assay and ultraviolet photodissociation mass spectrometry (UVPD) to demonstrate that RaxST catalyzes sulfation of tyrosine 22 of the Xoo Ax21 (activator of XA21-mediated immunity). These results demonstrate a previously undescribed post-translational modification in a prokaryotic species with implications extending to host immune response and bacterial cell-cell communication system. PMID:23093190

  10. Charge transfer photodissociation of phenol on Ag(111)

    NASA Astrophysics Data System (ADS)

    Lee, Junseok; Ryu, Sunmin; Ku, Jong Seok; Kim, Seong Keun

    2001-12-01

    The photochemistry of phenol on Ag(111) has been investigated by post-irradiation temperature programmed desorption (TPD). Ultraviolet (UV) irradiation at 355 and 266 nm was found to affect only the chemisorption layer in direct contact with the metal surface, while leaving the multilayer virtually intact. The main photoinduced reaction was found to be photodissociation of the O-H bond of phenol. Two new peaks were observed at the mass of phenol in the post-irradiation TPD spectrum at 335 K and 455 K. These peaks were assigned to the recombinative desorption of phenoxy with the hydrogen from O-H bond photodissociation and from thermal C-H bond fission, respectively. The photodissociation cross section was measured at different wavelengths and coverages. A charge transfer type photodissociation mechanism was proposed, where hot electrons generated in the substrate by UV photons attach to the affinity level of the adsorbed phenol. The transition to the transient anionic potential then leads to facile dissociation of O-H bond. The affinity level of phenol has been estimated to lie at 3.2-3.5 eV above the Fermi level for the 1 ML case.

  11. Production of reactive species using vacuum ultraviolet photodissociation as a tool for studying their effects in plasma medicine: simulations and measurements

    NASA Astrophysics Data System (ADS)

    Ono, Ryo; Tokumitsu, Yusuke; Zen, Shungo; Yonemori, Seiya

    2014-11-01

    We propose a method for producing OH, H, O, O3, and O2(a1Δg) using the vacuum ultraviolet photodissociation of H2O and O2 as a tool for studying the reaction processes of plasma medicine. For photodissociation, an H2O/He or O2/He mixture flowing in a quartz tube is irradiated by a Xe2 or Kr2 excimer lamp. The effluent can be applied to a target. Simulations show that the Xe2 lamp method can produce OH radicals within 0.1-1 ppm in the effluent at 5 mm from a quartz tube nozzle. This is comparable to those produced by a helium atmospheric-pressure plasma jet (He-APPJ) currently used in plasma medicine. The Xe2 lamp method also produces H atoms of, at most, 6 ppm. In contrast, the maximum O densities produced by the Xe2 and Kr2 lamp methods are 0.15 ppm and 2.5 ppm, respectively; these are much lower than those from He-APPJ (several tens of ppm). Both lamp methods can produce ozone at concentrations above 1000 ppm and O2(a1Δg) at tens of ppm. The validity of the simulations is verified by measuring the O3 and OH densities produced by the Xe2 lamp method using ultraviolet absorption and laser-induced fluorescence. The differences between the measured and simulated densities for O3 and OH are 20% and factors of 3-4, respectively.

  12. Photodissociation of Non-Covalent Peptide-Crown Ether Complexes

    PubMed Central

    Wilson, Jeffrey J.; Kirkovits, Gregory J.; Sessler, Jonathan L.; Brodbelt, Jennifer S.

    2008-01-01

    Highly chromogenic 18-crown-6-dipyrrolylquinoxaline coordinates primary amines of peptides, forming non-covalent complexes that can be transferred to the gas phase by electrospray ionization. The appended chromogenic crown ether facilitates efficient energy transfer to the peptide upon ultraviolet irradiation in the gas phase, resulting in diagnostic peptide fragmentation. Collisional activated dissociation (CAD) and infrared multiphoton dissociation (IRMPD) of these non-covalent complexes results only in their disassembly with the charge retained on either the peptide or crown ether, yielding no sequence ions. Upon UV photon absorption the intermolecular energy transfer is facilitated by the fast activation time scale of UVPD (< 10 ns) and by the collectively strong hydrogen bonding between the crown ether and peptide, thus allowing effective transfer of energy to the peptide moiety prior to disruption of the intermolecular hydrogen bonds. PMID:18077179

  13. On the ultraviolet photodissociation of H2Te

    NASA Astrophysics Data System (ADS)

    Alekseyev, Aleksey B.; Liebermann, Heinz-Peter; Wittig, Curt

    2004-11-01

    The photodissociation of H2Te through excitation in the first absorption band is investigated by means of multireference spin-orbit configuration interaction (CI) calculations. Bending potentials for low-lying electronic states of H2Te are obtained in C2v symmetry for Te-H distances fixed at the ground state equilibrium value of 3.14a0, as well as for the minimum energy path constrained to R1=R2. Asymmetric cuts of potential energy surfaces for excited states (at R1=3.14a0 and θ=90.3°) are obtained for the first time. It is shown that vibrational structure in the 380-400 nm region of the long wavelength absorption tail is due to transitions to 3A', which has a shallow minimum at large HTe-H separations. Transitions to this state are polarized in the molecular plane, and this state converges to the excited TeH(2Π1/2)+H(2S) limit. These theoretical data are in accord with the selectivity toward TeH(2Π1/2) relative to TeH(2Π3/2) that has been found experimentally for 355 nm H2Te photodissociation. The calculated 3A'←X˜A' transition dipole moment increases rapidly with HTe-H distance; this explains the observation of 3A' vibrational structure for low vibrational levels, despite unfavorable Franck-Condon factors. According to the calculated vertical energies and transition moment data, the maximum in the first absorption band at ≈245 nm is caused by excitation to 4A″, which has predominantly 21A″ (1B1 in C2v symmetry) character.

  14. Research on fluorescence from photoionization, photodissociation, and vacuum, along with bending quantrum study

    NASA Technical Reports Server (NTRS)

    Judge, D. L.

    1975-01-01

    Reports of research concerning the fluorescence of CS2 are presented. Fluorescence from fragments of CS2 vapor produced by vacuum ultraviolet radiation, and fluorescence from photoionization of CS2 vapor are discussed along with fluorescence produced by photodissociation of CS2, and fluorescence from photoionization of OCS.

  15. Photodissociation and photoionisation of atoms and molecules of astrophysical interest

    NASA Astrophysics Data System (ADS)

    Heays, A. N.; Bosman, A. D.; van Dishoeck, E. F.

    2017-06-01

    A new collection of photodissociation and photoionisation cross sections for 102 atoms and molecules of astrochemical interest has been assembled, along with a brief review of the basic physical processes involved. These have been used to calculate dissociation and ionisation rates, with uncertainties, in a standard ultraviolet interstellar radiation field (ISRF) and for other wavelength-dependent radiation fields, including cool stellar and solar radiation, Lyman-α dominated radiation, and a cosmic-ray induced ultraviolet flux. The new ISRF rates generally agree within 30% with our previous compilations, with a few notable exceptions. Comparison with other databases such as PHIDRATES is made. The reduction of rates in shielded regions was calculated as a function of dust, molecular and atomic hydrogen, atomic C, and self-shielding column densities. The relative importance of these shielding types depends on the atom or molecule in question and the assumed dust optical properties. All of the new data are publicly available from the Leiden photodissociation and ionisation database. Sensitivity of the calculated rates to variation of temperature and isotope, and uncertainties in measured or calculated cross sections, are tested and discussed. Tests were conducted on the new rates with an interstellar-cloud chemical model, and find general agreement (within a factor of two) in abundances obtained with the previous iteration of the Leiden database assuming an ISRF, and order-of-magnitude variations assuming various kinds of stellar radiation. The newly parameterised dust-shielding factors makes a factor-of-two difference to many atomic and molecular abundances relative to parameters currently in the UDfA and KIDA astrochemical reaction databases. The newly-calculated cosmic-ray induced photodissociation and ionisation rates differ from current standard values up to a factor of 5. Under high temperature and cosmic-ray-flux conditions the new rates alter the equilibrium

  16. Noncontact detection of homemade explosive constituents via photodissociation followed by laser-induced fluorescence.

    PubMed

    Wynn, C M; Palmacci, S; Kunz, R R; Rothschild, M

    2010-03-15

    Noncontact detection of the homemade explosive constituents urea nitrate, nitromethane and ammonium nitrate is achieved using photodissociation followed by laser-induced fluorescence (PD-LIF). Our technique utilizes a single ultraviolet laser pulse (approximately 7 ns) to vaporize and photodissociate the condensed-phase materials, and then to detect the resulting vibrationally-excited NO fragments via laser-induced fluorescence. PD-LIF excitation and emission spectra indicate the creation of NO in vibrationally-excited states with significant rotational energy, useful for low-background detection of the parent compound. The results for homemade explosives are compared to one another and 2,6-dinitrotoluene, a component present in many military explosives.

  17. THE PHOTODISSOCIATION OF FORMALDEHYDE IN COMETS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Feldman, Paul D., E-mail: pfeldman@jhu.edu

    2015-10-20

    Observations of comets in the 905–1180 Å spectral band made with the Far Ultraviolet Spectroscopic Explorer in 2001 and 2004 show unusual features in the fluorescent emissions of CO and H{sub 2}. These include emission from a non-thermal high-J rotational population of CO and solar Lyα induced fluorescence from excited vibrational levels of H{sub 2}, both of which are attributed to the photodissociation of formaldehyde. In this paper we model the large number of observed H{sub 2} lines and demonstrate the dependence of the pumping on the heliocentric velocity of the comet and the solar line profiles. We also derivemore » the rotational and vibrational populations of H{sub 2} and show that they are consistent with the results of laboratory studies of the photodissociation of H{sub 2}CO. In addition to the principal series of H i and O i, the residual spectrum is found to consist mainly of the Rydberg series of C i multiplets from which we derive the mean carbon column abundance in the coma. Fluorescent emissions from N i and N{sub 2} are also searched for.« less

  18. Analytic H I-to-H2 Photodissociation Transition Profiles

    NASA Astrophysics Data System (ADS)

    Bialy, Shmuel; Sternberg, Amiel

    2016-05-01

    We present a simple analytic procedure for generating atomic (H I) to molecular ({{{H}}}2) density profiles for optically thick hydrogen gas clouds illuminated by far-ultraviolet radiation fields. Our procedure is based on the analytic theory for the structure of one-dimensional H I/{{{H}}}2 photon-dominated regions, presented by Sternberg et al. Depth-dependent atomic and molecular density fractions may be computed for arbitrary gas density, far-ultraviolet field intensity, and the metallicity-dependent H2 formation rate coefficient, and dust absorption cross section in the Lyman-Werner photodissociation band. We use our procedure to generate a set of {{H}} {{I}}{-}{to}{-}{{{H}}}2 transition profiles for a wide range of conditions, from the weak- to strong-field limits, and from super-solar down to low metallicities. We show that if presented as functions of dust optical depth, the {{H}} {{I}} and {{{H}}}2 density profiles depend primarily on the Sternberg “α G parameter” (dimensionless) that determines the dust optical depth associated with the total photodissociated {{H}} {{I}} column. We derive a universal analytic formula for the {{H}} {{I}}{-}{to}{-}{{{H}}}2 transition points as a function of just α G. Our formula will be useful for interpreting emission-line observations of H I/{{{H}}}2 interfaces, for estimating star formation thresholds, and for sub-grid components in hydrodynamics simulations.

  19. Photodissociation dynamics of H2O at 111.5 nm by a vacuum ultraviolet free electron laser

    NASA Astrophysics Data System (ADS)

    Wang, Heilong; Yu, Yong; Chang, Yao; Su, Shu; Yu, Shengrui; Li, Qinming; Tao, Kai; Ding, Hongli; Yang, Jaiyue; Wang, Guanglei; Che, Li; He, Zhigang; Chen, Zhichao; Wang, Xingan; Zhang, Weiqing; Dai, Dongxu; Wu, Guorong; Yuan, Kaijun; Yang, Xueming

    2018-03-01

    Photodissociation dynamics of H2O via the F ˜ state at 111.5 nm were investigated using the high resolution H-atom Rydberg "tagging" time-of-flight (TOF) technique, in combination with the tunable vacuum ultraviolet free electron laser at the Dalian Coherent Light Source. The product translational energy distributions and angular distributions in both parallel and perpendicular directions were derived from the recorded TOF spectra. Based on these distributions, the quantum state distributions and angular anisotropy parameters of OH (X) and OH (A) products have been determined. For the OH (A) + H channel, highly rotationally excited OH (A) products have been observed. These products are ascribed to a fast direct dissociation on the B ˜ 1A1 state surface after multi-step internal conversions from the initial excited F ˜ state to the B ˜ state. While for the OH (X) + H channel, very highly rotationally excited OH (X) products with moderate vibrational excitation are revealed and attributed to the dissociation via a nonadiabatic pathway through the well-known two conical intersections between the B ˜ -state and the X ˜ -state surfaces.

  20. UV-Vis Action Spectroscopy Reveals a Conformational Collapse in Hydrogen-Rich Dinucleotide Cation Radicals.

    PubMed

    Korn, Joseph A; Urban, Jan; Dang, Andy; Nguyen, Huong T H; Tureček, František

    2017-09-07

    We report the generation of deoxyriboadenosine dinucleotide cation radicals by gas-phase electron transfer to dinucleotide dications and their noncovalent complexes with crown ether ligands. Stable dinucleotide cation radicals of a novel hydrogen-rich type were generated and characterized by tandem mass spectrometry and UV-vis photodissociation (UVPD) action spectroscopy. Electron structure theory analysis indicated that upon electron attachment the dinucleotide dications underwent a conformational collapse followed by intramolecular proton migrations between the nucleobases to give species whose calculated UV-vis absorption spectra matched the UVPD action spectra. Hydrogen-rich cation radicals generated from chimeric riboadenosine 5'-diesters gave UVPD action spectra that pointed to novel zwitterionic structures consisting of aromatic π-electron anion radicals intercalated between stacked positively charged adenine rings. Analogies with DNA ionization are discussed.

  1. Ultraviolet photodissociation dynamics of the n-propyl and i-propyl radicals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Song, Yu; Zheng, Xianfeng; Zhou, Weidong

    2015-06-14

    Ultraviolet (UV) photodissociation dynamics of jet-cooled n-propyl (n-C{sub 3}H{sub 7}) radical via the 3s Rydberg state and i-propyl (i-C{sub 3}H{sub 7}) radical via the 3p Rydberg states are studied in the photolysis wavelength region of 230–260 nm using high-n Rydberg atom time-of-flight and resonance enhanced multiphoton ionization techniques. The H-atom photofragment yield spectra of the n-propyl and i-propyl radicals are broad and in good agreement with the UV absorption spectra. The H + propene product translational energy distributions, P(E{sub T})’s, of both n-propyl and i-propyl are bimodal, with a slow component peaking around 5-6 kcal/mol and a fast one peakingmore » at ∼50 kcal/mol (n-propyl) and ∼45 kcal/mol (i-propyl). The fraction of the average translational energy in the total excess energy, 〈f{sub T}〉, is 0.3 for n-propyl and 0.2 for i-propyl, respectively. The H-atom product angular distributions of the slow components of n-propyl and i-propyl are isotropic, while that of the fast component of n-propyl is anisotropic (with an anisotropy parameter ∼0.8) and that of i-propyl is nearly isotropic. Site-selective loss of the β hydrogen atom is confirmed using the partially deuterated CH{sub 3}CH{sub 2}CD{sub 2} and CH{sub 3}CDCH{sub 3} radicals. The bimodal translational energy and angular distributions indicate two dissociation pathways to the H + propene products in the n-propyl and i-propyl radicals: (i) a unimolecular dissociation pathway from the hot ground-state propyl after internal conversion from the 3s and 3p Rydberg states and (ii) a direct, prompt dissociation pathway coupling the Rydberg excited states to a repulsive part of the ground-state surface, presumably via a conical intersection.« less

  2. UV Photofragmentation Dynamics of Protonated Cystine: Disulfide Bond Rupture.

    PubMed

    Soorkia, Satchin; Dehon, Christophe; Kumar, S Sunil; Pedrazzani, Mélanie; Frantzen, Emilie; Lucas, Bruno; Barat, Michel; Fayeton, Jacqueline A; Jouvet, Christophe

    2014-04-03

    Disulfide bonds (S-S) play a central role in stabilizing the native structure of proteins against denaturation. Experimentally, identification of these linkages in peptide and protein structure characterization remains challenging. UV photodissociation (UVPD) can be a valuable tool in identifying disulfide linkages. Here, the S-S bond acts as a UV chromophore and absorption of one UV photon corresponds to a σ-σ* transition. We have investigated the photodissociation dynamics of protonated cystine, which is a dimer of two cysteines linked by a disulfide bridge, at 263 nm (4.7 eV) using a multicoincidence technique in which fragments coming from the same fragmentation event are detected. Two types of bond cleavages are observed corresponding to the disulfide (S-S) and adjacent C-S bond ruptures. We show that the S-S cleavage leads to three different fragment ions via three different fragmentation mechanisms. The UVPD results are compared to collision-induced dissociation (CID) and electron-induced dissociation (EID) studies.

  3. Photodissociation of Small Molecules and Photoionization of Free Radicals Using the VUV Velocity-Map Imaging Photoion and Photoelectron Method

    NASA Astrophysics Data System (ADS)

    Gao, Hong

    The tunable vacuum ultraviolet (VUV) laser generated through the two-photon resonance-enhanced four-wave mixing scheme is combined with the newly developed time-slice velocity map imaging photoion method to study the photodissociation of small molecules in the VUV region, and with the velocity map imaging photoelectron method to study the photoionization of free radicals. The photodissociation dynamics of NO in the energy region around 13.5 eV has been investigated. Branching ratios of the three lowest dissociation channels of 12C 16O that produce C(3P) + O(3P), C( 1D) + O(3P) and C(3P) + O(1D) are measured for the first time in the VUV region from 102,500 cm-1 to 110,500 cm-1, valuable information of the dissociation dynamics for this prototype system has been deduced. We demonstrated an experiment that has two independently tunable VUV lasers and a time-slice velocity map imaging setup, this provides us a global way to perform systematic state-selected photodissociation of small molecules via state-selected detection of the atomic products in the VUV region. The velocity map imaging photoelectron method was successfully used to obtain the photoelectron spectrum of the propargyl radical (C3H3) via a single VUV photoionization process. The propargyl radical is generated by the 193 nm laser photodissociation of the precursor C3H3Cl. This is the first time that the velocity map imaging photoelectron method is used to get the photoelectron spectra of free radicals, indicating that it is a powerful technique for studying the photoionization of free radicals which are always hard to be produced with high enough number densities for spectroscopic studies. This dissertation is mainly based on the following peer-reviewed journal articles: 1. Hong Gao, Yang Pan, Lei Yang, Jingang Zhou, C. Y. Ng and William M. Jackson. "Time-slice velocity-map ion imaging studies of the Photodissociation of NO in the vacuum ultraviolet region", the Journal of Chemical Physics, 136, 134302

  4. Photodissociation of PbI2 in the ultraviolet: analysis of the A rightarrow X band of PbI

    NASA Astrophysics Data System (ADS)

    Rodriguez, G.; Herring, C. M.; Fraser, R. D.; Eden, J. G.

    1996-07-01

    Emission and absorption studies of lead moniodide (PbI) have been carried out by photodissociation of PbI2 vapor at one of several wavelengths (193, 248, 266, 308, and 351 nm) in the ultraviolet. Strong emission on the A \\rightarrow X2 Pi 1/2 band (14400-22800 cm -1 ; 440 \\similar-or-less lambda \\similar-or-less 695 nm) occurs when PbI2 is photodissociated at 248 or 266 nm. Also, absorption bands attributed to the B \\leftarrow X2 Pi 1/2,3/2 , D \\leftarrow X2 Pi 1/2,3/2 , and E \\leftarrow X2 Pi 1/2,3/2 transitions of the diatomic molecule have been observed at 290 and 380, 225 and 265, and 203 and 240 nm, respectively, as have emission bands peaking at 397.6, 531.6, 582.0, 595.1, 639.7, 685.9, and 707.9 nm that appear to arise from PbI2 itself. Analysis and computer simulations of the A \\rightarrow X2 Pi 1/2 emission spectra have resulted in identifications for virtually all (>120) of the observed vibrational bandheads. Several spectroscopic constants for the A and the X2 Pi 1/2 states of PbI have been determined to be Te(A)=20659+/-130 cm-1 , omega e\\prime =132.2+/-1.0cm -1 , omega e\\prime xe\\prime =1.91+/-0.06cm -1 , omega e\\prime \\prime=160.3+/-0.6cm-1 , and omega e\\prime \\primexe \\prime\\prime=0.24+/-0.03cm -1 . Also, the difference between the equilibrium internuclear separations for the X2 Pi 1/2 and the A states has been determined to be Delta Re=0.45+/-0.05 . The spontaneous-emission lifetime for the PbI(A) state and the rate constant for quenching of this state by PbI2 (in two-body collisions) have been measured to be (94.3+/-8.8) ns and (4.3+/-0.4) \\times 10-10 cm3s -1 , respectively.

  5. 3D-PDR: Three-dimensional photodissociation region code

    NASA Astrophysics Data System (ADS)

    Bisbas, T. G.; Bell, T. A.; Viti, S.; Yates, J.; Barlow, M. J.

    2018-03-01

    3D-PDR is a three-dimensional photodissociation region code written in Fortran. It uses the Sundials package (written in C) to solve the set of ordinary differential equations and it is the successor of the one-dimensional PDR code UCL_PDR (ascl:1303.004). Using the HEALpix ray-tracing scheme (ascl:1107.018), 3D-PDR solves a three-dimensional escape probability routine and evaluates the attenuation of the far-ultraviolet radiation in the PDR and the propagation of FIR/submm emission lines out of the PDR. The code is parallelized (OpenMP) and can be applied to 1D and 3D problems.

  6. The Ups and Downs of Repeated Cleavage and Internal Fragment Production in Top-Down Proteomics.

    PubMed

    Lyon, Yana A; Riggs, Dylan; Fornelli, Luca; Compton, Philip D; Julian, Ryan R

    2018-01-01

    Analysis of whole proteins by mass spectrometry, or top-down proteomics, has several advantages over methods relying on proteolysis. For example, proteoforms can be unambiguously identified and examined. However, from a gas-phase ion-chemistry perspective, proteins are enormous molecules that present novel challenges relative to peptide analysis. Herein, the statistics of cleaving the peptide backbone multiple times are examined to evaluate the inherent propensity for generating internal versus terminal ions. The raw statistics reveal an inherent bias favoring production of terminal ions, which holds true regardless of protein size. Importantly, even if the full suite of internal ions is generated by statistical dissociation, terminal ions are predicted to account for at least 50% of the total ion current, regardless of protein size, if there are three backbone dissociations or fewer. Top-down analysis should therefore be a viable approach for examining proteins of significant size. Comparison of the purely statistical analysis with actual top-down data derived from ultraviolet photodissociation (UVPD) and higher-energy collisional dissociation (HCD) reveals that terminal ions account for much of the total ion current in both experiments. Terminal ion production is more favored in UVPD relative to HCD, which is likely due to differences in the mechanisms controlling fragmentation. Importantly, internal ions are not found to dominate from either the theoretical or experimental point of view. Graphical abstract ᅟ.

  7. The Ups and Downs of Repeated Cleavage and Internal Fragment Production in Top-Down Proteomics

    NASA Astrophysics Data System (ADS)

    Lyon, Yana A.; Riggs, Dylan; Fornelli, Luca; Compton, Philip D.; Julian, Ryan R.

    2018-01-01

    Analysis of whole proteins by mass spectrometry, or top-down proteomics, has several advantages over methods relying on proteolysis. For example, proteoforms can be unambiguously identified and examined. However, from a gas-phase ion-chemistry perspective, proteins are enormous molecules that present novel challenges relative to peptide analysis. Herein, the statistics of cleaving the peptide backbone multiple times are examined to evaluate the inherent propensity for generating internal versus terminal ions. The raw statistics reveal an inherent bias favoring production of terminal ions, which holds true regardless of protein size. Importantly, even if the full suite of internal ions is generated by statistical dissociation, terminal ions are predicted to account for at least 50% of the total ion current, regardless of protein size, if there are three backbone dissociations or fewer. Top-down analysis should therefore be a viable approach for examining proteins of significant size. Comparison of the purely statistical analysis with actual top-down data derived from ultraviolet photodissociation (UVPD) and higher-energy collisional dissociation (HCD) reveals that terminal ions account for much of the total ion current in both experiments. Terminal ion production is more favored in UVPD relative to HCD, which is likely due to differences in the mechanisms controlling fragmentation. Importantly, internal ions are not found to dominate from either the theoretical or experimental point of view. [Figure not available: see fulltext.

  8. Sequential water molecule binding enthalpies for aqueous nanodrops containing a mono-, di- or trivalent ion and between 20 and 500 water molecules† †Electronic supplementary information (ESI) available: Detailed description of the experimental and computational modeling methods. Isolation, BIRD and UVPD sequence for [Ru(NH3)6]3+·(H2O)169–171, nanoESI spectra for 2+ and 3+ ions. Detailed description of the isotope distribution simulation program. Comparison between experimental and simulated 1+, 2+ and 3+ ion isotope distributions. Wavelength dependence of the deduced sequential binding enthalpies. Comparison of experimental UVPD binding enthalpies to the liquid drop model at different temperatures. Complete list of binding enthalpies and average number of water molecules lost upon UVPD. See DOI: 10.1039/c6sc04957e Click here for additional data file.

    PubMed Central

    Heiles, Sven; Cooper, Richard J.; DiTucci, Matthew J.

    2017-01-01

    Sequential water molecule binding enthalpies, ΔH n,n–1, are important for a detailed understanding of competitive interactions between ions, water and solute molecules, and how these interactions affect physical properties of ion-containing nanodrops that are important in aerosol chemistry. Water molecule binding enthalpies have been measured for small clusters of many different ions, but these values for ion-containing nanodrops containing more than 20 water molecules are scarce. Here, ΔH n,n–1 values are deduced from high-precision ultraviolet photodissociation (UVPD) measurements as a function of ion identity, charge state and cluster size between 20–500 water molecules and for ions with +1, +2 and +3 charges. The ΔH n,n–1 values are obtained from the number of water molecules lost upon photoexcitation at a known wavelength, and modeling of the release of energy into the translational, rotational and vibrational motions of the products. The ΔH n,n–1 values range from 36.82 to 50.21 kJ mol–1. For clusters containing more than ∼250 water molecules, the binding enthalpies are between the bulk heat of vaporization (44.8 kJ mol–1) and the sublimation enthalpy of bulk ice (51.0 kJ mol–1). These values depend on ion charge state for clusters with fewer than 150 water molecules, but there is a negligible dependence at larger size. There is a minimum in the ΔH n,n–1 values that depends on the cluster size and ion charge state, which can be attributed to the competing effects of ion solvation and surface energy. The experimental ΔH n,n–1 values can be fit to the Thomson liquid drop model (TLDM) using bulk ice parameters. By optimizing the surface tension and temperature change of the logarithmic partial pressure for the TLDM, the experimental sequential water molecule binding enthalpies can be fit with an accuracy of ±3.3 kJ mol–1 over the entire range of cluster sizes. PMID:28451364

  9. The early faint sun paradox: organic shielding of ultraviolet-labile greenhouse gases

    NASA Technical Reports Server (NTRS)

    Sagan, C.; Chyba, C.

    1997-01-01

    Atmospheric mixing ratios of approximately 10(-5 +/- 1) for ammonia on the early Earth would have been sufficient, through the resulting greenhouse warming, to counteract the temperature effects of the faint early sun. One argument against such model atmospheres has been the short time scale for ammonia photodissociation by solar ultraviolet light. Here it is shown that ultraviolet absorption by steady-state amounts of high-altitude organic solids produced from methane photolysis may have shielded ammonia sufficiently that ammonia resupply rates were able to maintain surface temperatures above freezing.

  10. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

    NASA Astrophysics Data System (ADS)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

    2018-01-01

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

  11. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

    PubMed

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

    2018-01-16

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

  12. Photoabsorption and photodissociation of molecules important in the interstellar medium

    NASA Technical Reports Server (NTRS)

    Lee, L. C.

    1985-01-01

    The photoabsorption and photodissociation cross sections of several interstellar molecules and radicals in the 105 to 210 nm region were measured. The research results accomplished are briefly described. Photoabsorption cross sections of OD and CN, and photoabsorption and photodissociation of HCl, and photoabsorption and photodissociation cross sections of CH3OH are discussed.

  13. Photodissociation Studies of Polyatomic Free Radicals

    DTIC Science & Technology

    1993-08-01

    photofragment, that varies with vibrational level, and appears to have a strong J dependence. We are currently in the process of modelling these effects, as well...have also begun to study the photodissociation dynamics of thionyl halides, The photodissociation of thionyl chloride (C12SO) is of interest as a model ...concerted three-body fragmentation mechanism as the primary dissociation channel. A Franck- Condon/golden rule model elucidates the geometry prior to

  14. Structural Characterization and Absolute Quantification of Microcystin Peptides Using Collision-Induced and Ultraviolet Photo-Dissociation Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Attard, Troy J.; Carter, Melissa D.; Fang, Mengxuan; Johnson, Rudolph C.; Reid, Gavin E.

    2018-05-01

    Microcystin (MC) peptides produced by cyanobacteria pose a hepatotoxic threat to human health upon ingestion from contaminated drinking water. While rapid MC identification and quantification in contaminated body fluids or tissue samples is important for patient treatment and outcomes, conventional immunoassay-based measurement strategies typically lack the specificity required for unambiguous determination of specific MC variants, whose toxicity can significantly vary depending on their structures. Furthermore, the unambiguous identification and accurate quantitation of MC variants using tandem mass spectrometry (MS/MS)-based methods can be limited due to a current lack of appropriate stable isotope-labeled internal standards. To address these limitations, we have systematically examined here the sequence and charge state dependence to the formation and absolute abundance of both "global" and "variant-specific" product ions from representative MC-LR, MC-YR, MC-RR, and MC-LA peptides, using higher-energy collisional dissociation (HCD)-MS/MS, ion-trap collision-induced dissociation (CID)-MS/MS and CID-MS3, and 193 nm ultraviolet photodissociation (UPVD)-MS/MS. HCD-MS/MS was found to provide the greatest detection sensitivity for both global and variant-specific product ions in each of the MC variants, except for MC-YR where a variant-specific product uniquely formed via UPVD-MS/MS was observed with the greatest absolute abundance. A simple methodology for the preparation and characterization of 18O-stable isotope-labeled MC reference materials for use as internal standards was also developed. Finally, we have demonstrated the applicability of the methods developed herein for absolute quantification of MC-LR present in human urine samples, using capillary scale liquid chromatography coupled with ultra-high resolution / accurate mass spectrometry and HCD-MS/MS.

  15. High-Resolution Photoionization, Photoelectron and Photodissociation Studies. Determination of Accurate Energetic and Spectroscopic Database for Combustion Radicals and Molecules

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ng, Cheuk-Yiu

    2016-04-25

    The main goal of this research program was to obtain accurate thermochemical and spectroscopic data, such as ionization energies (IEs), 0 K bond dissociation energies, 0 K heats of formation, and spectroscopic constants for radicals and molecules and their ions of relevance to combustion chemistry. Two unique, generally applicable vacuum ultraviolet (VUV) laser photoion-photoelectron apparatuses have been developed in our group, which have used for high-resolution photoionization, photoelectron, and photodissociation studies for many small molecules of combustion relevance.

  16. ROVIBRATIONALLY RESOLVED DIRECT PHOTODISSOCIATION THROUGH THE LYMAN AND WERNER TRANSITIONS OF H{sub 2} FOR FUV/X-RAY-IRRADIATED ENVIRONMENTS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gay, C. D.; Porter, R. L.; Stancil, P. C.

    Using ab initio potential curves and dipole transition moments, cross-section calculations were performed for the direct continuum photodissociation of H{sub 2} through the B{sup 1}{Sigma}{sup +}{sub u} <- X{sup 1}{Sigma}{sup +}{sub g} (Lyman) and C{sup 1}{Pi}{sub u} <- X{sup 1}{Sigma}{sup +}{sub g} (Werner) transitions. Partial cross-sections were obtained for wavelengths from 100 A to the dissociation threshold between the upper electronic state and each of the 301 bound rovibrational levels v''J'' within the ground electronic state. The resulting cross-sections are incorporated into three representative classes of interstellar gas models: diffuse clouds, photon-dominated regions, and X-ray-dominated regions (XDRs). The models, whichmore » used the CLOUDY plasma/molecular spectra simulation code, demonstrate that direct photodissociation is comparable to fluorescent dissociation (or spontaneous radiative dissociation, the Solomon process) as an H{sub 2} destruction mechanism in intense far-ultraviolet or X-ray-irradiated gas. In particular, changes in H{sub 2} rotational column densities are found to be as large as 20% in the XDR model with the inclusion of direct photodissociation. The photodestruction rate from some high-lying rovibrational levels can be enhanced by pumping from H Ly{beta} due to a wavelength coincidence with cross-section resonances resulting from quasi-bound levels of the upper electronic states. Given the relatively large size of the photodissociation data set, a strategy is described to create truncated, but reliable, cross-section data consistent with the wavelength resolving power of typical observations.« less

  17. Photodissociation Studies of Metal-Containing Clusters and Complexes

    NASA Astrophysics Data System (ADS)

    Pilgrim, Jeffrey Scott

    1995-01-01

    There have been two major areas of investigation for researchers working with laser ablation in molecular beams. The first area is the study of weakly-bound complexes. These complexes are bound by electrostatic interactions. In the present study the weakly bound interactions of the rare gases with the magnesium ion are investigated with electronic spectroscopy. The second major area is the study of metal and metal-containing clusters. Examples of previous investigations are the alkali metal clusters and the fullerenes. The present investigation is on metal -carbon clusters. The so-called metallo-carbohedrenes and metal-carbon nanocrystals are studied. Resonance enhanced photodissociation spectroscopy is used to obtain electronic excitation spectra of the Mg^+-rare gas species in the ultraviolet region. This investigation is facilitated by a reflectron time-of-flight mass spectrometer. The interaction of the rare gas with the metal ion is attributed to a "solvation" of the atomic ion transition. Simple bonding arguments predict that the excited state is more bound than the ground state for these complexes. This will result in a shift of the complex vibronic origin to lower energy from the atomic ion transition. This is exactly what is observed in the experiment with progressively larger shifts for the heavier rare gases. The electronic excitation spectra allow the vibrational frequencies and anharmonicities for these complexes to be obtained for the excited state. In turn, the excited state bond dissociation energies can be determined. Finally, conservation of energy allows calculation of the ground state bond dissociation energies. In the metal-carbon systems the stability of the metallo-carbohedrene, met-car, stoichiometry is shown to extend into the transition period at least to the iron group. Photodissociation with a 532 nm laser causes a loss of metal atoms for met-cars formed with first row transition metals and a loss of metal-carbon units for met

  18. Photodissociation of HBr/LiF(001): A quantum mechanical model

    NASA Technical Reports Server (NTRS)

    Seideman, Tamar

    1993-01-01

    The photodissociation dynamics of HBr adsorbed on a LiF(001) surface is studied using time-independent quantum mechanics. The photodissociation lineshape and the Br(P(sub 1/2)-2)/Br(P(sub 3/2)-2) yield ratio are computed and compared with the corresponding quantities for gas phase photodissociation. The angular distribution of the hydrogen photofragments following excitation of adsorbed HBr is computed and found to agree qualitatively with experimental data. The effect of polarization of the photon is illustrated and discussed. The field polarization is found to affect significantly the magnitude of the photodissociation signal but not the angular dependence of the photofragment distribution, in agreement with experiment and in accord with expectations for a strongly aligned adsorbed phase.

  19. Photodissociation of HBr/LiF(001) - A quantum mechanical model

    NASA Technical Reports Server (NTRS)

    Seideman, Tamar

    1993-01-01

    The photodissociation dynamics of HBr adsorbed on an LiF(001) surface is studied using time-independent quantum mechanics. The photodissociation line shape and the Br(2P(1/2))/Br(2P(3/2)) yield ratio are computed and compared with the corresponding quantities for gas phase photodissociation. The angular distribution of the hydrogen photofragments following excitation of adsorbed HBr is computed and found to agree qualitatively with experimental data. The effect of polarization of the photon is illustrated and discussed. We find the field polarization to affect significantly the magnitude of the photodissociation signal but not the angular dependence of the photofragment distribution, in agreement with experiment and in accord with expectations for a strongly aligned adsorbed phase.

  20. Time-dependent infrared emission following photodissociation of nitromethane and chloropicrin.

    PubMed

    Wade, Elisabeth A; Reak, Kristina E; Li, Sissi L; Clegg, Samuel M; Zou, Peng; Osborn, David L

    2006-04-06

    Nitromethane (CH(3)NO(2)) and its chlorinated analogue, chloropicrin (CCl(3)NO(2)), were photolyzed at 193, 248, and 266 nm, and the products were observed by time-dependent Fourier transform infrared emission spectroscopy. At 193 and 248 nm, the primary photodissociation pathway for nitromethane was cleavage of the C-N bond to produce CH(3) + NO(2)(A (2)B(2)). At 266 nm, weak emission was observed following photodissociation of nitromethane, but an infrared spectrum could not be obtained. The photodissociation of chloropicrin at 193 nm produced the analogous product channel CCl(3) + NO(2)(A (2)B(2)) in addition to several other product channels. At 248 and 266 nm, only CCl(3) + NO(2)(A (2)B(2)) was observed. The production of phosgene (CCl(2)O) from chloropicrin photodissociation was not observed in this study.

  1. Near ultraviolet photodissociation spectroscopy of Mn+(H2O) and Mn+(D2O)

    NASA Astrophysics Data System (ADS)

    Pearson, Wright L.; Copeland, Christopher; Kocak, Abdulkadir; Sallese, Zachary; Metz, Ricardo B.

    2014-11-01

    The electronic spectra of Mn+(H2O) and Mn+(D2O) have been measured from 30 000 to 35 000 cm-1 using photodissociation spectroscopy. Transitions are observed from the 7A1 ground state in which the Mn+ is in a 3d54s1 electronic configuration, to the 7B2 (3d54py) and 7B1 (3d54px) excited states with T0 = 30 210 and 32 274 cm-1, respectively. Each electronic transition has partially resolved rotational and extensive vibrational structure with an extended progression in the metal-ligand stretch at a frequency of ˜450 cm-1. There are also progressions in the in-plane bend in the 7B2 state, due to vibronic coupling, and the out-of-plane bend in the 7B1 state, where the calculation illustrates that this state is slightly non-planar. Electronic structure computations at the CCSD(T)/aug-cc-pVTZ and TD-DFT B3LYP/6-311++G(3df,3pd) level are also used to characterize the ground and excited states, respectively. These calculations predict a ground state Mn-O bond length of 2.18 Å. Analysis of the experimentally observed vibrational intensities reveals that this bond length decreases by 0.15 ± 0.015 Å and 0.14 ± 0.01 Å in the excited states. The behavior is accounted for by the less repulsive px and py orbitals causing the Mn+ to interact more strongly with water in the excited states than the ground state. The result is a decrease in the Mn-O bond length, along with an increase in the H-O-H angle. The spectra have well resolved K rotational structure. Fitting this structure gives spin-rotation constants ɛaa″ = -3 ± 1 cm-1 for the ground state and ɛaa' = 0.5 ± 0.5 cm-1 and ɛaa' = -4.2 ± 0.7 cm-1 for the first and second excited states, respectively, and A' = 12.8 ± 0.7 cm-1 for the first excited state. Vibrationally mediated photodissociation studies determine the O-H antisymmetric stretching frequency in the ground electronic state to be 3658 cm-1.

  2. The near ultraviolet photodissociation dynamics of 2- and 3-substituted thiophenols: Geometric vs. electronic structure effects

    NASA Astrophysics Data System (ADS)

    Marchetti, Barbara; Karsili, Tolga N. V.; Cipriani, Maicol; Hansen, Christopher S.; Ashfold, Michael N. R.

    2017-07-01

    The near ultraviolet spectroscopy and photodissociation dynamics of two families of asymmetrically substituted thiophenols (2- and 3-YPhSH, with Y = F and Me) have been investigated experimentally (by H (Rydberg) atom photofragment translational spectroscopy) and by ab initio electronic structure calculations. Photoexcitation in all cases populates the 11ππ* and/or 11πσ* excited states and results in S-H bond fission. Analyses of the experimentally obtained total kinetic energy release (TKER) spectra yield the respective parent S-H bond strengths, estimates of ΔE(A ˜ -X ˜ ), the energy splitting between the ground (X ˜ ) and first excited (A ˜ ) states of the resulting 2-(3-)YPhS radicals, and reveal a clear propensity for excitation of the C-S in-plane bending vibration in the radical products. The companion theory highlights roles for both geometric (e.g., steric effects and intramolecular H-bonding) and electronic (i.e., π (resonance) and σ (inductive)) effects in determining the respective parent minimum energy geometries, and the observed substituent and position-dependent trends in S-H bond strength and ΔE(A ˜ -X ˜ ). 2-FPhSH shows some clear spectroscopic and photophysical differences. Intramolecular H-bonding ensures that most 2-FPhSH molecules exist as the syn rotamer, for which the electronic structure calculations return a substantial barrier to tunnelling from the photoexcited 11ππ* state to the 11πσ* continuum. The 11ππ* ← S0 excitation spectrum of syn-2-FPhSH thus exhibits resolved vibronic structure, enabling photolysis studies with a greater parent state selectivity. Structure apparent in the TKER spectrum of the H + 2-FPhS products formed when exciting at the 11ππ* ← S0 origin is interpreted by assuming unintended photoexcitation of an overlapping resonance associated with syn-2-FPhSH(v33 = 1) molecules. The present data offer tantalising hints that such out-of-plane motion influences non-adiabatic coupling in the vicinity

  3. Photodissociation of ethylbenzene and n-propylbenzene in a molecular beam

    NASA Astrophysics Data System (ADS)

    Huang, Cheng-Liang; Jiang, Jyh-Chiang; Lee, Yuan T.; Ni, Chi-Kung

    2002-10-01

    The photodissociation of jet-cooled ethylbenzene and n-propylbenzene at both 193 and 248 nm was studied using vacuum ultraviolet photoionization/multimass ion imaging techniques. The photofragment translational energy distributions from both the molecules obtained at 193 nm show that the probability of portioning energy to product translational energy decreases monotonically with increasing translational energy. They indicate that the dissociation occurs from the ground electronic state. However, the photofragment translational energy distributions from both molecules obtained at 248 nm contain a fast and a slow component. 75% of ethylbenzene and 80% of n-propylbenzene following the 248 nm photoexcitation dissociate from electronic excited state, resulting in the fast component. The remaining 25% of ethylbenzene and 20% of n-propylbenzene dissociate through the ground electronic state, giving rise to the slow component. A comparison with an ab initio calculation suggests that the dissociation from the first triplet state corresponds to the fast component in translational energy distribution.

  4. Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang Chunfan; Su Hongmei; Sun Xuezhong

    2012-05-28

    Time-resolved infrared (TR-IR) absorption spectroscopy in both the femtosecond and nanosecond time domain has been applied to examine the photolysis of benzoic acid in acetonitrile solution following either 267 nm or 193 nm excitation. By combining the ultrafast and nanosecond TR-IR measurements, both the excited states and the photofragments have been detected and key mechanistic insights were obtained. We show that the solvent interaction modifies the excited state relaxation pathways and thus the population dynamics, leading to different photolysis behavior in solution from that observed in the gas phase. Vibrational energy transfer to solvents dissipates excitation energy efficiently, suppressing themore » photodissociation and depopulating the excited S{sub 2} or S{sub 3} state molecules to the lowest T{sub 1} state with a rate of {approx}2.5 ps after a delayed onset of {approx}3.7 ps. Photolysis of benzoic acid using 267 nm excitation is dominated by the formation of the T{sub 1} excited state and no photofragments could be detected. The results from TR-IR experiments using higher energy of 193 nm indicate that photodissociation proceeds more rapidly than the vibrational energy transfer to solvents and C-C bond fission becomes the dominant relaxation pathway in these experiments as featured by the prominent observation of the COOH photofragments and negligible yield of the T{sub 1} excited state. The measured ultrafast formation of T{sub 1} excited state supports the existence of the surface intersections of S{sub 2}/S{sub 1}, S{sub 2}/T{sub 2}, and S{sub 1}/T{sub 1}/T{sub 2}, and the large T{sub 1} quantum yield of {approx}0.65 indicates the importance of the excited state depopulation to triplet manifold as the key factor affecting the photophysical and photochemical behavior of the monomeric benzoic acid.« less

  5. Photodissociation of CS from Excited Rovibrational Levels

    NASA Astrophysics Data System (ADS)

    Pattillo, R. J.; Cieszewski, R.; Stancil, P. C.; Forrey, R. C.; Babb, J. F.; McCann, J. F.; McLaughlin, B. M.

    2018-05-01

    Accurate photodissociation cross sections have been computed for transitions from the X 1Σ+ ground electronic state of CS to six low-lying excited electronic states. New ab initio potential curves and transition dipole moment functions have been obtained for these computations using the multi-reference configuration interaction approach with the Davidson correction (MRCI+Q) and aug-cc-pV6Z basis sets. State-resolved cross sections have been computed for transitions from nearly the full range of rovibrational levels of the X 1Σ+ state and for photon wavelengths ranging from 500 Å to threshold. Destruction of CS via predissociation in highly excited electronic states originating from the rovibrational ground state is found to be unimportant. Photodissociation cross sections are presented for temperatures in the range between 1000 and 10,000 K, where a Boltzmann distribution of initial rovibrational levels is assumed. Applications of the current computations to various astrophysical environments are briefly discussed focusing on photodissociation rates due to the standard interstellar and blackbody radiation fields.

  6. Photodissociation dynamics and spectroscopy of free radical combustion intermediates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Osborn, David Lewis

    1996-12-01

    The photodissociation spectroscopy and dynamics of free radicals is studied by the technique of fast beam photofragment translational spectroscopy. Photodetachment of internally cold, mass-selected negative ions produces a clean source of radicals, which are subsequently dissociated and detected. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states of the radical. In addition, the photodissociation dynamics, product branching ratios, and bond energies are probed at fixed photon energies by measuring the translational energy, P(E T), and angular distribution of the recoiling fragments using a time- and position-sensitive detector. Ab initio calculationsmore » are combined with dynamical and statistical models to interpret the observed data. The photodissociation of three prototypical hydrocarbon combustion intermediates forms the core of this work.« less

  7. Photodissociation of the CH3Cl/+/ and N2O/+/ cations.

    NASA Technical Reports Server (NTRS)

    Dunbar, R. C.

    1971-01-01

    Use of the ion cyclotron resonance (icr) technique to observe the photodissociation of the cations CH3Cl(+) and N2O(+) in the gas phase. Ions were trapped in the icr cell for periods of the order of seconds, which permitted the photodissociation process to be observed with wavelength-selected light. A cyclotron resonance ejection technique was employed to show that CH3Cl(+) ions were being dissociated rather than the CH3ClH(+) ions which were also present. The photodissociation cross section for N2O(+) was found to be without strong wavelength dependence between 4000 and 6500 A. The cross section for CH3Cl(+) showed a large peak at 3150 A. Possible assignments of this peak are considered, and it is suggested that a photodissociation occurs through an ion excitation involving a change in occupation of the bonding or antibonding orbitals of the C-Cl bond.

  8. Photodissociation of nitromethane cluster anions.

    PubMed

    Goebbert, Daniel J; Khuseynov, Dmitry; Sanov, Andrei

    2010-08-28

    Three types of anionic fragments are observed in the photodissociation of nitromethane cluster anions, (CH(3)NO(2))(n)(-), n=1-6, at 355 nm: NO(2)(-)(CH(3)NO(2))(k), (CH(3)NO(2))(k)(-), and OH(-) (kphotodissociation of CH(3)NO(2)(-) requires lower energy photons because the photochemically active electron occupies a high energy pi* orbital (which is vacant in the neutral). Although the electronic states in the photodissociation of CH(3)NO(2) and CH(3)NO(2)(-) are different, the major fragments, CH(3)+NO(2) and CH(3)+NO(2)(-), respectively, both form via C-N bond cleavage.

  9. The efficiency of photodissociation for molecules in interstellar ices

    NASA Astrophysics Data System (ADS)

    Kalvāns, J.

    2018-05-01

    Processing by interstellar photons affects the composition of the icy mantles on interstellar grains. The rate of photodissociation in solids differs from that of molecules in the gas phase. The aim of this work was to determine an average, general ratio between photodissociation coefficients for molecules in ice and gas. A 1D astrochemical model was utilized to simulate the chemical composition for a line of sight through a collapsing interstellar cloud core, whose interstellar extinction changes with time. At different extinctions, the calculated column densities of icy carbon oxides and ammonia (relative to water ice) were compared to observations. The latter were taken from literature data of background stars sampling ices in molecular clouds. The best-fit value for the solid/gas photodissociation coefficient ratio was found to be ≈0.3. In other words, gas-phase photodissociation rate coefficients have to be reduced by a factor of 0.3 before applying them to icy species. A crucial part of the model is a proper inclusion of cosmic-ray induced desorption. Observations sampling gas with total extinctions in excess of ≈22 mag were found to be uncorrelated to modelling results, possibly because of grains being covered with non-polar molecules.

  10. Control of Ultracold Photodissociation with Magnetic Fields

    NASA Astrophysics Data System (ADS)

    McDonald, M.; Majewska, I.; Lee, C.-H.; Kondov, S. S.; McGuyer, B. H.; Moszynski, R.; Zelevinsky, T.

    2018-01-01

    Photodissociation of a molecule produces a spatial distribution of photofragments determined by the molecular structure and the characteristics of the dissociating light. Performing this basic reaction at ultracold temperatures allows its quantum mechanical features to dominate. In this regime, weak applied fields can be used to control the reaction. Here, we photodissociate ultracold diatomic strontium in magnetic fields below 10 G and observe striking changes in photofragment angular distributions. The observations are in excellent agreement with a multichannel quantum chemistry model that includes nonadiabatic effects and predicts strong mixing of partial waves in the photofragment energy continuum. The experiment is enabled by precise quantum-state control of the molecules.

  11. The intriguing near-ultraviolet photochemistry of H 2Te

    NASA Astrophysics Data System (ADS)

    Underwood, J.; Chastaing, D.; Lee, S.; Boothe, P.; Flood, T. C.; Wittig, C.

    2002-08-01

    The ultraviolet absorption spectrum of H 2Te has a long wavelength tail that extends to 400 nm. Photodissociation at 355 nm yields TeH( 2Π 1/2) selectively relative to the 2Π 3/2 ground state; the transition moments for these channels lie in, and perpendicular to, the molecular plane, respectively. Vibrational structure in the region 380-400 nm is consistent with a shallow well in the adiabat leading to 2Π 1/2, akin to the one in HI leading to I( 2P 1/2). These effects have no counterparts with the light Group 6A dihydrides.

  12. Ultrafast Photodissociation Dynamics of Nitromethane.

    PubMed

    Nelson, Tammie; Bjorgaard, Josiah; Greenfield, Margo; Bolme, Cindy; Brown, Katie; McGrane, Shawn; Scharff, R Jason; Tretiak, Sergei

    2016-02-04

    Nitromethane (NM), a high explosive (HE) with low sensitivity, is known to undergo photolysis upon ultraviolet (UV) irradiation. The optical transparency, homogeneity, and extensive study of NM make it an ideal system for studying photodissociation mechanisms in conventional HE materials. The photochemical processes involved in the decomposition of NM could be applied to the future design of controllable photoactive HE materials. In this study, the photodecomposition of NM from the nπ* state excited at 266 nm is being investigated on the femtosecond time scale. UV femtosecond transient absorption (TA) spectroscopy and excited state femtosecond stimulated Raman spectroscopy (FSRS) are combined with nonadiabatic excited state molecular dynamics (NA-ESMD) simulations to provide a unified picture of NM photodecomposition. The FSRS spectrum of the photoproduct exhibits peaks in the NO2 region and slightly shifted C-N vibrational peaks pointing to methyl nitrite formation as the dominant photoproduct. A total photolysis quantum yield of 0.27 and an nπ* state lifetime of ∼20 fs were predicted from NA-ESMD simulations. Predicted time scales revealed that NO2 dissociation occurs in 81 ± 4 fs and methyl nitrite formation is much slower having a time scale of 452 ± 9 fs corresponding to the excited state absorption feature with a decay of 480 ± 17 fs observed in the TA spectrum. Although simulations predict C-N bond cleavage as the primary photochemical process, the relative time scales are consistent with isomerization occurring via NO2 dissociation and subsequent rebinding of the methyl radical and nitrogen dioxide.

  13. Does photodissociation of molecular oxygen from myoglobin and hemoglobin yield singlet oxygen?

    PubMed

    Lepeshkevich, Sergei V; Stasheuski, Alexander S; Parkhats, Marina V; Galievsky, Victor A; Dzhagarov, Boris M

    2013-03-05

    Time-resolved luminescence measurements in the near-infrared region indicate that photodissociation of molecular oxygen from myoglobin and hemoglobin does not produce detectable quantities of singlet oxygen. A simple and highly sensitive method of luminescence quantification is developed and used to determine the upper limit for the quantum yield of singlet oxygen production. The proposed method was preliminarily evaluated using model data sets and confirmed with experimental data for aqueous solutions of 5,10,15,20-tetrakis(4-N-methylpyridyl) porphyrin. A general procedure for error estimation is suggested. The method is shown to provide a determination of the integral luminescence intensity in a wide range of values even for kinetics with extremely low signal-to-noise ratio. The present experimental data do not deny the possibility of singlet oxygen generation during the photodissociation of molecular oxygen from myoglobin and hemoglobin. However, the photodissociation is not efficient to yield singlet oxygen escaped from the proteins into the surrounding medium. The upper limits for the quantum yields of singlet oxygen production in the surrounding medium after the photodissociation for oxyhemoglobin and oxymyoglobin do not exceed 3.4×10(-3) and 2.3×10(-3), respectively. On the average, no more than one molecule of singlet oxygen from every hundred photodissociated oxygen molecules can succeed in escaping from the protein matrix. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. The Extreme-ultraviolet Emission from Sun-grazing Comets

    NASA Technical Reports Server (NTRS)

    Bryans, Paul; Pesnell, William D.

    2012-01-01

    The Atmospheric Imaging Assembly (AIA) on the Solar Dynamics Observatory has observed two Sun-grazing comets as they passed through the solar atmosphere. Both passages resulted in a measurable enhancement of extreme-ultraviolet (EUV) radiance in several of the AIA bandpasses.We explain this EUV emission by considering the evolution of the cometary atmosphere as it interacts with the ambient solar atmosphere. Molecules in the comet rapidly sublimate as it approaches the Sun. They are then photodissociated by the solar radiation field to create atomic species. Subsequent ionization of these atoms produces a higher abundance of ions than normally present in the corona and results in EUV emission in the wavelength ranges of the AIA telescope passbands.

  15. Photodissociable dimer reduction products of 2-thiopyrimidine derivatives.

    PubMed Central

    Wrona, M; Giziewicz, J; Shugar, D

    1975-01-01

    Both 4,6-dimethyl-2-thipyrimidine and its 1-methyl derivative undergo polarographic reduction in aqueous medium, via a 1e/1H+ reduction to a free radical which rapidly dimerizes to products isolates and identified as 4,4'-bis-(4,6-dimethyl-3,4-dihydropyrimidin-2-thione) and the corresponding 1-methyl dimer. The dimers may be oxidized electrolytically to regenerate the parent monomers. Both dimers also undergo photodissociation to quantitatively regenerate the parent monomers, in high quantum yield, 0.23 and 0.35 M/Einstein. The correlation between electrochemical and photochemical reductions of 2-thiopyrimidines are discussed, as well as the significance of the dimer photodissociation reactions in relation to nucleic acid photochemistry. PMID:28516

  16. Photodissociation of HCN and HNC isomers in the 7-10 eV energy range

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chenel, Aurelie; Roncero, Octavio, E-mail: octavio.roncero@csic.es; Aguado, Alfredo

    2016-04-14

    The ultraviolet photoabsorption spectra of the HCN and HNC isomers have been simulated in the 7-10 eV photon energy range. For this purpose, the three-dimensional adiabatic potential energy surfaces of the 7 lowest electronic states, and the corresponding transition dipole moments, have been calculated, at multireference configuration interaction level. The spectra are calculated with a quantum wave packet method on these adiabatic potential energy surfaces. The spectra for the 3 lower excited states, the dissociative electronic states, correspond essentially to predissociation peaks, most of them through tunneling on the same adiabatic state. The 3 higher electronic states are bound, hereaftermore » electronic bound states, and their spectra consist of delta lines, in the adiabatic approximation. The radiative lifetime towards the ground electronic states of these bound states has been calculated, being longer than 10 ns in all cases, much longer that the characteristic predissociation lifetimes. The spectra of HCN is compared with the available experimental and previous theoretical simulations, while in the case of HNC there are no previous studies to our knowledge. The spectrum for HNC is considerably more intense than that of HCN in the 7-10 eV photon energy range, which points to a higher photodissociation rate for HNC, compared to HCN, in astrophysical environments illuminated by ultraviolet radiation.« less

  17. Photodissociation of nitromethane cluster anions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Goebbert, Daniel J.; Khuseynov, Dmitry; Sanov, Andrei

    2010-08-28

    Three types of anionic fragments are observed in the photodissociation of nitromethane cluster anions, (CH{sub 3}NO{sub 2}){sub n}{sup -}, n=1-6, at 355 nm: NO{sub 2}{sup -}(CH{sub 3}NO{sub 2}){sub k}, (CH{sub 3}NO{sub 2}){sub k}{sup -}, and OH{sup -} (kphotodissociation of CH{sub 3}NO{sub 2}{sup -} requires lower energy photons because the photochemically active electron occupies a high energy {pi}{sup *} orbital (which is vacant in the neutral). Although the electronic states in the photodissociation of CH{sub 3}NO{sub 2} and CH{sub 3}NO{sub 2}{sup -} are different, the major fragments, CH{sub 3}+NO{sub 2} and CH{sub 3}+NO{sub 2}{sup -}, respectively, both form via C-N bond cleavage.« less

  18. Transition state region in the A-Band photodissociation of allyl iodide—A femtosecond extreme ultraviolet transient absorption study

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bhattacherjee, Aditi, E-mail: abhattacherjee@berkeley.edu, E-mail: andrewattar@berkeley.edu; Attar, Andrew R., E-mail: abhattacherjee@berkeley.edu, E-mail: andrewattar@berkeley.edu; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720

    2016-03-28

    Femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy based on a high-harmonic generation source is used to study the 266 nm induced A-band photodissociation dynamics of allyl iodide (CH{sub 2} =CHCH{sub 2}I). The photolysis of the C—I bond at this wavelength produces iodine atoms both in the ground ({sup 2}P{sub 3/2}, I) and spin-orbit excited ({sup 2}P{sub 1/2}, I*) states, with the latter as the predominant channel. Using XUV absorption at the iodine N{sub 4/5} edge (45–60 eV), the experiments constitute a direct probe of not only the long-lived atomic iodine reaction products but also the fleeting transition state region ofmore » the repulsive n{sub I}σ{sup ∗}{sub C—I} excited states. Specifically, three distinct features are identified in the XUV transient absorption spectrum at 45.3 eV, 47.4 eV, and 48.4 eV (denoted transients A, B, and C, respectively), which arise from the repulsive valence-excited nσ{sup ∗} states and project onto the high-lying core-excited states of the dissociating molecule via excitation of 4d(I) core electrons. Transients A and B originate from 4d(I) → n(I) core-to-valence transitions, whereas transient C is best assigned to a 4d(I) →σ{sup ∗}(C—I) transition. The measured differential absorbance of these new features along with the I/I* branching ratios known from the literature is used to suggest a more definitive assignment, albeit provisional, of the transients to specific dissociative states within the A-band manifold. The transients are found to peak around 55 fs–65 fs and decay completely by 145 fs–185 fs, demonstrating the ability of XUV spectroscopy to map the evolution of reactants into products in real time. The similarity in the energies of transients A and B with analogous features observed in methyl iodide [Attar et al. J. Phys. Chem. Lett. 6, 5072, (2015)] together with the new observation of transient C in the present work provides a more complete picture of the valence

  19. Advantage of spatial map ion imaging in the study of large molecule photodissociation

    NASA Astrophysics Data System (ADS)

    Lee, Chin; Lin, Yen-Cheng; Lee, Shih-Huang; Lee, Yin-Yu; Tseng, Chien-Ming; Lee, Yuan-Tseh; Ni, Chi-Kung

    2017-07-01

    The original ion imaging technique has low velocity resolution, and currently, photodissociation is mostly investigated using velocity map ion imaging. However, separating signals from the background (resulting from undissociated excited parent molecules) is difficult when velocity map ion imaging is used for the photodissociation of large molecules (number of atoms ≥ 10). In this study, we used the photodissociation of phenol at the S1 band origin as an example to demonstrate how our multimass ion imaging technique, based on modified spatial map ion imaging, can overcome this difficulty. The photofragment translational energy distribution obtained when multimass ion imaging was used differed considerably from that obtained when velocity map ion imaging and Rydberg atom tagging were used. We used conventional translational spectroscopy as a second method to further confirm the experimental results, and we conclude that data should be interpreted carefully when velocity map ion imaging or Rydberg atom tagging is used in the photodissociation of large molecules. Finally, we propose a modified velocity map ion imaging technique without the disadvantages of the current velocity map ion imaging technique.

  20. Surface chemistry in photodissociation regions

    NASA Astrophysics Data System (ADS)

    Esplugues, G. B.; Cazaux, S.; Meijerink, R.; Spaans, M.; Caselli, P.

    2016-06-01

    Context. The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Aims: Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. Methods: We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 117 chemical reactions occurring on grain surfaces covering different processes, such as adsorption, thermal desorption, chemical desorption, two-body reactions, photo processes, and cosmic-ray processes on dust grains. Results: We obtain abundances for different gas and solid species as a function of visual extinction, depending on the density and radiation field. We also analyse the rates of the formation of CO2 and H2O ices in different environments. In addition, we study how chemistry is affected by the presence/absence of ice mantles (bare dust or icy dust) and the impact of considering different desorption probabilities. Conclusions: The type of substrate (bare dust or icy dust) and the probability of desorption can significantly alter the chemistry occurring on grain surfaces, leading to differences of several orders of magnitude in the abundances of gas-phase species, such as CO, H2CO, and CH3OH. The type of substrate, together with the density and intensity of the radiation field, also determine the threshold extinction to form ices of CO2 and H2O. We also conclude that H2CO and CH3OH are mainly released into the gas phase of low, far-ultraviolet illuminated PDRs through chemical desorption upon two-body surface reactions, rather than through photodesorption.

  1. Charge-transfer photodissociation of adsorbed molecules via electron image states

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jensen, E. T.

    The 248 and 193 nm photodissociations of submonolayer quantities of CH{sub 3}Br and CH{sub 3}I adsorbed on thin layers of n-hexane indicate that the dissociation is caused by dissociative electron attachment from subvacuum level photoelectrons created in the copper substrate. The characteristics of this photodissociation-translation energy distributions and coverage dependences show that the dissociation is mediated by an image potential state which temporarily traps the photoelectrons near the n-hexane-vacuum interface, and then the charge transfers from this image state to the affinity level of a coadsorbed halomethane which then dissociates.

  2. Photoevaporation of Clumps in Photodissociation Regions

    NASA Technical Reports Server (NTRS)

    Gorti, Uma; Hollenbach, David; DeVincenzi, D. (Technical Monitor)

    2002-01-01

    We present the results of an investigation of the effects of Far Ultraviolet (FUV) radiation (6.0eV < hv < 13.6eV) from hot early type OB stars on clumps in star-forming molecular clouds. Clumps in FUV-illuminated regions (or photodissociation regions or PDRs) undergo external heating and photodissociation as they are exposed to the FUV field, resulting in a loss of cold, molecular lump mass as it is converted to warm atomic gas. The heating, if rapid, creates strong photoevaporative mass flows off the clump surfaces, and drives shocks into the clumps, compressing them to high densities. The clumps lose mass on relatively short timescales. The evolution of an individual clump is found to be sensitive to three dimensionless parameters: Nc0, the ratio of the initial column density of the clump to the column N(0) approx. 10(exp 21) cm(exp -2) of a warm FUV-heated surface region; upsilon, the ratio of the sound speed in the heated surface to that in the cold clump material: and t(FUV)t(c), the ratio of the "turn-on time" t(FUV) of the heating flux on a clump to its initial sound crossing-time t(c). The evolution also depends on whether a confining interclump medium exists, or whether the interclump region has negligible pressure, as is the case for turbulence-generated clumps. In this paper, we use spherical 1-D numerical hydrodynamic models as well as approximate analytical models to study the dependence of clump photoevaporation on the physical parameters of the clump, and to derive the dynamical evolution, mass loss rates and photoevaporative timescales of a clump for a variety of astrophysical situations. Turbulent clumps evolve so that their column densities are equal to a critical value determined by the local FUV field, and typically have short photo evaporation timescales, approx. 10(exp 4-5) years for a 1 M(solar mass) clump in a typical star-forming region (Nc0 = 10, upsilon = 10). Clumps with insufficient magnetic pressure support, and in strong FUV fields

  3. Electronic excitation energies, three-state intersections, and photodissociation mechanisms of benzaldehyde and acetophenone

    NASA Astrophysics Data System (ADS)

    Cui, Ganglong; Lu, You; Thiel, Walter

    2012-06-01

    We report a theoretical study on the electronically excited states and the mechanisms of photodissociation of C6H5CHO and C6H5COCH3. For both molecules, we find an S1/T2/T1 three-state intersection region, which allows for an efficient S1 → T1 intersystem crossing via the T2 state that acts as a relay. Consequently, T1 reactions become the major radical photodissociation channels. According to the computed energy profiles, T1 photodissociation mainly yields phenyl and formyl radicals in the case of benzaldehyde, and benzoyl and methyl radicals in the case of acetophenone, with different C-C bonds being cleaved preferentially. The computational results agree well with the available experimental data.

  4. Investigation of the excited state iodine lifetime in the photodissociation of perfluoroalkyl iodides

    NASA Technical Reports Server (NTRS)

    Cobb, Stephen H.

    1991-01-01

    An evaluation of prospective laser materials for a space-based solar pumped laser system over the past decade has resulted in the identification of the iodine photodissociation laser as that system best suited to solar-pumped high energy operation. The active medium for the solar-pumped iodine photodissociation laser is from the family of perfluoroalkyl iodides. These lasants have the general form C(n)F(2n + 1)I, often abbreviated as RI. These iodides are known to exhibit photodissociaiton of the C-I bond when irradiated by near UV photons. The focus was on the experimental determination of the lifetime of the excited iodine atom following photodissociation of C4F9I, and also to monitor fluorescence from the iodine molecule at 500 nm to determine if I2 is being produced in the process. Photodissociation is achieved using an XeCl excimer laser with an output wavelength of 308 nm. The XeCl beam is focused into the middle of a cylindrical quartz cell containing the lasant. The laser pulse is detected with a fast risetime photomultiplier tube as it exits the cell. Other aspects of the investigation are discussed.

  5. Photodissociation Spectroscopy of Anionic Transition Metal Complexes

    NASA Astrophysics Data System (ADS)

    Kaufman, Sydney Hamilton

    Transition metal complexes play an important role in many aspects of chemistry; whether in supporting biological functions, as catalysts for organic reactions, in the environment, or in industry. This thesis is comprised of gas-phase spectroscopic studies of four transition metal species with implications for many different chemical applications. Most knowledge of the target molecules in this thesis are derived from studies in the condensed phase, where the chemical environment can change molecular properties. As a result, it is difficult to gain an understanding of the intrinsic properties in solution as well as a molecular-level picture of chemical reactions that take place where many oxidation states, molecular species, and solvent interactions occur. By isolating one particular species in the gas phase, we are able to observe how each species interacts with light independent of perturbing effects of solvent and counter ions. In this thesis, we perform spectroscopic experiments on mass-selected ions in the gas phase, where we are able to gain information on intrinsic molecular properties without the influence of a condensed phase chemical environment. We employ photodissociation spectroscopy, where we mass-select a particular ionic species from solution and irradiate that molecular ion with the output of a tunable laser in the ultraviolet and visible regions. By monitoring the fragments produced, we can obtain an electronic absorption spectrum of the isolated species as well as gain insight into the photochemistry of the ions under study from the fragmentation pathways observed. We combine this method with solution absorption spectra as well as electronic structure calculations.

  6. Photodissociation of ultracold diatomic strontium molecules with quantum state control.

    PubMed

    McDonald, M; McGuyer, B H; Apfelbeck, F; Lee, C-H; Majewska, I; Moszynski, R; Zelevinsky, T

    2016-07-07

    Chemical reactions at ultracold temperatures are expected to be dominated by quantum mechanical effects. Although progress towards ultracold chemistry has been made through atomic photoassociation, Feshbach resonances and bimolecular collisions, these approaches have been limited by imperfect quantum state selectivity. In particular, attaining complete control of the ground or excited continuum quantum states has remained a challenge. Here we achieve this control using photodissociation, an approach that encodes a wealth of information in the angular distribution of outgoing fragments. By photodissociating ultracold (88)Sr2 molecules with full control of the low-energy continuum, we access the quantum regime of ultracold chemistry, observing resonant and nonresonant barrier tunnelling, matter-wave interference of reaction products and forbidden reaction pathways. Our results illustrate the failure of the traditional quasiclassical model of photodissociation and instead are accurately described by a quantum mechanical model. The experimental ability to produce well-defined quantum continuum states at low energies will enable high-precision studies of long-range molecular potentials for which accurate quantum chemistry models are unavailable, and may serve as a source of entangled states and coherent matter waves for a wide range of experiments in quantum optics.

  7. The photodissociation and chemistry of CO isotopologues: applications to interstellar clouds and circumstellar disks

    NASA Astrophysics Data System (ADS)

    Visser, R.; van Dishoeck, E. F.; Black, J. H.

    2009-08-01

    Aims: Photodissociation by UV light is an important destruction mechanism for carbon monoxide (CO) in many astrophysical environments, ranging from interstellar clouds to protoplanetary disks. The aim of this work is to gain a better understanding of the depth dependence and isotope-selective nature of this process. Methods: We present a photodissociation model based on recent spectroscopic data from the literature, which allows us to compute depth-dependent and isotope-selective photodissociation rates at higher accuracy than in previous work. The model includes self-shielding, mutual shielding and shielding by atomic and molecular hydrogen, and it is the first such model to include the rare isotopologues C17O and 13C17O. We couple it to a simple chemical network to analyse CO abundances in diffuse and translucent clouds, photon-dominated regions, and circumstellar disks. Results: The photodissociation rate in the unattenuated interstellar radiation field is 2.6 × 10-10 s-1, 30% higher than currently adopted values. Increasing the excitation temperature or the Doppler width can reduce the photodissociation rates and the isotopic selectivity by as much as a factor of three for temperatures above 100 K. The model reproduces column densities observed towards diffuse clouds and PDRs, and it offers an explanation for both the enhanced and the reduced N(12CO)/N(13CO) ratios seen in diffuse clouds. The photodissociation of C17O and 13C17O shows almost exactly the same depth dependence as that of C18O and 13C18O, respectively, so 17O and 18O are equally fractionated with respect to 16O. This supports the recent hypothesis that CO photodissociation in the solar nebula is responsible for the anomalous 17O and 18O abundances in meteorites. Grain growth in circumstellar disks can enhance the N(12CO)/N(C17O) and N(12CO)/N(C18O) ratios by a factor of ten relative to the initial isotopic abundances. Tables [see full textsee full text]-[see full textsee full text] are only

  8. Photodissociation of CO2 and quenching of metastables

    NASA Technical Reports Server (NTRS)

    Slanger, T. G.

    1978-01-01

    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.

  9. Isotope separation by selective photodissociation of glyoxal

    DOEpatents

    Marling, John B.

    1976-01-01

    Dissociation products, mainly formaldehyde and carbon monoxide, enriched in a desired isotope of carbon, oxygen, or hydrogen are obtained by the selective photodissociation of glyoxal wherein glyoxal is subjected to electromagnetic radiation of a predetermined wavelength such that photon absorption excites and induces dissociation of only those molecules of glyoxal containing the desired isotope.

  10. Photodissociation of CF2ICF2I in solid para-hydrogen: infrared spectra of anti- and gauche-˙C2F4I radicals.

    PubMed

    Haupa, Karolina Anna; Lim, Manho; Lee, Yuan-Pern

    2018-05-09

    The photolysis of 1,2-diiodotetrafluoroethane (CF2ICF2I) has served as a prototypical system in ultrafast reaction dynamics. Even though the intermediates, anti- and gauche-iodotetrafluoroethyl (˙C2F4I) radicals, have been characterized with electron diffraction and X-ray diffraction, their infrared spectra are unreported. We report the formation and infrared identification of these radical intermediates upon ultraviolet photodissociation of CF2ICF2I in solid para-hydrogen (p-H2) at 3.3 K. Lines at 1364.9/1358.5, 1283.2, 1177.1, 1162.2, 1126.8, 837.3, 658.0, 574.2, and 555.2 cm-1 are assigned to anti-˙C2F4I, and lines at 1325.9, 1259.7, 1143.4, 1063.4, 921.0, and 765.3 cm-1 to gauche-˙C2F4I. A secondary photodissociation leading to C2F4 was also observed. The assignments were derived according to behavior on secondary photolysis, comparison of the vibrational wavenumbers and the IR intensities of the observed lines with values predicted with the B3PW91/aug-cc-pVTZ-pp method. This spectral identification provides valuable information for future direct spectral probes of these important intermediates.

  11. Photodissociation Regions in the Interstellar Medium of Galaxies

    NASA Technical Reports Server (NTRS)

    Hollenbach, David J.; Tielens, A. G. G. M.; DeVincenzi, Donald L. (Technical Monitor)

    1999-01-01

    The interstellar medium of galaxies is the reservoir out of which stars are born and into which stars inject newly created elements as they age. The physical properties of the interstellar medium are governed in part by the radiation emitted by these stars. Far-ultraviolet (6 eV less than h(nu) less than 13.6 eV) photons from massive stars dominate the heating and influence the chemistry of the neutral atomic gas and much of the molecular gas in galaxies. Predominantly neutral regions of the interstellar medium in which the heating and chemistry are regulated by far ultraviolet photons are termed Photo-Dissociation Regions (PDRs). These regions are the origin of most of the non-stellar infrared (IR) and the millimeter and submillimeter CO emission from galaxies. The importance of PDRs has become increasingly apparent with advances in IR and submillimeter astronomy. The IR emission from PDRs includes fine structure lines of C, C+, and O; rovibrational lines of H2, rotational lines of CO; broad middle features of polycyclic aromatic hydrocarbons; and a luminous underlying IR continuum from interstellar dust. The transition of H to H2 and C+ to CO occurs within PDRs. Comparison of observations with theoretical models of PDRs enables one to determine the density and temperature structure, the elemental abundances, the level of ionization, and the radiation field. PDR models have been applied to interstellar clouds near massive stars, planetary nebulae, red giant outflows, photoevaporating planetary disks around newly formed stars, diffuse clouds, the neutral intercloud medium, and molecular clouds in the interstellar radiation field-in summary, much of the interstellar medium in galaxies. Theoretical PDR models explain the observed correlations of the [CII] 158 microns with the COJ = 1-0 emission, the COJ = 1-0 luminosity with the interstellar molecular mass, and the [CII] 158 microns plus [OI] 63 microns luminosity with the IR continuum luminosity. On a more global

  12. UV Photodissociation Action Spectroscopy of Haloanilinium Ions in a Linear Quadrupole Ion Trap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Hansen, Christopher S.; Kirk, Benjamin B.; Blanksby, Stephen J.; O'Hair, Richard. A. J.; Trevitt, Adam J.

    2013-06-01

    UV-vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availability of, ion trapping technologies and tunable laser sources. This study outlines in detail an instrumental arrangement, combining a commercial ion-trap mass spectrometer and tunable nanosecond pulsed laser source, for performing fully automated photodissociation action spectroscopy on gas-phase ions. The components of the instrumentation are outlined, including the optical and electronic interfacing, in addition to the control software for automating the experiment and performing online analysis of the spectra. To demonstrate the utility of this ensemble, the photodissociation action spectra of 4-chloroanilinium, 4-bromoanilinium, and 4-iodoanilinium cations are presented and discussed. Multiple photoproducts are detected in each case and the photoproduct yields are followed as a function of laser wavelength. It is shown that the wavelength-dependent partitioning of the halide loss, H loss, and NH3 loss channels can be broadly rationalized in terms of the relative carbon-halide bond dissociation energies and processes of energy redistribution. The photodissociation action spectrum of (phenyl)Ag2 + is compared with a literature spectrum as a further benchmark.

  13. Infrared Photodissociation Spectroscopy of Metal Ion -WATER Complexes

    NASA Astrophysics Data System (ADS)

    Bandyopadhyay, B.; Carnegie, P. D.; Duncan, M. A.

    2011-06-01

    Metal ion-water complexes are produced in a supersonic expansion cluster source via laser vaporization technique. Infrared photodissociation spectroscopy has been performed in the O-H stretch region. DFT calculations have also been carried out to obtain the structures and vibrational frequencies. Infrared spectra show partially resolved rotational structures which will be analyzed.

  14. Atomic carbon emission from photodissociation of CO2. [planetary atmospheric chemistry

    NASA Technical Reports Server (NTRS)

    Wu, C. Y. R.; Phillips, E.; Lee, L. C.; Judge, D. L.

    1978-01-01

    Atomic carbon fluorescence, C I 1561, 1657, and 1931 A, has been observed from photodissociation of CO2, and the production cross sections have been measured. A line emission source provided the primary photons at wavelengths from threshold to 420 A. The present results suggest that the excited carbon atoms are produced by total dissociation of CO2 into three atoms. The cross sections for producing the O I 1304-A fluorescence through photodissociation of CO2 are found to be less than 0.01 Mb in the wavelength region from 420 to 835 A. The present data have implications with respect to photochemical processes in the atmospheres of Mars and Venus.

  15. Photodissociation of pernitric acid (HO2NO2) at 248 nm

    NASA Technical Reports Server (NTRS)

    Macleod, Helene; Smith, Gregory P.; Golden, David M.

    1989-01-01

    The photodissociation of pernitric acid (PNA) was studied at 248 nm. The quantum yield for production of OH radicals is 34 + or - 16 percent. The yield of OH from PNA was measured relative to that of H2O2. The translational and rotational energy content of the OH photofragment from PNA was characterized. A fluorescent emission was also observed and characterized. It is attributed to electronically excited NO2 produced in the PNA photodissociation. A maximum yield of 30 percent for NO2 production was determined. The intensity of this emission, and a mass spectrometric peak at m/e = 33, were found to be useful means of characterizing the purity of the PNA sample.

  16. Semiclassical Wigner theory of photodissociation in three dimensions: Shedding light on its basis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Arbelo-González, W.; CNRS, Institut des Sciences Moléculaires, UMR 5255, 33405 Talence; Université Bordeaux, Institut des Sciences Moléculaires, UMR 5255, 33405 Talence

    2015-04-07

    The semiclassical Wigner theory (SCWT) of photodissociation dynamics, initially proposed by Brown and Heller [J. Chem. Phys. 75, 186 (1981)] in order to describe state distributions in the products of direct collinear photodissociations, was recently extended to realistic three-dimensional triatomic processes of the same type [Arbelo-González et al., Phys. Chem. Chem. Phys. 15, 9994 (2013)]. The resulting approach, which takes into account rotational motions in addition to vibrational and translational ones, was applied to a triatomic-like model of methyl iodide photodissociation and its predictions were found to be in nearly quantitative agreement with rigorous quantum results, but at a muchmore » lower computational cost, making thereby SCWT a potential tool for the study of polyatomic reaction dynamics. Here, we analyse the main reasons for this agreement by means of an elementary model of fragmentation explicitly dealing with the rotational motion only. We show that our formulation of SCWT makes it a semiclassical approximation to an approximate planar quantum treatment of the dynamics, both of sufficient quality for the whole treatment to be satisfying.« less

  17. Photodissociation of quantum state-selected diatomic molecules yields new insight into ultracold chemistry

    NASA Astrophysics Data System (ADS)

    McDonald, Mickey; McGuyer, Bart H.; Lee, Chih-Hsi; Apfelbeck, Florian; Zelevinsky, Tanya

    2016-05-01

    When a molecule is subjected to a sufficiently energetic photon it can break apart into fragments through a process called ``photodissociation''. For over 70 years this simple chemical reaction has served as a vital experimental tool for acquiring information about molecular structure, since the character of the photodissociative transition can be inferred by measuring the 3D photofragment angular distribution (PAD). While theoretical understanding of this process has gradually evolved from classical considerations to a fully quantum approach, experiments to date have not yet revealed the full quantum nature of this process. In my talk I will describe recent experiments involving the photodissociation of ultracold, optical lattice-trapped, and fully quantum state-resolved 88Sr2 molecules. Optical absorption images of the PADs produced in these experiments reveal features which are inherently quantum mechanical in nature, such as matter-wave interference between output channels, and are sensitive to the quantum statistics of the molecular wavefunctions. The results of these experiments cannot be predicted using quasiclassical methods. Instead, we describe our results with a fully quantum mechanical model yielding new intuition about ultracold chemistry.

  18. Laser induced fluorescence spectrum analysis of OH from photo-dissociation of water in gas phase

    NASA Astrophysics Data System (ADS)

    Li, Guohua; Ye, Jingfeng; Zhang, Zhengrong; Wang, Sheng; Hu, Zhiyun; Zhao, Xinyan

    2017-05-01

    The OH can be generated from photo-dissociation of water in the gas phase, and the generated OH has served in tagging velocimetry using the time-flight method. The hydroxyl tagging mechanism has the advantages of non-seeding, kindly flow following character, but its application in the reaction region is limited for the fluorescence interference from nascent OH. In this paper, we explored the laser induced fluorescence spectrum of OH both from burning and photodissociation. A photo-dissociation laser induced fluorescence (PD-LIF) system with optical multichannel analysis instrument (OMA) for spectrum analysis was developed. Based on multichannel mechanism, the LIF spectrum of OH from photo-dissociation and burning were acquired simultaneously. The temporal spectrum profiles of dissociation OH both in flame and air were taken by varying the pump-probe delay. The normalized emission spectrum in flame showed a process of rotational relaxation while in air the spectrum was almost not changed. The fluorescence intensity was precisely proportional to the base states population, so we can get certain states that the OH from dissociation was predominant from the fluorescence intensity ratio of OH. This result can be further utilized for hydroxyl tagging velocimetry technology (HTV) which was less affected by burning OH.

  19. Branching ratios for TlBr photodissociation with 2660 A radiation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    White, J.C.; Zdasiuk, G.A.

    1978-09-01

    Radiation from a Nd:YAG laser was used to study the selective photodissociation of TlBr into the Tl metastable state, 6p/sup 2/P/sub 3/2/, as a potential candidate for stimulated Roman up-converters.(AIP)

  20. Photodissociation dynamics of the ortho- and para-xylyl radicals

    NASA Astrophysics Data System (ADS)

    Pachner, Kai; Steglich, Mathias; Hemberger, Patrick; Fischer, Ingo

    2017-08-01

    The photodissociation dynamics of the C8H9 isomers ortho- and para-xylyl are investigated in a free jet. The xylyl radicals are generated by flash pyrolysis from 2-(2-methylphenyl)- and 2-(4-methylphenyl) ethyl nitrite and are excited into the D3 state. REMPI- spectra show vibronic structure and the origin of the transition is identified at 32 291 cm-1 for the para- and at 32 132 cm-1 for the ortho-isomer. Photofragment H-atom action spectra show bands at the same energy and thus confirm H-atom loss from xylyl radicals. To gain further insight into the photodissociation dynamics, velocity map images of the hydrogen atom photofragments are recorded. Their angular distribution is isotropic and the translational energy release is in agreement with a dissociation to products in their electronic ground state. Photodissociation of para-xylyl leads to the formation of para-xylylene (C8H8), while the data for ortho-xylyl agree much better with the isomer benzocyclobutene as the dominant molecular fragment rather than ortho-xylylene. In computations we identified a new pathway for the reaction ortho-xylyl → benzocyclobutene + H with a barrier of 3.39 eV (27 340 cm-1), which becomes accessible at the employed excitation energy. It proceeds via a combination of scissoring and rotational motion of the -CH2 and -CH3 groups. However, the observed rate constants measured by delaying the excitation and ionization laser with respect to each other are significantly faster than computed ones, indicating intrinsic non-RRKM behaviour. A comparably high value of around 30% of the excess energy is released as translation of the H-atom photofragment.

  1. Photodissociation dynamics of the ortho- and para-xylyl radicals.

    PubMed

    Pachner, Kai; Steglich, Mathias; Hemberger, Patrick; Fischer, Ingo

    2017-08-28

    The photodissociation dynamics of the C 8 H 9 isomers ortho- and para-xylyl are investigated in a free jet. The xylyl radicals are generated by flash pyrolysis from 2-(2-methylphenyl)- and 2-(4-methylphenyl) ethyl nitrite and are excited into the D 3 state. REMPI- spectra show vibronic structure and the origin of the transition is identified at 32 291 cm -1 for the para- and at 32 132 cm -1 for the ortho-isomer. Photofragment H-atom action spectra show bands at the same energy and thus confirm H-atom loss from xylyl radicals. To gain further insight into the photodissociation dynamics, velocity map images of the hydrogen atom photofragments are recorded. Their angular distribution is isotropic and the translational energy release is in agreement with a dissociation to products in their electronic ground state. Photodissociation of para-xylyl leads to the formation of para-xylylene (C 8 H 8 ), while the data for ortho-xylyl agree much better with the isomer benzocyclobutene as the dominant molecular fragment rather than ortho-xylylene. In computations we identified a new pathway for the reaction ortho-xylyl → benzocyclobutene + H with a barrier of 3.39 eV (27 340 cm -1 ), which becomes accessible at the employed excitation energy. It proceeds via a combination of scissoring and rotational motion of the -CH 2 and -CH 3 groups. However, the observed rate constants measured by delaying the excitation and ionization laser with respect to each other are significantly faster than computed ones, indicating intrinsic non-RRKM behaviour. A comparably high value of around 30% of the excess energy is released as translation of the H-atom photofragment.

  2. Proposed Molecular Beam Determination of Energy Partition in the Photodissociation of Polyatomic Molecules

    DOE R&D Accomplishments Database

    Zare, P. N.; Herschbach, D. R.

    1964-01-29

    Conventional photochemical experiments give no information about the partitioning of energy between translational recoil and internal excitation of the fragment molecules formed in photodissociation of a polyatomic molecule. In a molecular beam experiment, it becomes possible to determine the energy partition from the form of the laboratory angular distribution of one of the photodissociation products. A general kinematic analysis is worked out in detail, and the uncertainty introduced by the finite angular resolution of the apparatus and the velocity spread in the parent beam is examined. The experimental requirements are evaluated for he photolysis of methyl iodide by the 2537 angstrom Hg line.

  3. Photodissociation spectroscopy of the dysprosium monochloride molecular ion

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dunning, Alexander, E-mail: alexander.dunning@gmail.com; Schowalter, Steven J.; Puri, Prateek

    2015-09-28

    We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl{sup +}. The photodissociation cross section for the photon energy range 35 500 cm{sup −1} to 47 500 cm{sup −1} is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43 000 cm{sup −1}. The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl{sup +} is extremely complex due to the presence of multiple open electronic shells,more » including the 4f{sup 10} configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy{sup +} ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.« less

  4. The Photodissociation of Nitromethane at 193 nm.

    DTIC Science & Technology

    1983-02-28

    available energy for product translational + internal energy is 90 kcal/mole. As the largest amount of energy that goes into translational energy in the...CATAL.O8 NUMIER 0 R 92-545/21W83 P 3-/ 4. TITLE (and Subtlee) S. TYPE OF REPORT A PEI4o0 COVERED THE PHOTODISSOCIATION OF NITROMETHANE AT 193 NM Technical S...been investigated by two independent and comple- *_ mentary techniques, product emission spectroscopy and molecular beam photofragment translational

  5. Photoisomerization and photodissociation dynamics of reactive free radicals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bise, Ryan T.

    2000-08-01

    The photofragmentation pathways of chemically reactive free radicals have been examined using the technique of fast beam photofragment translational spectroscopy. Measurements of the photodissociation cross-sections, product branching ratios, product state energy distributions, and angular distributions provide insight into the excited state potential energy surfaces and nonadiabatic processes involved in the dissociation mechanisms. Photodissociation spectroscopy and dynamics of the predissociativemore » $$\\tilde{A}$$ 2A 1 and $$\\tilde{B}$$ 2A 2 states of CH 3S have been investigated. At all photon energies, CH 3 + S( 3P j), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH 3 umbrella mode and the S( 3P j) fine-structure distribution from which the nature of the coupled repulsive surfaces is inferred. Dissociation rates are deduced from the photofragment angular distributions, which depend intimately on the degree of vibrational excitation in the C-S stretch. Nitrogen combustion radicals, NCN, CNN and HNCN have also been studied. For all three radicals, the elimination of molecular nitrogen is the primary reaction channel. Excitation to linear excited triplet and singlet electronic states of the NCN radical generates resolved vibrational structure of the N 2 photofragment. The relatively low fragment rotational excitation suggests dissociation via a symmetric C 2V transition state. Resolved vibrational structure of the N 2 photofragment is also observed in the photodissociation of the HNCN radical. The fragment vibrational and rotational distributions broaden with increased excitation energy. Simple dissociation models suggest that the HNCN radical isomerizes to a cyclic intermediate (c-HCNN) which then dissociates via a tight cyclic transition state. In contrast to the radicals mentioned above, resolved vibrational structure was not observed for the ICNN radical

  6. Velocity distributions of hydrogen atoms and hydroxyl radicals produced through solar photodissociation of water

    NASA Astrophysics Data System (ADS)

    Wu, C. Y. R.; Chen, F. Z.

    1993-04-01

    The velocity distributions of H and OH fragments produced through solar photodissociation of gaseous H2O molecules under collisionless conditions are presented. The calculations are carried out using: the most recently available absolute partial cross sections for the production of H and OH through photodissociation of H2O from its absorption onset at 1860 A down to 500 A; the newly available vibrational and rotational energy distributions of both the excited and ground state OH photofragments; the calculated cross sections for the total dissociation processes; and the integrated solar flux in 10 A increments from 500 to 1860 A in the continuum regions and the specific wavelength and flux at the bright solar lines. The calculated results show that the H atoms and the OH radicals produced exhibit multiple velocity groups. Since most current cometary modeling uses a single velocity of 20 km/sec associated with the photodissociation of H2O, the present results may be useful in interpreting the many peaks observed in the velocity distributions of the H Lyman alpha and H alpha of comets.

  7. Linkage and Anomeric Differentiation in Trisaccharides by Sequential Fragmentation and Variable-Wavelength Infrared Photodissociation

    NASA Astrophysics Data System (ADS)

    Tan, Yanglan; Polfer, Nicolas C.

    2015-02-01

    Carbohydrates and their derivatives play important roles in biological systems, but their isomeric heterogeneity also presents a considerable challenge for analytical techniques. Here, a stepwise approach using infrared multiple-photon dissociation (IRMPD) via a tunable CO2 laser (9.2-10.7 μm) was employed to characterize isomeric variants of glucose-based trisaccharides. After the deprotonated trisaccharides were trapped and fragmented to disaccharide C2 fragments in a Fourier transform ion cyclotron resonance (FTICR) cell, a further variable-wavelength infrared irradiation of the C2 ion produced wavelength-dependent dissociation patterns that are represented as heat maps. The photodissociation patterns of these C2 fragments are shown to be strikingly similar to the photodissociation patterns of disaccharides with identical glycosidic bonds. Conversely, the photodissociation patterns of different glycosidic linkages exhibit considerable differences. On the basis of these results, the linkage position and anomericity of glycosidic bonds of disaccharide units in trisaccharides can be systematically differentiated and identified, providing a promising approach to characterize the structures of isomeric oligosaccharides.

  8. Photodissociation in the atmosphere of Mars - Impact of high resolution, temperature-dependent CO2 cross-section measurements

    NASA Technical Reports Server (NTRS)

    Anbar, A. D.; Allen, M.; Nair, H. A.

    1993-01-01

    We have investigated the impact of high resolution, temperature-dependent CO2 cross-section measurements, reported by Lewis and Carver (1983), on calculations of photodissociation rate coefficients in the Martian atmosphere. We find that the adoption of 50 A intervals for the purpose of computational efficiency results in errors in the calculated values for photodissociation of CO2, H2O, and O2 which are generally not above 10 percent, but as large as 20 percent in some instances. These are acceptably small errors, especially considering the uncertainties introduced by the large temperature dependence of the CO2 cross section. The inclusion of temperature-dependent CO2 cross sections is shown to lead to a decrease in the diurnally averaged rate of CO2 photodissociation as large as 33 percent at some altitudes, and increases of as much as 950 percent and 80 percent in the photodissociation rate coefficients of H2O and O2, respectively. The actual magnitude of the changes depends on the assumptions used to model the CO2 absorption spectrum at temperatures lower than the available measurements, and at wavelengths longward of 1970 A.

  9. Fate of artificial sweeteners through wastewater treatment plants and water treatment processes

    PubMed Central

    Li, Shaoli; Ren, Yuhang; Fu, Yingying; Gao, Xingsheng; Jiang, Cong; Wu, Gang; Ren, Hongqiang

    2018-01-01

    Five full-scale wastewater treatment plants (WWTPs) in China using typical biodegradation processes (SBR, oxidation ditch, A2/O) were selected to assess the removal of four popular artificial sweeteners (ASs). All four ASs (acesulfame (ACE), sucralose (SUC), cyclamate (CYC) and saccharin (SAC)) were detected, ranging from 0.43 to 27.34μg/L in the influent. Higher concentrations of ASs were measured in winter. ACE could be partly removed by 7.11–50.76% through biodegradation and especially through the denitrifying process. The A2/O process was the most efficient at biodegrading ASs. Adsorption (by granular activated carbon (GAC) and magnetic resin) and ultraviolet radiation-based advanced oxidation processes (UV/AOPs) were evaluated to remove ASs in laboratory-scale tests. The amounts of resin adsorbed were 3.33–18.51 times more than those of GAC except for SUC. The adsorption ability of resin decreased in the order of SAC > ACE > CYC > SUC in accordance with the pKa. Degradation of ASs followed pseudo-first-order kinetics in UV/H2O2 and UV/PDS. When applied to the secondary effluent, ASs could be degraded from 30.87 to 99.93% using UV/PDS in 30 minutes and UV/PDS was more efficient and economic. PMID:29293534

  10. Fate of artificial sweeteners through wastewater treatment plants and water treatment processes.

    PubMed

    Li, Shaoli; Ren, Yuhang; Fu, Yingying; Gao, Xingsheng; Jiang, Cong; Wu, Gang; Ren, Hongqiang; Geng, Jinju

    2018-01-01

    Five full-scale wastewater treatment plants (WWTPs) in China using typical biodegradation processes (SBR, oxidation ditch, A2/O) were selected to assess the removal of four popular artificial sweeteners (ASs). All four ASs (acesulfame (ACE), sucralose (SUC), cyclamate (CYC) and saccharin (SAC)) were detected, ranging from 0.43 to 27.34μg/L in the influent. Higher concentrations of ASs were measured in winter. ACE could be partly removed by 7.11-50.76% through biodegradation and especially through the denitrifying process. The A2/O process was the most efficient at biodegrading ASs. Adsorption (by granular activated carbon (GAC) and magnetic resin) and ultraviolet radiation-based advanced oxidation processes (UV/AOPs) were evaluated to remove ASs in laboratory-scale tests. The amounts of resin adsorbed were 3.33-18.51 times more than those of GAC except for SUC. The adsorption ability of resin decreased in the order of SAC > ACE > CYC > SUC in accordance with the pKa. Degradation of ASs followed pseudo-first-order kinetics in UV/H2O2 and UV/PDS. When applied to the secondary effluent, ASs could be degraded from 30.87 to 99.93% using UV/PDS in 30 minutes and UV/PDS was more efficient and economic.

  11. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Aguado, Alfredo; Roncero, Octavio; Zanchet, Alexandre

    The impact of the photodissociation of HCN and HNC isomers is analyzed in different astrophysical environments. For this purpose, the individual photodissociation cross sections of HCN and HNC isomers have been calculated in the 7–13.6 eV photon energy range for a temperature of 10 K. These calculations are based on the ab initio calculation of three-dimensional adiabatic potential energy surfaces of the 21 lower electronic states. The cross sections are then obtained using a quantum wave packet calculation of the rotational transitions needed to simulate a rotational temperature of 10 K. The cross section calculated for HCN shows significant differencesmore » with respect to the experimental one, and this is attributed to the need to consider non-adiabatic transitions. Ratios between the photodissociation rates of HCN and HNC under different ultraviolet radiation fields have been computed by renormalizing the rates to the experimental value. It is found that HNC is photodissociated faster than HCN by a factor of 2.2 for the local interstellar radiation field and 9.2 for the solar radiation field, at 1 au. We conclude that to properly describe the HNC/HCN abundance ratio in astronomical environments illuminated by an intense ultraviolet radiation field, it is necessary to use different photodissociation rates for each of the two isomers, which are obtained by integrating the product of the photodissociation cross sections and ultraviolet radiation field over the relevant wavelength range.« less

  12. Rovibrationally-Resolved Direct Photodissociation Through The Lyman And Werner Transitions Of H_{2}

    NASA Astrophysics Data System (ADS)

    Gay, Christopher; Stancil, P. C.

    2008-03-01

    Direct photodissociation cross sections have been obtained for the Lyman and Werner transitions of H2 using a combination of ab initio and experimentally derived potential curves and dipole transition moments. The partial cross sections have been evaluated for transitions from all 301 rovibrational levels (v'',J'') of the ground electronic state and over a wavelength range that extends from 10nm to the dissociation threshold for each particular rovibrational state. For UV-irradiated molecular gas with column densities of 1016-1019cm-2, direct photodissociation can compete with the Solomon process as an H2 destruction process. This research was supported by NASA grant NNG06GJ11G from the Astrophysics Theory Program.

  13. High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N

    NASA Astrophysics Data System (ADS)

    Heays, A. N.; Dickenson, G. D.; Salumbides, E. J.; de Oliveira, N.; Joyeux, D.; Nahon, L.; Lewis, B. R.; Ubachs, W.

    2011-12-01

    The first comprehensive high-resolution photoabsorption spectrum of 14N15N has been recorded using the Fourier-transform spectrometer attached to the Desirs beamline at the Soleil synchrotron. Observations are made in the extreme ultraviolet and span 100 000-109 000 cm-1 (100-91.7 nm). The observed absorption lines have been assigned to 25 bands and reduced to a set of transition energies, f values, and linewidths. This analysis has verified the predictions of a theoretical model of N2 that simulates its photoabsorption and photodissociation cross section by solution of an isotopomer independent formulation of the coupled-channel Schrödinger equation. The mass dependence of predissociation linewidths and oscillator strengths is clearly evident and many local perturbations of transition energies, strengths, and widths within individual rotational series have been observed.

  14. Review of ultraviolet absorption cross sections of a series of alternative fluorocarbons

    NASA Technical Reports Server (NTRS)

    Molina, Mario J.

    1990-01-01

    Solar photolysis is likely to contribute to the stratospheric destruction of those alternative fluorocarbons (HFC's) which have two or more chlorine atoms bonded to the same carbon atom. Two of the eight HFC's considered here fall into this category, namely HFC-123 and HFC141b. For these two species there is good agreement among the various measurements of the ultraviolet cross sections in the wavelength region which is important for atmospheric photodissociation, that is, around 200 nm. There is also good agreement for HFC-124, HFC-22 and HFC-142b. These are the three species which contain one chlorine atom per molecule. The agreement in the measurements is poor for the other species, i.e., those that do not contain chlorine, except in so far as to corroborate that solar photolysis should be negligible relative to destruction by hydroxyl radicals.

  15. Photodissociation of Gaseous Ions Formed by Laser Desorption.

    DTIC Science & Technology

    1986-09-20

    produced by separate pathways from the (M-I)- ion or from consecutive photodissociations. Hesperidin : In the negative ion LD mass spectrum of this compound...an ion of m/z r𔃼 was produced from the sodium salt of hesperidin phosphoric acid ester. This ion was observed to dissociate by loss of the attached...Experimental conditions are same as in the top spectrum. Figure 8. Top. Negative ions formed by laser desorption from Na-salt of hesperidin phosphoric acid ester

  16. Carbon recombination lines as a diagnostic of photodissociation regions

    NASA Technical Reports Server (NTRS)

    Natta, A.; Walmsley, C. M.; Tielens, A. G. G. M.

    1994-01-01

    We have observed the C91 alpha radio recombination line toward the Orion H II region. This narrow (approximately 3-5 km per sec full width at half maximum (FWHM)) line is spatially very extended (approximately 8 arcmin or 1 pc). These charateristics compare well with the observed characteristics of the C II fine structure line at 158 microns. Thus, the C91 alpha line originates in the predominantly neutral photodissociation regions separating the H II region from the molecular cloud. We have developed theoretical models for the C II radio recombination lines from photodissociation regions. The results show that the I(C91 alpha)/I(C158) intensity ratio is a sensitive function of the temperature and density of the emitting gas. We have also extended theoretical models for photodissociation regions to include the C II recombination lines. Comparison with these models show that, in the central portion of the Orion region, the C91 alpha line originates in dense (10(exp 6) per cu cm), warm (500-1000 K) gas. Even at large projected distances (approximately 1 pc), the inferred density is still high (10(exp 5) per cu cm) and implies extremely high thermal pressures. As in the case of the (C II) 158 microns line, the large extent of the C91 alpha line shows that (FUV) photons can penetrate to large distances from the illuminating source. The decline of the intensity of the incident radiation field with distance from Theta(sup 1) C seems to be dominated by geometrical dilution, rather than dust extinction. Finally, we have used our models to calculate the intensity of the 9850 A recombination line of C II. The physical conditions inferred from this line are in good agreement with those determined from the radio recombination and the far-infrared fine-structure lines. We show that the ratio of the 9850 A to the C91 alpha lines is a very good probe of very high density clumps.

  17. Ultraviolet Spectra of Comets Observed with the International Ultraviolet Explorer Satellite Observatory.

    NASA Astrophysics Data System (ADS)

    Weaver, Harold Anthony, Jr.

    Ultraviolet spectra of seven comets observed with the International Ultraviolet Explorer (IUE) satellite are presented. Observations of comet Bradfield (1979 X) made in early 1980 allow a comprehensive study of the production of water by this comet. By comparing the observations to the predictions of two water models of the coma (Haser and vectorial), it is determined that these measurements support the idea of a comet composed principally of water ice. The vaporization of the water has a rather unexpected heliocentric variation, decreasing as r('-3.7) over the entire range of observations. Atomic carbon is relatively abundant in the coma of comet Bradfield; the production rate of carbon is roughly 5-10% of the water production rate. Analysis of the spatial brightness profiles of the strongest atomic carbon emission does not reveal the identity of the source of the observed carbon, but the data are apparently inconsistent with a photodissociation source that is either CO or CO(,2). A comparison of the ultraviolet spectrum of periodic comet Encke, recorded by the IUE between 1980 October 24 and November 5, with similar spectra of short and long period comets shows the gaseous composition of P/Encke to be virtually identical to that of the other comets. If P/Encke is indeed the remains of a once giant comet, this similarity implies a homogeneous structure for the cometary ice nucleus. The OH(0,0) band brightness distribution shows a spatial variation similar to the visible fan-shaped image of the comet. Comets P/Tuttle (1980h), P/Stephan-Oterma (1980g), and Meier (1980q) were observed during November-December 1980 with IUE, while comets P/Borrelly (1980i) and Panther (1980u) were observed with IUE on 6 March 1981. The spectra of these comets are compared with those of comets Bradfield (1979 X) and P/Encke, as well as with each other. In order to simplify the interpretation of the data and to minimize the dependence upon a specific model, the spectra are compared at

  18. Photodissociation Dynamics of Phenol: Multistate Trajectory Simulations including Tunneling

    DOE PAGES

    Xu, Xuefei; Zheng, Jingjing; Yang, Ke R.; ...

    2014-10-27

    We report multistate trajectory simulations, including coherence, decoherence, and multidimensional tunneling, of phenol photodissociation dynamics. The calculations are based on full-dimensional anchor-points reactive potential surfaces and state couplings fit to electronic structure calculations including dynamical correlation with an augmented correlation-consistent polarized valence double-ζ basis set. The calculations successfully reproduce the experimentally observed bimodal character of the total kinetic energy release spectra and confirm the interpretation of the most recent experiments that the photodissociation process is dominated by tunneling. Analysis of the trajectories uncovers an unexpected dissociation pathway for one quantum excitation of the O–H stretching mode of the S 1more » state, namely, tunneling in a coherent mixture of states starting in a smaller R OH (~0.9–1.0 Å) region than has previously been invoked. The simulations also show that most trajectories do not pass close to the S 1–S 2 conical intersection (they have a minimum gap greater than 0.6 eV), they provide statistics on the out-of-plane angles at the locations of the minimum energy adiabatic gap, and they reveal information about which vibrational modes are most highly activated in the products.« less

  19. Imaging the photodissociation dynamics of the methyl radical from the 3s and 3pz Rydberg states

    PubMed Central

    Marggi Poullain, Sonia; Chicharro, David V.; Zanchet, Alexandre; González, Marta G.; Rubio-Lago, Luis; Senent, María L.; García-Vela, Alberto; Bañares, Luis

    2016-01-01

    The photodissociation dynamics of the methyl radical from the 3s and 3pz Rydberg states have been studied using velocity map and slice ion imaging in combination with pump-probe nanosecond laser pulses. The reported translational energy and angular distributions of the H(2S) photofragment detected by (2+1) REMPI highlight different dissociation mechanisms for the 3s and 3pz Rydberg states. A narrow peak in the translational energy distribution and an anisotropic angular distribution characterizes the fast 3s photodissociation, while for the 3pz state Boltzmann-type translational energy and isotropic angular distributions are found. High level ab initio calculations have been performed in order to elucidate the photodissociation mechanisms from the two Rydberg states and to rationalize the experimental results. The calculated potential energy curves highlight a typical predissociation mechanism for the 3s state, characterized by the coupling between the 3s Rydberg state and a valence repulsive state. On the other hand, the photodissociation on the 3pz state is initiated by a predissociation process due to the coupling between the 3pz Rydberg state and a valence repulsive state and constrained, later on, by two conical intersections that allow the system to relax to lower electronic states. Such mechanism opens different reaction pathways leading to CH2 photofragments in different electronic states and inducing a transfer of energy between translational and internal modes. PMID:27296907

  20. Ab initio studies on the photodissociation dynamics of the 1,1-difluoroethyl radical

    NASA Astrophysics Data System (ADS)

    Fritsche, Lukas; Bach, Andreas; Chen, Peter

    2018-02-01

    Born-Oppenheimer molecular dynamics trajectory calculations at the HCTH147/6-31G** level of theory simulate the dissociation dynamics of photolytically excited 1,1-difluoroethyl radicals. EOMCCSD/AUG-cc-pVDZ calculations show that an excitation energy of 94.82 kcal/mol is necessary to initiate photodissociation reactions. In contrast to photodissociation dynamics of ethyl radicals where a large discrepancy between actual dissociation rates and rates that are predicted by statistical rate theories, we find reaction rates of 5.1 × 1011 s-1 for the dissociation of an H atom, which is in perfect accord with what is predicted by Rice-Ramsperger-Kassel-Marcus (RRKM) calculations and there is no indication of any nonstatistical effects. However, our trajectory calculations show a much larger fraction of C-C bond breakage reaction of 56% occurring than that expected by RRKM (only 16%).

  1. Ab initio studies on the photodissociation dynamics of the 1,1-difluoroethyl radical.

    PubMed

    Fritsche, Lukas; Bach, Andreas; Chen, Peter

    2018-02-28

    Born-Oppenheimer molecular dynamics trajectory calculations at the HCTH147/6-31G** level of theory simulate the dissociation dynamics of photolytically excited 1,1-difluoroethyl radicals. EOMCCSD/AUG-cc-pVDZ calculations show that an excitation energy of 94.82 kcal/mol is necessary to initiate photodissociation reactions. In contrast to photodissociation dynamics of ethyl radicals where a large discrepancy between actual dissociation rates and rates that are predicted by statistical rate theories, we find reaction rates of 5.1 × 10 11 s -1 for the dissociation of an H atom, which is in perfect accord with what is predicted by Rice-Ramsperger-Kassel-Marcus (RRKM) calculations and there is no indication of any nonstatistical effects. However, our trajectory calculations show a much larger fraction of C-C bond breakage reaction of 56% occurring than that expected by RRKM (only 16%).

  2. New ab initio potential surfaces and three-dimensional quantum dynamics for transition state spectroscopy in ozone photodissociation

    NASA Astrophysics Data System (ADS)

    Yamashita, Koichi; Morokuma, Keiji; Le Quéré, Frederic; Leforestier, Claude

    1992-04-01

    New ab initio potential energy surfaces (PESs) of the ground and B ( 1B 2) states of ozone have been calculated with the CASSCF-SECI/DZP method to describe the three-dimensional photodissociation process. The dissociation energy of the ground state and the vertical barrier height of the B PES are obtained to be 0.88 and 1.34 eV, respectively, in better agreement with the experimental values than the previous calculation. The photodissociation autocorrelation function, calculated on the new B PES, based on exact three-dimensional quantum dynamics, reproduces well the main recurrence feature extracted from the experimental spectra.

  3. Photodissociation of OCS: deviations between theory and experiment, and the importance of higher order correlation effects.

    PubMed

    Schmidt, J A; Olsen, J M H

    2014-11-14

    The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 136, 131101 (2012); J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 2(1)A' (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 1(1)A″ (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO.

  4. Photodissociation of the CH3O and CH3S radical molecules: An ab initio electronic structure study

    PubMed Central

    Bouallagui, A.; Zanchet, A.; Yazidi, O.; Jaïdane, N.; Bañares, L.; Senent, M.L.; García-Vela, A.

    2018-01-01

    The electronic states and the spin-orbit couplings between them involved in the photodissociation process of the radical molecules CH3X, CH3X → CH3 + X(X = O, S), taking place after the Ā(2A1) ← X̄(2E) transition, have been investigated using highly correlated ab initio techniques. A two-dimensional representation of both the potential-energy surfaces (PESs) and the couplings is generated. This description includes the C-X dissociative mode and the CH3 umbrella mode. Spin-orbit effects are found to play a relevant role on the shape of the excited state potential-energy surfaces, particularly in the CH3S case where the spin-orbit couplings are more than twice more intense than in CH3O. The potential surfaces and couplings reported here for the present set of electronic states allow for the first complete description of the above photodissociation process. The different photodissociation mechanisms are analyzed and discussed in the light of the results obtained. PMID:29143005

  5. Bond-selective photodissociation of partially deuterated ammonia molecules: Photodissociations of vibrationally excited NHD2 in the 5νNH state and NH2D in the 5νND state

    NASA Astrophysics Data System (ADS)

    Akagi, Hiroshi; Yokoyama, Keiichi; Yokoyama, Atsushi

    2004-03-01

    Ultraviolet photodissociation of NHD2 excited to the fourth overtone state of the NH stretching mode (5νNH) and NH2D excited to that of the ND stretching mode (5νND) has been investigated by using a crossed laser and molecular beams method. Branching ratio between the NH and ND bond dissociations has been determined by utilizing a (2+1) resonance enhanced multiphoton ionization scheme of H and D atoms. For the photolysis of NHD2 in the 5νNH state, the NH dissociation cross section is 5.1±1.4 times as large as the ND dissociation cross section per bond. On the other hand, for the photolysis of NH2D in the 5νND state, the ratio of the NH dissociation cross section per bond to the ND dissociation cross section decreases to 0.68±0.16. In comparison with the branching ratios for the photolysis of vibrationally unexcited NH2D and NHD2 [Koda and Back, Can. J. Chem. 55, 1380 (1977)], the present results indicate that the excitation of the NH stretching mode enhances the NH dissociation with ca. two times larger NH/ND branching ratio, whereas the excitation of the ND stretching mode results in the preferential ND dissociation with ca. 3-4 times larger ND/NH branching ratio than that for the vibrational ground states. The mechanism of the bond-selective enhancement has been discussed in terms of the energetics and dynamics of wave packet.

  6. Photodissociation dynamics of Mo(CO) sub 6 at 266 and 355 nm: CO photofragment kinetic-energy and internal-state distributions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Buntin, S.A.; Cavanagh, R.R.; Richter, L.J.

    1991-06-15

    The internal-state and kinetic-energy distributions of the CO photofragments from the 266 and 355 nm photolysis of Mo(CO){sub 6} have been measured under collision-free conditions using vacuum-ultraviolet laser-induced fluorescence. The rotational-state distributions for CO({ital v}{double prime}=0) and ({ital v}{double prime}=1) are well represented by Boltzmann distributions with effective rotational temperatures'' of {ital T}{sub {ital r}}({ital v}{double prime}=0)=950{plus minus}70 K and {ital T}{sub {ital r}}({ital v}{double prime}=1)=935{plus minus}85 K for 266 nm and {ital T}{sub {ital r}}({ital v}{double prime}=0)=750{plus minus}70 K and {ital T}{sub {ital r}}({ital v}{double prime}=1)=1150{plus minus}250 K for 355 nm photolysis. The CO({ital v}{double prime}=1/{ital v}{double prime}=0) vibrational-statemore » ratios for 266 and 355 nm photolysis are 0.19{plus minus}0.03 and 0.09{plus minus}0.02, respectively. The Doppler-broadened CO photofragment line shapes indicate that the translational energy distributions are isotropic and Maxwellian. There is no photolysis-laser wavelength or internal-state dependence to the extracted translational temperatures.'' The observed energy partitioning and kinetic-energy distributions are inconsistent with an impulsive ejection of a single CO ligand. CO photofragment line shapes for 266 nm photolysis are not consistent with a mechanism involving the repulsive ejection of the first CO ligand, followed by the statistical decomposition of the Mo(CO){sub 5} fragment. While phase-space theories do not predict quantitatively the energy disposal, the photodissociation mechanism appears to be dominated by statistical considerations. The results also suggest that the photodissociation of Mo(CO){sub 6} at 266 and 355 nm involves a common initial state'' and that similar exit channel effects are operative.« less

  7. A conformational study of protonated noradrenaline by UV-UV and IR dip double resonance laser spectroscopy combined with an electrospray and a cold ion trap method.

    PubMed

    Wako, Hiromichi; Ishiuchi, Shun-Ichi; Kato, Daichi; Féraud, Géraldine; Dedonder-Lardeux, Claude; Jouvet, Christophe; Fujii, Masaaki

    2017-05-03

    The conformer-selected ultraviolet (UV) and infrared (IR) spectra of protonated noradrenaline were measured using an electrospray/cryogenic ion trap technique combined with photo-dissociation spectroscopy. By comparing the UV photo dissociation (UVPD) spectra with the UV-UV hole burning (HB) spectra, it was found that five conformers coexist under ultra-cold conditions. Based on the spectral features of the IR dip spectra of each conformer, two different conformations on the amine side chain were identified. Three conformers (group I) were assigned to folded and others (group II) to extended structures by comparing the observed IR spectra with the calculated ones. Observation of the significantly less-stable extended conformers strongly suggests that the extended structures are dominant in solution and are detected in the gas phase by kinetic trapping. The conformers in each group are assignable to rotamers of OH orientations in the catechol ring. By comparing the UV-UV HB spectra and the calculated Franck-Condon spectra obtained by harmonic vibrational analysis of the S 1 state, with the aid of relative stabilization energies of each conformer in the S 0 state, the absolute orientations of catechol OHs of the observed five conformers were successfully determined. It was found that the 0-0 transition of one folded conformer is red-shifted by about 1000 cm -1 from the others. The significant red-shift was explained by a large contribution of the πσ* state to S 1 in the conformer in which an oxygen atom of the meta-OH group is close to the ammonium group.

  8. Ab initio implementation of quantum trajectory mean-field approach and dynamical simulation of the N{sub 2}CO photodissociation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xie, Binbin; Liu, Lihong; Cui, Ganglong

    2015-11-21

    In this work, the recently introduced quantum trajectory mean-field (QTMF) approach is implemented and employed to explore photodissociation dynamics of diazirinone (N{sub 2}CO), which are based on the high-level ab initio calculation. For comparison, the photodissociation process has been simulated as well with the fewest-switches surface hopping (FSSH) and the ab initio multiple spawning (AIMS) methods. Overall, the dynamical behavior predicted by the three methods is consistent. The N{sub 2}CO photodissociation at λ > 335 nm is an ultrafast process and the two C—N bonds are broken in a stepwise way, giving birth to CO and N{sub 2} as themore » final products in the ground state. Meanwhile, some noticeable differences were found in the QTMF, FSSH, and AIMS simulated time constants for fission of the C—N bonds, excited-state lifetime, and nonadiabatic transition ratios in different intersection regions. These have been discussed in detail. The present study provides a clear evidence that direct ab initio QTMF approach is one of the reliable tools for simulating nonadiabatic dynamics processes.« less

  9. Estimation of the quantum efficiency of the photodissociation of HbO2 and HbCO

    NASA Astrophysics Data System (ADS)

    Gisbrecht, A. I.; Mamilov, S. A.; Esman, S. S.; Asimov, M. M.

    2016-01-01

    The paper presents our results on the study of the efficiency of inter-fractional changes in hemoglobin molecules depending on the laser radiation parameters. The evaluation of the quantum efficiency of light interaction in vivo with oxyhemoglobin (HbO2) and carboxyhemoglobin (HbCO) in the blood at wavelengths for 525 and 605 nm is presented. The photodissociation yield of 11% for HbO2 and 79% for HbCO are measured at the wavelength of 525 nm and 10 % for HbO2 and 76 % for HbCO at a wavelength of 605 nm. Thus, the quantum yield of photodissociation of the HbCO is considerably higher, which ensures high efficiency of photodecomposition of the HbCO in the blood. The obtained results can be used in the clinical phototherapy practice for effective treatment of CO poisoning.

  10. Photodissociation of cis-, trans-, and 1,1-dichloroethylene in the ultraviolet range: characterization of Cl((2)P(J)) elimination.

    PubMed

    Hua, Linqiang; Zhang, Xiaopeng; Lee, Wei-Bin; Chao, Meng-Hsuan; Zhang, Bing; Lin, King-Chuen

    2010-01-14

    By using photofragment velocity imaging detection coupled with a (2 + 1) resonance-enhanced multiphoton ionization technique, the elimination channel of spin-orbit chlorine atoms in photodissociation of cis-, trans-, and 1,1-dichloroethylene at two photolysis wavelengths of 214.5 and 235 nm is investigated. Translational energy and angular distributions of Cl((2)P(J)) fragmentation are acquired. The Cl((2)P(J)) fragments are produced by two competing channels. The fast dissociation component with higher translational energy is characterized by a Gaussian distribution, resulting from a curve crossing of the initially excited (pi, pi*) state to nearby repulsive (pi, sigma*) and/or (n, sigma*). In contrast, the slow component with a lower translational energy is characterized by a Boltzmann distribution, which dissociates on the vibrationally hot ground state relaxed from the (pi, pi*) state via internal conversion. cis-C(2)H(2)Cl(2) is found to have a larger branching of Boltzmann component than the other two isomers. The fraction of available energy partitioning into translation increases along the trend of cis- < trans- < 1,1-C(2)H(2)Cl(2). This trend may be fitted by a rigid radical model and interpreted by means of a torque generated during the C-Cl bond cleavage. The anisotropy parameters are determined, and the transition dipole moments are expected to be essentially along the C horizontal lineC bond axis. The results are also predicted theoretically. The relative quantum yields of Cl((2)P(J)) have a similar value for the three isomers at the two photolysis wavelengths.

  11. UV/H2O2 and UV/PDS Treatment of Trimethoprim and Sulfamethoxazole in Synthetic Human Urine: Transformation Products and Toxicity.

    PubMed

    Zhang, Ruochun; Yang, Yongkui; Huang, Ching-Hua; Li, Na; Liu, Hang; Zhao, Lin; Sun, Peizhe

    2016-03-01

    Elimination of pharmaceuticals in source-separated human urine is a promising approach to minimize the pharmaceuticals in the environment. Although the degradation kinetics of pharmaceuticals by UV/H2O2 and UV/peroxydisulfate (PDS) processes has been investigated in synthetic fresh and hydrolyzed urine, comprehensive evaluation of the advanced oxidation processes (AOPs), such as product identification and toxicity testing, has not yet been performed. This study identified the transformation products of two commonly used antibiotics, trimethoprim (TMP) and sulfamethoxazole (SMX), by UV/H2O2 and UV/PDS in synthetic urine matrices. The effects of reactive species, including •OH, SO4(•-), CO3(•-), and reactive nitrogen species, on product generation were investigated. Multiple isomeric transformation products of TMP and SMX were observed, especially in the reaction with hydroxyl radical. SO4(•-) and CO3(•-) reacted with pharmaceuticals by electron transfer, thus producing similar major products. The main reactive species deduced on the basis of product generation are in good agreement with kinetic simulation of the advanced oxidation processes. A strain identified as a polyphosphate-accumulating organism was used to investigate the antimicrobial activity of the pharmaceuticals and their products. No antimicrobial property was detected for the transformation products of either TMP or SMX. Acute toxicity employing luminescent bacterium Vibrio qinghaiensis indicated 20-40% higher inhibitory effect of TMP and SMX after treatment. Ecotoxicity was estimated by quantitative structure-activity relationship analysis using ECOSAR.

  12. Photodissociation Cross Sections and Spectroscopy of Atmospheric Positive Ions

    DTIC Science & Technology

    1979-03-13

    MP 79-1 * ATNR~ e _____________________ CONTRAg T’. NUMNER(s) G. P. Smith, L. C. Lee, P. CCobJ. R. I . DA 9--C- /EPeter o J.: T.1 MoseASy PEFRMN...Photodissociation of positive ions can be an important power-loss process in e -beam and gas discharge lasers, and a genctal model should prove useful...monJel ca.l)olatioa i detibed is, Apm4i 0, 4 PHOTON ENERGY (eV) 1.5 2.0 2.5 3.0 3.5 24k NONO+ E 20E °This work Vanderhoff 0 . -Model calculation 16- z 0_ m

  13. The OH rotational population and photodissociation of H{sub 2}O in DG Tauri

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Carr, John S.; Najita, Joan R.

    2014-06-10

    We analyze the OH rotational emission in the Spitzer Space Telescope mid-infrared spectrum of the T Tauri star DG Tau. OH is observed in emission from upper level energies of 1900 K to 28,000 K. The rotational diagram cannot be fit with any single combination of temperature and column density and has slopes that correspond to excitation temperatures ranging from 200 K to 6000 K. The relative Λ-doublet population within each rotational level is not equal, showing that the OH population is not in thermal equilibrium. The symmetric Λ-doublet state is preferred in all rotational states, with an average ofmore » 0.5 for the population ratio of the anti-symmetric to symmetric state. We show that the population distribution of the high rotational lines and the Λ-doublet ratio are consistent with the formation of OH following the photo-dissociation of H{sub 2}O by FUV photons in the second absorption band of water (∼1150-1400 Å), which includes Lyα. Other processes, OH formation from either photo-dissociation of water in the first absorption band (1450-1900 Å) or the reaction O({sup 1} D) + H{sub 2}, or collisional excitation, cannot explain the observed emission in the high rotational states but could potentially contribute to the population of lower rotational levels. These results demonstrate that the photodissociation of water is active in DG Tau and support the idea that the hot rotational OH emission commonly observed in Classical T Tauri stars is due to the dissociation of H{sub 2}O by FUV radiation.« less

  14. Ultrafast photodissociation dynamics of 1,4-diiodobenzene

    NASA Astrophysics Data System (ADS)

    Stankus, Brian; Zotev, Nikola; Rogers, David M.; Gao, Yan; Odate, Asami; Kirrander, Adam; Weber, Peter M.

    2018-05-01

    The photodissociation dynamics of 1,4-diiodobenzene is investigated using ultrafast time-resolved photoelectron spectroscopy. Following excitation by laser pulses at 271 nm, the excited-state dynamics is probed by resonance-enhanced multiphoton ionization with 405 nm probe pulses. A progression of Rydberg states, which come into resonance sequentially, provide a fingerprint of the dissociation dynamics of the molecule. The initial excitation decays with a lifetime of 33 ± 4 fs, in good agreement with a previous study. The spectrum is interpreted by reference to ab initio calculations at the CASPT2(18,14) level, including spin-orbit coupling. We propose that both the 5B1 and 6B1 states are excited initially, and based on the calculations, we identify diabatic spin-orbit coupled states corresponding to the main dissociation pathways.

  15. Insights into the deactivation of 5-bromouracil after ultraviolet excitation

    NASA Astrophysics Data System (ADS)

    Peccati, Francesca; Mai, Sebastian; González, Leticia

    2017-03-01

    5-Bromouracil is a nucleobase analogue that can replace thymine in DNA strands and acts as a strong radiosensitizer, with potential applications in molecular biology and cancer therapy. Here, the deactivation of 5-bromouracil after ultraviolet irradiation is investigated in the singlet and triplet manifold by accurate quantum chemistry calculations and non-adiabatic dynamics simulations. It is found that, after irradiation to the bright ππ* state, three main relaxation pathways are, in principle, possible: relaxation back to the ground state, intersystem crossing (ISC) and C-Br photodissociation. Based on accurate MS-CASPT2 optimizations, we propose that ground-state relaxation should be the predominant deactivation pathway in the gas phase. We then employ different electronic structure methods to assess their suitability to carry out excited-state dynamics simulations. MRCIS (multi-reference configuration interaction including single excitations) was used in surface hopping simulations to compute the ultrafast ISC dynamics, which mostly involves the 1nOπ* and 3ππ* states. This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'.

  16. Insights into the deactivation of 5-bromouracil after ultraviolet excitation

    PubMed Central

    2017-01-01

    5-Bromouracil is a nucleobase analogue that can replace thymine in DNA strands and acts as a strong radiosensitizer, with potential applications in molecular biology and cancer therapy. Here, the deactivation of 5-bromouracil after ultraviolet irradiation is investigated in the singlet and triplet manifold by accurate quantum chemistry calculations and non-adiabatic dynamics simulations. It is found that, after irradiation to the bright ππ* state, three main relaxation pathways are, in principle, possible: relaxation back to the ground state, intersystem crossing (ISC) and C–Br photodissociation. Based on accurate MS-CASPT2 optimizations, we propose that ground-state relaxation should be the predominant deactivation pathway in the gas phase. We then employ different electronic structure methods to assess their suitability to carry out excited-state dynamics simulations. MRCIS (multi-reference configuration interaction including single excitations) was used in surface hopping simulations to compute the ultrafast ISC dynamics, which mostly involves the 1nOπ* and 3ππ* states. This article is part of the themed issue ‘Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces’. PMID:28320905

  17. Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

    NASA Technical Reports Server (NTRS)

    Zhao, Z.; Stickel, R. E.; Wine, P. H.

    1995-01-01

    Tunable diode laser absorption spectroscopy has been coupled with excimer laser flash photolysis to measure the quantum yield for CO production from 248 nm photodissociation of carbonyl sulfide (OCS) relative to the well-known quantum yield for CO production from 248 nm photolysis of phosgene (Cl2CO2). The temporal resolution of the experiments was sufficient to distinguish CO formed directly by photodissociation from that formed by subsequent S((sup 3)P(sub J)) reaction with OCS. Under the experimental conditions employed, CO formation via the fast S((sup 1)D(sub 2)) + OCS reaction was minimal. Measurements at 297K and total pressures from 4 to 100 Torr N2 + N2O show the CO yield to be greater than 0.95 and most likely unity. This result suggests that the contribution of OCS as a precursor to the lower stratospheric sulfate aerosol layer is somewhat larger than previously thought.

  18. Massive isotopic effect in vacuum UV photodissociation of N2 and implications for meteorite data

    PubMed Central

    Chakraborty, Subrata; Muskatel, B. H.; Jackson, Teresa L.; Ahmed, Musahid; Levine, R. D.; Thiemens, Mark H.

    2014-01-01

    Nitrogen isotopic distributions in the solar system extend across an enormous range, from −400‰, in the solar wind and Jovian atmosphere, to about 5,000‰ in organic matter in carbonaceous chondrites. Distributions such as these require complex processing of nitrogen reservoirs and extraordinary isotope effects. While theoretical models invoke ion-neutral exchange reactions outside the protoplanetary disk and photochemical self-shielding on the disk surface to explain the variations, there are no experiments to substantiate these models. Experimental results of N2 photolysis at vacuum UV wavelengths in the presence of hydrogen are presented here, which show a wide range of enriched δ15N values from 648‰ to 13,412‰ in product NH3, depending upon photodissociation wavelength. The measured enrichment range in photodissociation of N2, plausibly explains the range of δ15N in extraterrestrial materials. This study suggests the importance of photochemical processing of the nitrogen reservoirs within the solar nebula. PMID:25267643

  19. New insights into photodissociation dynamics of cyclobutanone from the AIMS dynamic simulation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, Lihong; Fang, Wei-Hai, E-mail: fangwh@bnu.edu.cn

    2016-04-14

    In this work, the combined electronic structure calculations and non-adiabatic dynamics simulations were performed for understanding mechanistic photodissociation of cyclobutanone at ∼248 nm. Besides the stationary and intersection structures reported before, two new conical intersections between the ground (S{sub 0}) and the first excited singlet (S{sub 1}) states were determined in the present study, which were confirmed to be the new S{sub 1} → S{sub 0} funnels by the ab initio multiple spawning dynamic simulation, giving rise to products in the S{sub 0} state selectively. The time evolution of the S{sub 1} electronic population was fitted with the pure exponentialmore » formulae, from which the S{sub 1} lifetime was estimated to be 484.0 fs. The time constant for the S{sub 1} α-cleavage is calculated to be 176.6 fs, which is based on the present dynamics simulation. As a result of the ultrafast S{sub 1} processes, the statistical distribution of the excess energies is prevented in the S{sub 1} state. The S{sub 1} dynamic effect (the nonergodic behavior) was predicted to be an important factor that is responsible for the wavelength dependence of the branching ratio of photodissociation products, which will be discussed in detail.« less

  20. Multiple product pathways in photodissociation of nitromethane at 213 nm

    NASA Astrophysics Data System (ADS)

    Sumida, Masataka; Kohge, Yasunori; Yamasaki, Katsuyoshi; Kohguchi, Hiroshi

    2016-02-01

    In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π* transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH3, NO(X 2Π, A 2Σ+), and O(3PJ) photofragments. The rotationally state-resolved scattering distribution of the CH3 fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH3 fragment indicated the production of the NO2 counter-product in the electronic excited state, wherein 1 2B2 was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O(3PJ) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A 2Σ+) fragment, which was detected by ionization spectroscopy via the Rydberg ←A 2Σ+ transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH3 + NO2,CH3 + NO + O,CH3O + NO, and CH3NO + O, following the π → π* transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.

  1. Multiple product pathways in photodissociation of nitromethane at 213 nm.

    PubMed

    Sumida, Masataka; Kohge, Yasunori; Yamasaki, Katsuyoshi; Kohguchi, Hiroshi

    2016-02-14

    In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π(*) transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH3, NO(X (2)Π, A (2)Σ(+)), and O((3)PJ) photofragments. The rotationally state-resolved scattering distribution of the CH3 fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH3 fragment indicated the production of the NO2 counter-product in the electronic excited state, wherein 1 (2)B2 was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O((3)PJ) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A (2)Σ(+)) fragment, which was detected by ionization spectroscopy via the Rydberg ← A (2)Σ(+) transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH3 + NO2,CH3 + NO + O,CH3O + NO, and CH3NO + O, following the π → π(*) transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.

  2. Photodissociation pathways and lifetimes of protonated peptides and their dimers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Aravind, G.; Klaerke, B.; Rajput, J.

    2012-01-07

    Photodissociation lifetimes and fragment channels of gas-phase, protonated YA{sub n} (n = 1,2) peptides and their dimers were measured with 266 nm photons. The protonated monomers were found to have a fast dissociation channel with an exponential lifetime of {approx}200 ns while the protonated dimers show an additional slow dissociation component with a lifetime of {approx}2 {mu}s. Laser power dependence measurements enabled us to ascribe the fast channel in the monomer and the slow channel in the dimer to a one-photon process, whereas the fast dimer channel is from a two-photon process. The slow (1 photon) dissociation channel in themore » dimer was found to result in cleavage of the H-bonds after energy transfer through these H-bonds. In general, the dissociation of these protonated peptides is non-prompt and the decay time was found to increase with the size of the peptides. Quantum RRKM calculations of the microcanonical rate constants also confirmed a statistical nature of the photodissociation processes in the dipeptide monomers and dimers. The classical RRKM expression gives a rate constant as an analytical function of the number of active vibrational modes in the system, estimated separately on the basis of the equipartition theorem. It demonstrates encouraging results in predicting fragmentation lifetimes of protonated peptides. Finally, we present the first experimental evidence for a photo-induced conversion of tyrosine-containing peptides into monocyclic aromatic hydrocarbon along with a formamide molecule both found in space.« less

  3. Electronic spectroscopy and photodissociation dynamics of Co(2+)-methanol clusters: Co2+ (CH3OH)n (n = 4-7).

    PubMed

    Thompson, Christopher J; Faherty, Kieron P; Stringer, Kay L; Metz, Ricardo B

    2005-03-07

    Solvated cluster ions Co2+ (CH3OH)n (n = 4-7) have been produced by electrospray and studied using photofragment spectroscopy. There are notable differences between the photodissociation spectra of these complexes and the analogous water complexes. Co2+ (CH3OH)6 absorbs significantly more strongly than Co2+ (H2O)6. The photodissociation spectra of Co2+ (CH3OH)n (n = 4, 5 and 6) are very similar, which suggests that they share the Co2+ (CH3OH)4 chromophore, with additional solvent molecules in the second shell. In contrast, our earlier studies indicate that Co2+ (H2O)6 is six coordinate, and its spectrum is significantly different from that of Co2+ (H2O)4. The larger clusters Co2+ (CH3OH)n (n = 5-7) dissociate by simple loss of one or more solvent molecules. Larger clusters tend to lose more solvent molecules, especially at higher photon energies. As with the corresponding water cluster, Co2+ (CH3OH)4 photodissociates by proton transfer through a salt-bridge intermediate. This is accompanied by a modest kinetic energy release of 170 kJ mol(-1) and occurs with a lifetime of 145 ns.

  4. Transient isomers in the photodissociation of bromoiodomethane

    NASA Astrophysics Data System (ADS)

    Marcellini, Moreno; Nasedkin, Alexandr; Zietz, Burkhard; Petersson, Jonas; Vincent, Jonathan; Palazzetti, Federico; Malmerberg, Erik; Kong, Qingyu; Wulff, Michael; van der Spoel, David; Neutze, Richard; Davidsson, Jan

    2018-04-01

    The photochemistry of halomethanes is fascinating for the complex cascade reactions toward either the parent or newly synthesized molecules. Here, we address the structural rearrangement of photodissociated CH2IBr in methanol and cyclohexane, probed by time-resolved X-ray scattering in liquid solution. Upon selective laser cleavage of the C-I bond, we follow the reaction cascade of the two geminate geometrical isomers, CH2I-Br and CH2Br-I. Both meta-stable isomers decay on different time scales, mediated by solvent interaction, toward the original parent molecule. We observe the internal rearrangement of CH2Br-I to CH2I-Br in cyclohexane by extending the time window up to 3 μs. We track the photoproduct kinetics of CH2Br-I in methanol solution where only one isomer is observed. The effect of the polarity of solvent on the geminate recombination pathways is discussed.

  5. Primary quantum yields of NO2 photodissociation

    NASA Technical Reports Server (NTRS)

    Gardner, Edward P.; Sperry, Paul D.; Calvert, Jack G.

    1987-01-01

    The quantum yields of formation of NO, O2, and NO2 loss are measured for NO2 vapor at low pressures (0.13-0.30 torr) irradiated at 334-405 nm wavelengths and temperature in the range 273-370 K in order to study the primary quantum efficiencies of NO2 photodecomposition. The temperature and wavelength dependences of the primary quantum efficiencies are examined. It is observed that the primary quantum efficiencies increase rapidly from near zero at 424 nm to near unity for excitation at wavelengths less than 394 nm. The theory of Pitts et al. (1964) that the energy deficiency for photodissociation of NO2 excited at wavelengths greater than 397.9 nm is due to the rotational and vibrational energy of the NO2 molecules is confirmed by the data. Values for the primary quantum yields of NO2 photodecomposition as a function of wavelength are presented.

  6. The photodissociation lifetimes of the OH and OD radicals in comets

    NASA Technical Reports Server (NTRS)

    Singh, P. D.; Van Dishoeck, E. F.; Dalgarno, A.

    1983-01-01

    The photodissociation rates of OH and OD molecules due to absorption of solar radiation in the X(2)Pi-A(2)Sigma(+) electronic transition are calculated to lie between 3.5 and 6.7 x 10 to the -6th/sec for OH for heliocentric velocities between -60 and +60 km/sec and at about 4.7 x 10 to the -7th/sec for OD at 1 AU from the sun. The corresponding lifetimes, which are upper bounds to the actual lifetimes, are generally consistent with the observational cometary data.

  7. 157 nm Photodissociation of Dipeptide Ions Containing N-Terminal Arginine

    NASA Astrophysics Data System (ADS)

    Webber, Nathaniel; He, Yi; Reilly, James P.

    2014-02-01

    Twenty singly-charged dipeptide ions with N-terminal arginine were photodissociated using 157 nm light in both a linear ion-trap mass spectrometer and a MALDI-TOF-TOF mass spectrometer. Analogous to previous work on dipeptides containing C-terminal arginine, this set of samples enabled insights into the photofragmentation propensities associated with individual residues. In addition to familiar products such as a-, d-, and immonium ions, m2 and m2+13 ions were also observed. Certain side chains tended to cleave between their β and γ carbons without necessarily forming d- or w-type ions, and a few other ions were produced by the high-energy fragmentation of multiple bonds.

  8. Photoabsorption and photodissociation of molecules important in the interstellar medium

    NASA Technical Reports Server (NTRS)

    Lee, Long C.; Suto, Masako

    1991-01-01

    The photoabsorption, photodissociation, and fluorescence cross sections of interstellar molecules are measured at 90 to 250 nm. These quantitative optical data are needed for the understanding of the formation and destruction processes of molecules under the intense interstellar UV radiation field. Research covering the following topics is presented: (1) fluorescences from photoexcitation of CH4, CH3OH, and CH3SH; (2) NO gamma emission from photoexcitation of NO; (3) photoexcitation cross sections of aromatic molecules; (4) IR emission from UV excitation of HONO2; (5) IR emission from UV excitation of benzene and methyl-derivitives; and (6) IR emission from UV excitation of polycyclic aromatic hydrocarbon molecules.

  9. Initial state-specific photodissociation dynamics of pyrrole via 1 π σ ∗/ S 0 conical intersection initiated with optimally controlled UV-laser pulses

    NASA Astrophysics Data System (ADS)

    Nandipati, K. R.; Kanakati, Arun Kumar; Singh, H.; Lan, Z.; Mahapatra, S.

    2017-09-01

    Optimal initiation of quantum dynamics of N-H photodissociation of pyrrole on the S0-1πσ∗(1A2) coupled electronic states by UV-laser pulses in an effort to guide the subsequent dynamics to dissociation limits is studied theoretically. Specifically, the task of designing optimal laser pulses that act on initial vibrational states of the system for an effective UV-photodissociation is considered by employing optimal control theory. The associated control mechanism(s) for the initial state dependent photodissociation dynamics of pyrrole in the presence of control pulses is examined and discussed in detail. The initial conditions determine implicitly the variation in the dissociation probabilities for the two channels, upon interaction with the field. The optimal pulse corresponds to the objective fixed as maximization of overall reactive flux subject to constraints of reasonable fluence and quantum dynamics. The simple optimal pulses obtained by the use of genetic algorithm based optimization are worth an experimental implementation given the experimental relevance of πσ∗-photochemistry in recent times.

  10. Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

    2015-07-01

    Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90 %). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize product yields and to identify side products. The present work demonstrates that UV-LED arrays are a viable alternative to current Hg lamp setups.

  11. Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 22A(3s) Rydberg state

    NASA Astrophysics Data System (ADS)

    Xie, Changjian; Guo, Hua

    2018-01-01

    The choice of the active degrees of freedom (DOFs) is a pivotal issue in a reduced-dimensional model of quantum dynamics when a full-dimensional one is not feasible. Here, several five-dimensional (5D) models are used to investigate the nonadiabatic photodissociation dynamics of the hydroxymethyl (CH2OH) radical, which possesses nine internal DOFs, in its lowest absorption band. A normal-mode based scheme is used to identify the active and spectator modes, and its predictions are confirmed by 5D quantum dynamical calculations. Our results underscore the important role of the CO stretching mode in the photodissociation dynamics of CH2OH, originating from the photo-induced promotion of an electron from the half-occupied π*CO antibonding orbital to a carbon Rydberg orbital.

  12. Multiple product pathways in photodissociation of nitromethane at 213 nm

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sumida, Masataka; Kohge, Yasunori; Yamasaki, Katsuyoshi

    2016-02-14

    In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π{sup *} transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH{sub 3}, NO(X {sup 2}Π, A {sup 2}Σ{sup +}), and O({sup 3}P{sub J}) photofragments. The rotationally state-resolved scattering distribution of the CH{sub 3} fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH{sub 3} fragment indicated the production of themore » NO{sub 2} counter-product in the electronic excited state, wherein 1 {sup 2}B{sub 2} was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O({sup 3}P{sub J}) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A {sup 2}Σ{sup +}) fragment, which was detected by ionization spectroscopy via the Rydberg ←A {sup 2}Σ{sup +} transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH{sub 3} + NO{sub 2},CH{sub 3} + NO + O,CH{sub 3}O + NO, and CH{sub 3}NO + O, following the π → π{sup *} transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.« less

  13. The photodissociation dynamics of alkyl radicals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Giegerich, Jens; Fischer, Ingo, E-mail: ingo.fischer@uni-wuerzburg.de

    2015-01-28

    The photodisscociation dynamics of the alkyl radicals i-propyl (CH(CH{sub 3}){sub 2}) and t-butyl (C(CH{sub 3}){sub 3}) are investigated by H-atom photofragment imaging. While i-propyl is excited at 250 nm, the photodynamics of t-butyl are explored over a large energy range using excitation wavelengths between 347 nm and 233 nm. The results are compared to those obtained previously for ethyl, CH{sub 3}CH{sub 2}, and to those reported for t-butyl using 248 nm excitation. The translational energy (E{sub T}) distribution of the H-atom photofragments is bimodal and appears rather similar for all three radicals. The low E{sub T} part of the distributionmore » shows an isotropic photofragment angular distribution, while the high E{sub T} part is associated with a considerable anisotropy. Thus, for t-butyl, two H-atom loss channels of roughly equal importance have been identified in addition to the CH{sub 3}-loss channel reported previously. A mechanism for the photodissociation of alkyl radicals is suggested that is based on interactions between Rydberg- and valence states.« less

  14. Photodissociation of the carbon monoxide dication in the (3)Σ(-) manifold: Quantum control simulation towards the C(2+) + O channel.

    PubMed

    Vranckx, S; Loreau, J; Vaeck, N; Meier, C; Desouter-Lecomte, M

    2015-10-28

    The photodissociation and laser assisted dissociation of the carbon monoxide dication X(3)Π CO(2+) into the (3)Σ(-) states are investigated. Ab initio electronic structure calculations of the adiabatic potential energy curves, radial nonadiabatic couplings, and dipole moments for the X (3)Π state are performed for 13 excited (3)Σ(-) states of CO(2+). The photodissociation cross section, calculated by time-dependent methods, shows that the C(+) + O(+) channels dominate the process in the studied energy range. The carbon monoxide dication CO(2+) is an interesting candidate for control because it can be produced in a single, long lived, v = 0 vibrational state due to the instability of all the other excited vibrational states of the ground (3)Π electronic state. In a spectral range of about 25 eV, perpendicular transition dipoles couple this (3)Π state to a manifold of (3)Σ(-) excited states leading to numerous C(+) + O(+) channels and a single C(2+) + O channel. This unique channel is used as target for control calculations using local control theory. We illustrate the efficiency of this method in order to find a tailored electric field driving the photodissociation in a manifold of strongly interacting electronic states. The selected local pulses are then concatenated in a sequence inspired by the "laser distillation" strategy. Finally, the local pulse is compared with optimal control theory.

  15. Protein relaxation without a geminate phase in nanosecond photodissociated CO carp hemoglobin

    NASA Astrophysics Data System (ADS)

    Loupiac, Camille; Kruk, Nicolay; Valat, Pierre; Alpert, Bernard

    1999-03-01

    Transient heme-protein interactions upon passing from ligated to deligated carp hemoglobin were observed through time-resolved optical spectra following nanosecond CO photodissociation. The spectral evolution of the heme, in the nanosecond and microsecond time ranges, shows a protein conformational relaxation and the absence of a geminate CO recombination in carp hemoglobin. The comparison of the phenomena in carp and human hemoglobin implies that the physical basis of the geminate rebinding in human hemoglobin should involve an out-of-equilibrium protein conformation, close to a dissipative structure defined by the thermodynamics of Prigogine.

  16. [Photodissociation of Acetylene and Acetone using Step-Scan Time-Resolved FTIR Emission Spectroscopy

    NASA Technical Reports Server (NTRS)

    McLaren, Ian A.; Wrobel, Jacek D.

    1997-01-01

    The photodissociation of acetylene and acetone was investigated as a function of added quenching gas pressures using step-scan time-resolved FTIR emission spectroscopy. Its main components consist of Bruker IFS88, step-scan Fourier Transform Infrared (FTIR) spectrometer coupled to a flow cell equipped with Welsh collection optics. Vibrationally excited C2H radicals were produced from the photodissociation of acetylene in the unfocused experiments. The infrared (IR) emission from these excited C2H radicals was investigated as a function of added argon pressure. Argon quenching rate constants for all C2H emission bands are of the order of 10(exp -13)cc/molecule.sec. Quenching of these radicals by acetylene is efficient, with a rate constant in the range of 10(exp -11) cc/molecule.sec. The relative intensity of the different C2H emission bands did not change with the increasing argon or acetylene pressure. However, the overall IR emission intensity decreased, for example, by more than 50% when the argon partial pressure was raised from 0.2 to 2 Torr at fixed precursor pressure of 160mTorr. These observations provide evidence for the formation of a metastable C2H2 species, which are collisionally quenched by argon or acetylene. Problems encountered in the course of the experimental work are also described.

  17. DFT/TDDFT study on the photodissociation mechanism of the original monascus red and orange pigments

    NASA Astrophysics Data System (ADS)

    Liu, Yi; Wu, Li; Lv, Qingzhang

    2015-06-01

    The weak photostability has to some extent restricted the wide utilization of monascus pigments in food industries, and their photobleaching mechanism is unclear yet. Density functional theory and time-dependent density functional theory at B3LYP/6-311+G(d,p) level have been performed to optimize the geometries of ground states, single and triplet excited-states of the original monascus red and orange pigments, the possible photodissociation mechanism of which is analyzed according to the calculated data. It is the break of the chromophores, conjugated π bonds which has induced their decoloration. The photodissociation of these pigments involves three steps, excitation of the large conjugated π system, water addition to the singlet or triplet excited-state, and Norrish type I photochemical cleavage reactions of the side chains. The former two steps are much more important steps which have led to the destruction of the chromophores and the fading of the four original monascus red and orange pigments. According to the photobleaching mechanism obtained, one could find some solutions to enhance the photostability of these monascus colorants during the food processing process and extend the shelf life of the foods added with monascus pigments.

  18. Ultraviolet Extensions

    NASA Technical Reports Server (NTRS)

    2008-01-01

    [figure removed for brevity, see original site] Side-by-Side Comparison Click on image for larger view

    This ultraviolet image from NASA's Galaxy Evolution Explorer shows the Southern Pinwheel galaxy, also know as Messier 83 or M83. It is located 15 million light-years away in the southern constellation Hydra.

    Ultraviolet light traces young populations of stars; in this image, young stars can be seen way beyond the main spiral disk of M83 up to 140,000 light-years from its center. Could life exist around one of these far-flung stars? Scientists say it's unlikely because the outlying regions of a galaxy are lacking in the metals required for planets to form.

    The image was taken at scheduled intervals between March 15 and May 20, 2007. It is one of the longest-exposure, or deepest, images ever taken of a nearby galaxy in ultraviolet light. Near-ultraviolet light (or longer-wavelength ultraviolet light) is colored yellow, and far-ultraviolet light is blue.

    What Lies Beyond the Edge of a Galaxy The side-by-side comparison shows the Southern Pinwheel galaxy, or M83, as seen in ultraviolet light (right) and at both ultraviolet and radio wavelengths (left). While the radio data highlight the galaxy's long, octopus-like arms stretching far beyond its main spiral disk (red), the ultraviolet data reveal clusters of baby stars (blue) within the extended arms.

    The ultraviolet image was taken by NASA's Galaxy Evolution Explorer between March 15 and May 20, 2007, at scheduled intervals. Back in 2005, the telescope first photographed M83 over a shorter period of time. That picture was the first to reveal far-flung baby stars forming up to 63,000 light-years from the edge of the main spiral disk. This came as a surprise to astronomers because a galaxy's outer territory typically lacks high densities of star-forming materials.

    The newest picture of M83 from the Galaxy Evolution Explorer is shown at the right, and was taken over a longer period of

  19. Tracking the photodissociation dynamics of liquid nitromethane at 266 nm by femtosecond time-resolved broadband transient grating spectroscopy

    NASA Astrophysics Data System (ADS)

    Wu, Honglin; Song, Yunfei; Yu, Guoyang; Wang, Yang; Wang, Chang; Yang, Yanqiang

    2016-05-01

    Femtosecond time-resolved transient grating (TG) technique was employed to get insight into the photodissociation mechanism of liquid nitromethane (NM). Broadband white-light continuum was introduced as the probe to observe the evolution of electronic excited states of NM molecules and the formation of photodissociation products simultaneously. The reaction channel of liquid NM under 266 nm excitation was obtained that NM molecules in excited state S2 relax through two channels: about 73% relax to low lying S1 state through S2/S1 internal conversion with a time constant of 0.24 ps and then go back to the ground state through S1/S0 internal conversion; the other 27% will dissociate with a time constant of 2.56 ps. NO2 was found to be one of the products from the experimental TG spectra, which confirmed that C-N bond rupture was the primary dissociation channel of liquid NM.

  20. Photodissociation of methyl formate: Conical intersections, roaming and triple fragmentation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lin, King-Chuen; Tsai, Po-Yu; Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan

    2015-12-31

    The photodissociation channels of methyl formate have been extensively investigated by two different advanced experimental techniques, ion imaging and Fourier-Transform-Infrared emission spectroscopy, combined with quantum chemical calculations and molecular dynamics simulations. Our aim is to characterize the role of alternative routes to the conventional transition-state mediated pathway: the roaming and the triple fragmentation processes. The photolysis experiments, carried out at a range of laser wavelengths in the vicinity of the triple fragmentation threshold, beside the simulation of large bunches of classical trajectories with different initial conditions, have shown that both mechanisms share a common path that involves a conical intersectionmore » during the relaxation process from the electronic excited state S{sub 1} to the ground state S{sub 0}.« less

  1. An alternative laser driven photodissociation mechanism of pyrrole via π*1σ/S0 conical intersection

    NASA Astrophysics Data System (ADS)

    Nandipati, K. R.; Lan, Z.; Singh, H.; Mahapatra, S.

    2017-06-01

    A first principles quantum dynamics study of N-H photodissociation of pyrrole on the S0-1π σ*(A12) coupled electronic states is carried out with the aid of an optimally designed UV-laser pulse. A new photodissociation path, as compared to the conventional barrier crossing on the π*1σ state, opens up upon electronic transitions under the influence of pump-dump laser pulses, which efficiently populate both the dissociation channels. The interplay of electronic transitions due both to vibronic coupling and the laser pulse is observed in the control mechanism and discussed in detail. The proposed control mechanism seems to be robust, and not discussed in the literature so far, and is expected to trigger future experiments on the π*1σ photochemistry of molecules of chemical and biological importance. The design of the optimal pulses and their application to enhance the overall dissociation probability is carried out within the framework of optimal control theory. The quantum dynamics of the system in the presence of pulse is treated by solving the time-dependent Schrödinger equation in the semi-classical dipole approximation.

  2. Ultrafast High Harmonic, Soft X-Ray Probing of Molecular Dynamics

    DTIC Science & Technology

    2013-04-30

    590 L/s scroll pump and a titanium sublimation pump . A TOF-PES has been designed and constructed to analyze the energy of the photoelectrons...are studied using the quasi-continuous vacuum ultraviolet light of the Advanced Light Source at Lawrence Berkeley National Laboratory. The molecular...34), the method of high order harmonic generation of ultrashort vacuum ultraviolet pulses was used to investigate molecular photodissociation, ultrafast

  3. Complex quantum Hamilton-Jacobi equation with Bohmian trajectories: Application to the photodissociation dynamics of NOCl

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chou, Chia-Chun, E-mail: ccchou@mx.nthu.edu.tw

    2014-03-14

    The complex quantum Hamilton-Jacobi equation-Bohmian trajectories (CQHJE-BT) method is introduced as a synthetic trajectory method for integrating the complex quantum Hamilton-Jacobi equation for the complex action function by propagating an ensemble of real-valued correlated Bohmian trajectories. Substituting the wave function expressed in exponential form in terms of the complex action into the time-dependent Schrödinger equation yields the complex quantum Hamilton-Jacobi equation. We transform this equation into the arbitrary Lagrangian-Eulerian version with the grid velocity matching the flow velocity of the probability fluid. The resulting equation describing the rate of change in the complex action transported along Bohmian trajectories is simultaneouslymore » integrated with the guidance equation for Bohmian trajectories, and the time-dependent wave function is readily synthesized. The spatial derivatives of the complex action required for the integration scheme are obtained by solving one moving least squares matrix equation. In addition, the method is applied to the photodissociation of NOCl. The photodissociation dynamics of NOCl can be accurately described by propagating a small ensemble of trajectories. This study demonstrates that the CQHJE-BT method combines the considerable advantages of both the real and the complex quantum trajectory methods previously developed for wave packet dynamics.« less

  4. Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light emitting diodes

    NASA Astrophysics Data System (ADS)

    Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

    2015-01-01

    Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90%). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize products yields and to identify side products. The use of UV-LED arrays offers many advantages over conventional Hg lamp setups, including greater light output over a narrower wavelength range, lower power consumption, and minimal generation of heat.

  5. Research in extreme ultraviolet and far ultraviolet astronomy

    NASA Technical Reports Server (NTRS)

    Labov, S. E.

    1985-01-01

    Instruments designed to explore different aspects of far and extreme ultraviolet cosmic radiation were studied. The far ultraviolet imager (FUVI) was flown on the Aries sounding rocket. Its unique large format 75mm detector mapped out the far ultraviolet background radiation with a resolution of only a few arc minutes. Analysis of this data indicates to what extent the FUVI background is extra galactic in origin. A power spectrum of the spatial fluctuations will have direct consequences for galactic evolution.

  6. Rotational and angular distributions of NO products from NO-Rg(Rg = He, Ne, Ar) complex photodissociation

    DOE PAGES

    Heather L. Holmes-Ross; Hall, Gregory E.; Valenti, Rebecca J.; ...

    2016-01-29

    In this study, we present the results of an investigation into the rotational and angular distributions of the NO A ~ state fragment following photodissociation of the NO-He, NO-Ne and NO-Ar van der Waals complexed excited via the A ~ ← X ~ transition. For each complex the dissociation is probed for several values of E a, the available energy above the dissociation threshold.

  7. Measurement of the photodissociation of the deuteron at energies relevant to Big Bang nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Hannaske, R.; Bemmerer, D.; Beyer, R.; Birgersson, E.; Ferrari, A.; Grosse, E.; Junghans, A. R.; Kempe, M.; Kögler, T.; Kosev, K.; Marta, M.; Massarczyk, R.; Matic, A.; Schilling, K. D.; Schramm, G.; Schwengner, R.; Wagner, A.; Yakorev, D.

    2016-01-01

    The photodissociation of the deuteron is a key reaction in Big Bang nucleosynthesis, but is only sparsely measured in the relevant energy range. To determine the cross section of the d(γ,n)p reaction we used pulsed bremsstrahlung and measured the time-of-flight of the neutrons. In this article, we describe how the efficiency of the neutron detectors was experimentally determined and how the modification of the neutron spectrum by parts of the experimental setup was simulated and corrected.

  8. Optical control of ground-state atomic orbital alignment: Cl(2P3/2) atoms from HCl(v=2,J=1) photodissociation.

    PubMed

    Sofikitis, Dimitris; Rubio-Lago, Luis; Martin, Marion R; Ankeny Brown, Davida J; Bartlett, Nathaniel C-M; Alexander, Andrew J; Zare, Richard N; Rakitzis, T Peter

    2007-10-14

    H(35)Cl(v=0,J=0) molecules in a supersonic expansion were excited to the H(35)Cl(v=2,J=1,M=0) state with linearly polarized laser pulses at about 1.7 microm. These rotationally aligned J=1 molecules were then selectively photodissociated with a linearly polarized laser pulse at 220 nm after a time delay, and the velocity-dependent alignment of the (35)Cl((2)P(32)) photofragments was measured using 2+1 REMPI and time-of-flight mass spectrometry. The (35)Cl((2)P(32)) atoms are aligned by two mechanisms: (1) the time-dependent transfer of rotational polarization of the H(35)Cl(v=2,J=1,M=0) molecule to the (35)Cl((2)P(32)) nuclear spin [which is conserved during the photodissociation and thus contributes to the total (35)Cl((2)P(32)) photofragment atomic polarization] and (2) the alignment of the (35)Cl((2)P(32)) electronic polarization resulting from the photoexcitation and dissociation process. The total alignment of the (35)Cl((2)P(32)) photofragments from these two mechanisms was found to vary as a function of time delay between the excitation and the photolysis laser pulses, in agreement with theoretical predictions. We show that the alignment of the ground-state (35)Cl((2)P(32)) atoms, with respect to the photodissociation recoil direction, can be controlled optically. Potential applications include the study of alignment-dependent collision effects.

  9. Products and yields from O3 photodissociation at 1576 A

    NASA Technical Reports Server (NTRS)

    Taherian, M. R.; Slanger, T. G.

    1985-01-01

    An analysis has been made of the primary atomic and molecular products arising from O3 photodissociation at 1576 A. The yield of oxygen atoms is 1.90 + or - 0.30, of which 71 percent are O(3P) and 29 percent are O(1D). Since a primary yield greater than unity can only be a consequence of three-fragment dissociation, these results suggest that fragmentation into three O(3P) atoms, and production of O(1D) plus a singlet oxygen molecule, have comparable yields. Observation of prompt emission in the 7300-8100 A spectral region indicates that the singlet O2 is O2(b 1Sigma + g). Vibrational levels in the range v = 0-6 have been detected, the distribution corresponding to a vibrational temperature of 1000 K.

  10. Photodissociation dynamics of the methyl perthiyl radical at 248 and 193 nm using fast-beam photofragment translational spectroscopy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Harrison, Aaron W.; Ryazanov, Mikhail; Sullivan, Erin N.

    2016-07-14

    The photodissociation dynamics of the methyl perthiyl radical (CH{sub 3}SS) have been investigated using fast-beam coincidence translational spectroscopy. Methyl perthiyl radicals were produced by photodetachment of the CH{sub 3}SS{sup −} anion followed by photodissociation at 248 nm (5.0 eV) and 193 nm (6.4 eV). Photofragment mass distributions and translational energy distributions were measured at each dissociation wavelength. Experimental results show S atom loss as the dominant (96%) dissociation channel at 248 nm with a near parallel, anisotropic angular distribution and translational energy peaking near the maximal energy available to ground state CH{sub 3}S and S fragments, indicating that the dissociationmore » occurs along a repulsive excited state. At 193 nm, S atom loss remains the major fragmentation channel, although S{sub 2} loss becomes more competitive and constitutes 32% of the fragmentation. The translational energy distributions for both channels are very broad at this wavelength, suggesting the formation of the S{sub 2} and S atom products in several excited electronic states.« less

  11. Tuning the ultrafast photodissociation dynamics of CH3Br on ultrathin MgO films by reducing the layer thickness to the 2D limit

    NASA Astrophysics Data System (ADS)

    Vaida, Mihai E.; Bernhardt, Thorsten M.

    2017-11-01

    The femtosecond-laser induced photodissociation of CH3Br adsorbed at sub-monolayer coverage on a solid surface was investigated by time-resolved pump-probe mass spectrometry. To tune the interaction of the CH3Br molecules with the substrate, an Mo(1 0 0) surface was covered with ultrathin insulating MgO layers of variable thickness. By gradually decreasing the magnesia layer thickness to the 2D limit the photodissociation dynamics observed by detection of the methyl fragment indicates an energetic lowering of the relevant methyl bromide excited states due to the increasing spatial proximity of the metallic support. Potential orientational effects of the methyl bromide adsorption geometry are also considered.

  12. An alternative laser driven photodissociation mechanism of pyrrole via πσ*1∕S0 conical intersection.

    PubMed

    Nandipati, K R; Lan, Z; Singh, H; Mahapatra, S

    2017-06-07

    A first principles quantum dynamics study of N-H photodissociation of pyrrole on the S 0 - 1 πσ * (A21) coupled electronic states is carried out with the aid of an optimally designed UV-laser pulse. A new photodissociation path, as compared to the conventional barrier crossing on the πσ*1 state, opens up upon electronic transitions under the influence of pump-dump laser pulses, which efficiently populate both the dissociation channels. The interplay of electronic transitions due both to vibronic coupling and the laser pulse is observed in the control mechanism and discussed in detail. The proposed control mechanism seems to be robust, and not discussed in the literature so far, and is expected to trigger future experiments on the πσ*1 photochemistry of molecules of chemical and biological importance. The design of the optimal pulses and their application to enhance the overall dissociation probability is carried out within the framework of optimal control theory. The quantum dynamics of the system in the presence of pulse is treated by solving the time-dependent Schrödinger equation in the semi-classical dipole approximation.

  13. An alternative laser driven photodissociation mechanism of pyrrole via πσ*1∕S0 conical intersection

    PubMed Central

    Nandipati, K. R.; Lan, Z.; Singh, H.; Mahapatra, S.

    2017-01-01

    A first principles quantum dynamics study of N–H photodissociation of pyrrole on the S0−1πσ*(A21) coupled electronic states is carried out with the aid of an optimally designed UV-laser pulse. A new photodissociation path, as compared to the conventional barrier crossing on the πσ*1 state, opens up upon electronic transitions under the influence of pump-dump laser pulses, which efficiently populate both the dissociation channels. The interplay of electronic transitions due both to vibronic coupling and the laser pulse is observed in the control mechanism and discussed in detail. The proposed control mechanism seems to be robust, and not discussed in the literature so far, and is expected to trigger future experiments on the πσ*1 photochemistry of molecules of chemical and biological importance. The design of the optimal pulses and their application to enhance the overall dissociation probability is carried out within the framework of optimal control theory. The quantum dynamics of the system in the presence of pulse is treated by solving the time-dependent Schrödinger equation in the semi-classical dipole approximation. PMID:28595406

  14. A Far-ultraviolet Fluorescent Molecular Hydrogen Emission Map of the Milky Way Galaxy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jo, Young-Soo; Min, Kyoung-Wook; Seon, Kwang-Il

    We present the far-ultraviolet (FUV) fluorescent molecular hydrogen (H{sub 2}) emission map of the Milky Way Galaxy obtained with FIMS/SPEAR covering ∼76% of the sky. The extinction-corrected intensity of the fluorescent H{sub 2} emission has a strong linear correlation with the well-known tracers of the cold interstellar medium (ISM), including color excess E(B–V) , neutral hydrogen column density N (H i), and H α emission. The all-sky H{sub 2} column density map was also obtained using a simple photodissociation region model and interstellar radiation fields derived from UV star catalogs. We estimated the fraction of H{sub 2} ( f {submore » H2}) and the gas-to-dust ratio (GDR) of the diffuse ISM. The f {sub H2} gradually increases from <1% at optically thin regions where E(B–V) < 0.1 to ∼50% for E(B–V)  = 3. The estimated GDR is ∼5.1 × 10{sup 21} atoms cm{sup −2} mag{sup −1}, in agreement with the standard value of 5.8 × 10{sup 21} atoms cm{sup −2} mag{sup −1}.« less

  15. Vacuum ultraviolet photoionization mass spectrometric study of cyclohexene.

    PubMed

    Chen, Jun; Cao, Maoqi; Wei, Bin; Ding, Mengmeng; Shan, Xiaobin; Liu, Fuyi; Sheng, Liusi

    2016-02-01

    In this work, photoionization and dissociation of cyclohexene have been studied by means of coupling a reflectron time-of-flight mass spectrometer with the tunable vacuum ultraviolet (VUV) synchrotron radiation. The adiabatic ionization energy of cyclohexene as well as the appearance energies of its fragment ions C6 H9 (+) , C6 H7 (+) , C5 H7 (+) , C5 H5 (+) , C4 H6 (+) , C4 H5 (+) , C3 H5 (+) and C3 H3 (+) were derived from the onset of the photoionization efficiency (PIE) curves. The optimized structures for the transition states and intermediates on the ground state potential energy surfaces related to photodissociation of cyclohexene were characterized at the ωB97X-D/6-31+g(d,p) level. The coupled cluster method, CCSD(T)/cc-pVTZ, was employed to calculate the corresponding energies with the zero-point energy corrections by the ωB97X-D/6-31+g(d,p) approach. Combining experimental and theoretical results, possible formation pathways of the fragment ions were proposed and discussed in detail. The retro-Cope rearrangement was found to play a crucial role in the formation of C4 H6 (+) , C4 H5 (+) and C3 H5 (+) . Intramolecular hydrogen migrations were observed as dominant processes in most of the fragmentation pathways of cyclohexene. The present research provides a clear picture of the photoionization and dissociation processes of cyclohexene in the 8- to 15.5-eV photon energy region. Copyright © 2016 John Wiley & Sons, Ltd.

  16. Noncontact optical detection of explosive particles via photodissociation followed by laser-induced fluorescence.

    PubMed

    Wynn, C M; Palmacci, S; Kunz, R R; Aernecke, M

    2011-09-12

    High-sensitivity (ng/cm²) optical detection of the explosive 2,4,6-trinitrotoluene (TNT) is demonstrated using photodissociation followed by laser-induced fluorescence (PD-LIF). Detection occurs rapidly, within 6 laser pulses (~7 ns each) at a range of 15 cm. Dropcasting is used to create calibrated samples covering a wide range of TNT concentrations; and a correspondence between fractional area covered by TNT and PD-LIF signal strength is observed. Dropcast data are compared to that of an actual fingerprint. These results demonstrate that PD-LIF could be a viable means of rapidly and remotely scanning surfaces for trace explosive residues.

  17. Photodissociation Efficiency Spectroscopy Study of the Rydberg Excited Ion-Pair States of Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Feng, Qiang; Xu, Yun-Feng; Sun, Jin-Da; Tian, Shan-Xi; Shan, Xiao-Bin; Liu, Fu-Yi; Sheng, Liu-Si

    2009-10-01

    Photodissociation efficiency spectrum of anionic oxygen atom produced via ion-pair dissociations of carbon dioxide is recorded by means of the synchrotron radiation excitation (XUV photon energy 17.40-20.00 eV). The present spectrum is assigned as the Rydberg-like excited ion-pair states, i.e., Tanaka-Ogawa and Henning series, tilde C2Σg+ (CO+2) vibrational ground-state and excitation series. Three Rydberg series, npσu, npπu, and nfu, converging to tilde C2Σg+ (0, 0, 0), show the higher cross sections.

  18. A velocity-map imaging study of methyl non-resonant multiphoton ionization from the photodissociation of CH3I in the A-band

    PubMed Central

    Poullain, Sonia Marggi; Chicharro, David V.; Rubio-Lago, Luis; García-Vela, Alberto

    2017-01-01

    Chemical reaction dynamics and, particularly, photodissociation in the gas phase are generally studied using pump–probe schemes where a first laser pulse induces the process under study and a second one detects the produced fragments. Providing an efficient detection of ro-vibrationally state-selected photofragments, the resonance enhanced multiphoton ionization (REMPI) technique is, without question, the most popular approach used for the probe step, while non-resonant multiphoton ionization (NRMPI) detection of the products is scarce. The main goal of this work is to test the sensitivity of the NRMPI technique to fragment vibrational distributions arising from molecular photodissociation processes. We revisit the well-known process of methyl iodide photodissociation in the A-band at around 280 nm, using the velocity-map imaging technique in conjunction with NRMPI of the methyl fragment. The detection wavelength, carefully selected to avoid any REMPI transition, was scanned between 325 and 335 nm seeking correlations between the different observables—the product vibrational, translational and angular distributions—and the excitation wavelength of the probe laser pulse. The experimental results have been discussed on the base of quantum dynamics calculations of photofragment vibrational populations carried out on available ab initio potential-energy surfaces using a four-dimensional model. This article is part of the themed issue ‘Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces’. PMID:28320907

  19. Lone-pair interactions and photodissociation of compressed nitrogen trifluoride

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kurzydłowski, D., E-mail: dkurzydlowski@uw.edu.pl; Department of Biogeochemistry, Max Planck Institute for Chemistry, 55128 Mainz; Wang, H. B.

    2014-08-14

    High-pressure behavior of nitrogen trifluoride (NF{sub 3}) was investigated by Raman and IR spectroscopy at pressures up to 55 GPa and room temperature, as well as by periodic calculations up to 100 GPa. Experimentally, we find three solid-solid phase transitions at 9, 18, and 39.5 GPa. Vibrational spectroscopy indicates that in all observed phases NF{sub 3} remains in the molecular form, in contrast to the behavior of compressed ammonia. This finding is confirmed by density functional theory calculations, which also indicate that the phase transitions of compressed NF{sub 3} are governed by the interplay between lone‑pair interactions and efficient moleculemore » packing. Although nitrogen trifluoride is molecular in the whole pressure range studied, we show that it can be photodissociated by mid-IR laser radiation. This finding paves the way for the use of NF{sub 3} as an oxidizing and fluorinating agent in high-pressure reactions.« less

  20. From planes to bowls: Photodissociation of the bisanthenequinone cation

    NASA Astrophysics Data System (ADS)

    Chen, Tao; Zhen, Junfeng; Wang, Ying; Linnartz, Harold; Tielens, Alexander G. G. M.

    2018-01-01

    We present a combined experimental and theoretical study of the photodissociation of the bisanthenequinone (C28H12O2) cation, Bq+. The experiments show that, upon photolysis, the Bq+ cation does not dehydrogenate, but instead fragments through the sequential loss of the two neutral carbonyl groups, causing the formation of five-membered carbon cycles. Quantum chemical calculations confirm this Bq+ → [Bq - CO]+ → [Bq - 2CO]+ sequence as the energetically most favorable reaction pathway. For the first CO loss, a transition state with a barrier of ∼3.2 eV is found, substantially lower than the lowest calculated H loss dissociation pathway (∼4.9 eV). A similar situation applies for the second CO loss channel (∼3.8 eV vs. ∼4.7 eV), but where the first dissociation step does not strongly alter the planar PAH geometry, the second step transforms the molecule into a bowl-shaped one.

  1. Dynamic photolytical actinometry of the vacuum-ultraviolet radiation produced by multichannel surface discharges of submicrosecond duration.

    PubMed

    Tcheremiskine, V I; Uteza, O P; Sentis, M L; Mikheev, L D

    2007-06-01

    Absolute measurements of the vacuum-ultraviolet (VUV) radiation power produced by a planar broadband optical source of submicrosecond light pulse duration are carried out in the transient regime of formation of a photodissociation (bleaching) wave in a photodecomposing absorptive medium. The source is based on a multichannel surface discharge initiated in ArN(2) gas mixtures on the area of approximately 0.1 m(2). The energetic characteristics of the produced VUV radiation are determined on the basis of spatially and temporally resolved observations of the pulsed photolysis of XeF(2) vapors. It is shown that the photon flux intensity produced by the source within the spectral range of 120-200 nm reaches 1.1 x 10(23) photonscm(2) s corresponding to the effective brightness temperature of discharge plasma of 20 kK and to the intrinsic efficiency of the discharge VUV emission of 3.2%. Numerical simulations of the photolysis process show a rather weak sensitivity of the results to the fraction of discharge radiation emitted into the line spectrum, as well as to the angular distribution of emitted radiation. The spectral band of measurements can be selected according to the choice of parent photodecomposing particles.

  2. Psoralen-ultraviolet A treatment with Psoralen-ultraviolet B therapy in the treatment of psoriasis.

    PubMed

    Ahmed Asim, Sadaf; Ahmed, Sitwat; Us-Sehar, Najam

    2013-05-01

    To compare the conventional psoralen-ultraviolet A treatment with psoralen-ultraviolet B therapy in the treatment of psoriasis. We studied 50 patients of plaque type psoriasis who were selected to receive either conventional psoralen-ultraviolet A or psoralen-ultraviolet B treatment. There was no significant difference between the two treatment groups in the number of patients whose skin cleared of psoriasis or the number of exposures required for clearance. Profile of side effects and disease status was also similar after three months of follow up. Psoralen-ultraviolet B treatment is as effective as conventional psoralen-ultraviolet A in the treatment of psoriasis. Further long term studies are needed to assess the safety of psoralen-ultraviolet B.

  3. Psoralen-ultraviolet A treatment with Psoralen-ultraviolet B therapy in the treatment of psoriasis

    PubMed Central

    Ahmed Asim, Sadaf; Ahmed, Sitwat; us-Sehar, Najam

    2013-01-01

    Objective: To compare the conventional psoralen-ultraviolet A treatment with psoralen-ultraviolet B therapy in the treatment of psoriasis. Methodology: We studied 50 patients of plaque type psoriasis who were selected to receive either conventional psoralen-ultraviolet A or psoralen-ultraviolet B treatment. Results: There was no significant difference between the two treatment groups in the number of patients whose skin cleared of psoriasis or the number of exposures required for clearance. Profile of side effects and disease status was also similar after three months of follow up. Conclusion: Psoralen-ultraviolet B treatment is as effective as conventional psoralen-ultraviolet A in the treatment of psoriasis. Further long term studies are needed to assess the safety of psoralen-ultraviolet B. PMID:24353623

  4. TD-DFT Insight into Photodissociation of Co-C Bond in Coenzyme B12

    NASA Astrophysics Data System (ADS)

    Kozlowski, Pawel; Liu, Hui; Kornobis, Karina; Lodowski, Piotr; Jaworska, Maria

    2013-12-01

    Coenzyme B12 (AdoCbl) is one of the most biologically active forms of vitamin B12, and continues to be a topic of active research interest. The mechanism of Co-C bond cleavage in AdoCbl, and the corresponding enzymatic reactions are however, not well understood at the molecular level. In this work, time-dependent density functional theory (TD-DFT) has been applied to investigate the photodissociation of coenzyme B12. To reduce computational cost, while retaining the major spectroscopic features of AdoCbl, a truncated model based on ribosylcobalamin (RibCbl) was used to simulate Co-C photodissociation. Equilibrium geometries of RibCbl were obtained by optimization at the DFT/BP86/TZVP level of theory, and low-lying excited states were calculated by TD-DFT using the same functional and basis set. The calculated singlet states, and absorption spectra were simulated in both the gas phase, and water, using the polarizable continuum model (PCM). Both spectra were in reasonable agreement with experimental data, and potential energy curves based on vertical excitations were plotted to explore the nature of Co-C bond dissociation. It was found that a repulsive 3(σCo-C → σ*Co-C) triplet state became dissociative at large Co-C bond distance, similar to a previous observation for methylcobalamin (MeCbl). Furthermore, potential energy surfaces (PESs) obtained as a function of both Co-CRib and Co-NIm distances, identify the S1 state as a key intermediate generated during photoexcitation of RibCbl, attributed to a mixture of a MLCT (metal-to-ligand charge transfer) and a σ bonding-ligand charge transfer (SBLCT) states.

  5. Correlated Photodissociation Dynamics of Small Molecules: Carbonyl Sulfide and Carbon Suboxide

    NASA Astrophysics Data System (ADS)

    Strauss, Charlie Elliott Murton

    1990-01-01

    The photodissociation of OCS and of C _3O_2 at 157.6 nm have been studied with full quantum state resolution of all fragments. Correlation of the independently measured fragment state distributions has been achieved without coincidence measurement via a maximum entropy method. For the experiments, dilute concentrations seeded in helium were expanded in a supersonic free jet, and the final state distribution of the CO, S, and C fragments were probed by tunable vacuum-ultraviolet laser induced fluorescence within 300 nanoseconds after photolysis by F_2 laser radiation. For OCS: Sulfur is produced almost entirely in its (^1S) state. Ground electronic state CO is produced in vibrational levels nu = 0 - 3 in the approximate ratio (1.0):(1.0):(0.5):(0.3). The rotational distribution for each vibrational level is nearly Boltzmann, with temperatures that decrease from 1350 K for nu = 0 to 780 K for nu = 3. CO Doppler profiles demonstrate that the absorption transition is of parallel character (beta = 1.8 +/- 0.2) and that the CO velocity and angular momentum vectors are perpendicular to one another. C_3O_2 dissociates into three fragments. Carbon is produced in its ^3P and ^1D states in the ratio (0.97):(0.03). CO is produced in vibrational levels nu = 0 - 4 in the ratio (0.57):(0.27):(0.1):(0.05):(<0.01). The rotational distributions are nearly Boltzmann with temperatures that increase from 3430 K for nu = 0 to 4670 K for nu = 2. Doppler profiles reveal the dissociation is nearly isotropic. The dissociation most likely proceeds in two steps via an intermediate electronically excited C_2O. A maximum likelihood method based upon information theory is developed to abstract the correlation between the final states for reactions of multiple independently measured fragment species. Methods for ascribing dynamical mechanisms to the inferred joint probability distribution are discussed. A 'decoupled' surprisal analysis technique appropriate to distributions coupled by

  6. Signatures of a conical intersection in photofragment distributions and absorption spectra: Photodissociation in the Hartley band of ozone

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Picconi, David; Grebenshchikov, Sergy Yu., E-mail: Sergy.Grebenshchikov@ch.tum.de

    Photodissociation of ozone in the near UV is studied quantum mechanically in two excited electronic states coupled at a conical intersection located outside the Franck-Condon zone. The calculations, performed using recent ab initio PESs, provide an accurate description of the photodissociation dynamics across the Hartley/Huggins absorption bands. The observed photofragment distributions are reproduced in the two electronic dissociation channels. The room temperature absorption spectrum, constructed as a Boltzmann average of many absorption spectra of rotationally excited parent ozone, agrees with experiment in terms of widths and intensities of diffuse structures. The exit channel conical intersection contributes to the coherent broadeningmore » of the absorption spectrum and directly affects the product vibrational and translational distributions. The photon energy dependences of these distributions are strikingly different for fragments created along the adiabatic and the diabatic paths through the intersection. They can be used to reverse engineer the most probable geometry of the non-adiabatic transition. The angular distributions, quantified in terms of the anisotropy parameter β, are substantially different in the two channels due to a strong anticorrelation between β and the rotational angular momentum of the fragment O{sub 2}.« less

  7. Photodissociative Cross-Linking of Non-covalent Peptide-Peptide Ion Complexes in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Nguyen, Huong T. H.; Andrikopoulos, Prokopis C.; Rulíšek, Lubomír; Shaffer, Christopher J.; Tureček, František

    2018-05-01

    We report a gas-phase UV photodissociation study investigating non-covalent interactions between neutral hydrophobic pentapeptides and peptide ions incorporating a diazirine-tagged photoleucine residue. Phenylalanine (Phe) and proline (Pro) were chosen as the conformation-affecting residues that were incorporated into a small library of neutral pentapeptides. Gas-phase ion-molecule complexes of these peptides with photo-labeled pentapeptides were subjected to photodissociation. Selective photocleavage of the diazirine ring at 355 nm formed short-lived carbene intermediates that underwent cross-linking by insertion into H-X bonds of the target peptide. The cross-link positions were established from collision-induced dissociation tandem mass spectra (CID-MS3) providing sequence information on the covalent adducts. Effects of the amino acid residue (Pro or Phe) and its position in the target peptide sequence were evaluated. For proline-containing peptides, interactions resulting in covalent cross-links in these complexes became more prominent as proline was moved towards the C-terminus of the target peptide sequence. The photocross-linking yields of phenylalanine-containing peptides depended on the position of both phenylalanine and photoleucine. Density functional theory calculations were used to assign structures of low-energy conformers of the (GLPMG + GLL*LK + H)+ complex. Born-Oppenheimer molecular dynamics trajectory calculations were used to capture the thermal motion in the complexes within 100 ps and determine close contacts between the incipient carbene and the H-X bonds in the target peptide. This provided atomic-level resolution of potential cross-links that aided spectra interpretation and was in agreement with experimental data. [Figure not available: see fulltext.

  8. Photodissociation dynamics of CH{sub 3}C(O)SH in argon matrix: A QM/MM nonadiabatic dynamics simulation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xia, Shu-Hua; Liu, Xiang-Yang; Fang, Qiu

    2015-11-21

    In this work, we have first employed the combined quantum mechanics/molecular mechanics (QM/MM) method to study the photodissociation mechanism of thioacetic acid CH{sub 3}C(O)SH in the S{sub 1}, T{sub 1}, and S{sub 0} states in argon matrix. CH{sub 3}C(O)SH is treated quantum mechanically using the complete active space self-consistent field and complete active space second-order perturbation theory methods; argon matrix is described classically using Lennard-Jones potentials. We find that the C-S bond fission is predominant due to its small barriers of ca. 3.0 and 1.0 kcal/mol in the S{sub 1} and T{sub 1} states. It completely suppresses the nearby C—Cmore » bond fission. After the bond fission, the S{sub 1} radical pair of CH{sub 3}CO and SH can decay to the S{sub 0} and T{sub 1} states via internal conversion and intersystem crossing, respectively. In the S{sub 0} state, the radical pair can either recombine to form CH{sub 3}C(O)SH or proceed to form molecular products of CH{sub 2}CO and H{sub 2}S. We have further employed our recently developed QM/MM generalized trajectory-based surface-hopping method to simulate the photodissociation dynamics of CH{sub 3}C(O)SH. In 1 ps dynamics simulation, 56% trajectories stay at the Franck-Condon region; the S{sub 1} C—S bond fission takes place in the remaining 44% trajectories. Among all nonadiabatic transitions, the S{sub 1} → S{sub 0} internal conversion is major (55%) but the S{sub 1} → T{sub 1} intersystem crossing is still comparable and cannot be ignored, which accounts for 28%. Finally, we have found a radical channel generating the molecular products of CH{sub 2}CO and H{sub 2}S, which is complementary to the concerted molecular channel. The present work sets the stage for simulating photodissociation dynamics of similar thio-carbonyl systems in matrix.« less

  9. Photodissociation spectroscopy of the Mg + -CO2 complex and its isotopic analogs

    NASA Astrophysics Data System (ADS)

    Yeh, C. S.; Willey, K. F.; Robbins, D. L.; Pilgrim, J. S.; Duncan, M. A.

    1993-02-01

    Mg+-CO2 ion-molecule cluster complexes are produced by laser vaporization in a pulsed nozzle cluster source. The vibronic spectroscopy in these complexes is studied with mass-selected photodissociation spectroscopy in a reflectron time-of-flight mass spectrometer. Two excited electronic states are observed (2) 2Σ+ and 2Π. The 2Π state has a vibrational progression in the metal-CO2 stretching mode (ωe'=381.8 cm-1). The complexes are linear (Mg+-OCO) and are bound by the charge-quadrupole interaction. The dissociation energy (D0`) is 14.7 kcal/mol. Corresponding spectra are measured for each of the 24, 25, and 26 isotopes of magnesium. These results are compared to theoretical predictions made by Bauschlicher and co-workers.

  10. Observations of molecular and atomic gas in photodissociation regions. [interstellar chemistry

    NASA Technical Reports Server (NTRS)

    Jaffe, D. T.; Howe, J. E.

    1989-01-01

    Dense gas at the ionized/neutral boundaries of molecular clouds illuminated by far-UV photons plays an important role in the appearance of the neutral interstellar medium. It also is a laboratory for the study of UV-photochemistry and of a number of heating and cooling phenomena not seen elsewhere. Fine structure lines of neutral and low ionization potential species dominate the cooling in the outer part of the photodissociation regions. Observations of these lines show that the regions are dense and highly clumped. Observations of H2 and CO show that heating by UV photons plays a significant role in the excitation of molecular lines near the H II/neutral boundary. Warm CO is more abundant in these regions than predicted by the standard theoretical models. Optical reflection nebulas provide an ideal laboratory for the study of photodissocciation region phenomena.

  11. Schrödinger–Langevin equation with quantum trajectories for photodissociation dynamics

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chou, Chia-Chun, E-mail: ccchou@mx.nthu.edu.tw

    The Schrödinger–Langevin equation is integrated to study the wave packet dynamics of quantum systems subject to frictional effects by propagating an ensemble of quantum trajectories. The equations of motion for the complex action and quantum trajectories are derived from the Schrödinger–Langevin equation. The moving least squares approach is used to evaluate the spatial derivatives of the complex action required for the integration of the equations of motion. Computational results are presented and analyzed for the evolution of a free Gaussian wave packet, a two-dimensional barrier model, and the photodissociation dynamics of NOCl. The absorption spectrum of NOCl obtained from themore » Schrödinger–Langevin equation displays a redshift when frictional effects increase. This computational result agrees qualitatively with the experimental results in the solution-phase photochemistry of NOCl.« less

  12. Radical formation in the coma from photodissociation of ice grains

    NASA Technical Reports Server (NTRS)

    Jackson, William M.; Gerth, Christopher

    1990-01-01

    Long ago visual observations of comets suggested that there are jets in comets but it has only been recently that A'Hearn et al. have proven that some of these jets are due to emission from the CN radical. Recent studies in the lab have shown that CN radicals can be ejected directly into the gas phase from the photolysis of frozen vapors if the parent molecular has been excited to repulsive excited state. This later observation suggests that the jets that have been observed may be due to photodissociation of icy grains in the coma. A theory of radical formation from icy grains is presented. It is shown that direct formation of free radicals in the coma is an effective way to produce radicals from icy grains in the coma. The model predicts that icy grains could produce from 6 to 800,000 OH radicals/s per grain depending upon whether the radius of the grain is 0.3 to 100 micron.

  13. Isomer-specific detection in the UV photodissociation of the propargyl radical by chirped-pulse mm-wave spectroscopy in a pulsed quasi-uniform flow.

    PubMed

    Broderick, Bernadette M; Suas-David, Nicolas; Dias, Nureshan; Suits, Arthur G

    2018-02-21

    Isomer-specific detection and product branching fractions in the UV photodissociation of the propargyl radical is achieved through the use of chirped-pulse Fourier-transform mm-wave spectroscopy in a pulsed quasi-uniform flow (CPUF). Propargyl radicals are produced in the 193 nm photodissociation of 1,2-butadiene. Absorption of a second photon leads to H atom elimination giving three possible C 3 H 2 isomers: singlets cyclopropenylidene (c-C 3 H 2 ) and propadienylidene (l-C 3 H 2 ), and triplet propargylene ( 3 HCCCH). The singlet products and their appearance kinetics in the flow are directly determined by rotational spectroscopy, but due to the negligible dipole moment of propargylene, it is not directly monitored. However, we exploit the time-dependent kinetics of H-atom catalyzed isomerization to infer the branching to propargylene as well. We obtain the overall branching among H loss channels to be 2.9% (+1.1/-0.5) l-C 3 H 2 + H, 16.8% (+3.2/-1.3) c-C 3 H 2 + H, and 80.2 (+1.8/-4.2) 3 HCCCH + H. Our findings are qualitatively consistent with earlier RRKM calculations in that the major channel in the photodissociation of the propargyl radical at 193 nm is to 3 HCCCH + H; however, a greater contribution to the energetically most favorable isomer, c-C 3 H 2 + H is observed in this work. We do not detect the predicted HCCC + H 2 channel, but place an upper bound on its yield of 1%.

  14. Research in extreme ultraviolet and far ultraviolet astronomy

    NASA Technical Reports Server (NTRS)

    Bowyer, C. S.

    1985-01-01

    The Far Ultraviolet imager (FUVI) was flown on the Aries class sounding rocket 24.015, producing outstanding results. The diffuse extreme ultraviolet (EUV) background spectrometer which is under construction is described. It will be launched on the Black Brant sounding rocket flight number 27.086. Ongoing design studies of a high resolution spectrometer are discussed. This instrument incorporates a one meter normal incidence mirror and will be suitable for an advanced Spartan mission.

  15. Ultraviolet absorption hygrometer

    DOEpatents

    Gersh, M.E.; Bien, F.; Bernstein, L.S.

    1986-12-09

    An ultraviolet absorption hygrometer is provided including a source of pulsed ultraviolet radiation for providing radiation in a first wavelength region where water absorbs significantly and in a second proximate wavelength region where water absorbs weakly. Ultraviolet radiation in the first and second regions which has been transmitted through a sample path of atmosphere is detected. The intensity of the radiation transmitted in each of the first and second regions is compared and from this comparison the amount of water in the sample path is determined. 5 figs.

  16. Photodissociation and caging of HBr and HI molecules on the surface of large rare gas clusters.

    PubMed

    Baumfalk, R; Nahler, N H; Buck, U

    2001-01-01

    Photodissociation experiments were carried out at a wavelength of 243 nm for single HBr and HI molecules adsorbed on the surface of large Nen, Arn, Krn and Xen clusters. The average size is about = 130; the size ranges = 62-139 for the system HBr-Arn and = 110-830 for HI-Xen were covered. In this way the dependence of the photodissociation dynamics on both the size and the rare gas host cluster was investigated. The main observable is the kinetic energy distribution of the outgoing H atoms. The key results are that we do not find any size dependence for either system but that we observe a strong dependence on the rare gas clusters. All systems exhibit H atoms with no energy loss that indicate direct cage exit and those with nearly zero energy that are an indication of complete caging. The intensity ratio of caged to uncaged H atoms is largest for Nen, decreases with increasing mass of the cage atoms, and is weakest for Xen. On the basis of accompanying calculations this behaviour is attributed to the large amplitude motion of the light H atom. This leads to direct cage exit and penetration of the atom through the cluster with different energy transfer per collision depending on the rare gas atoms. The differences between HBr and HI molecules are attributed to different surface states, a flat and an encapsulated site.

  17. Photodissociation of phenol via nonadiabatic tunneling: Comparison of two ab initio based potential energy surfaces

    NASA Astrophysics Data System (ADS)

    Xie, Changjian; Guo, Hua

    2017-09-01

    The nonadiabatic tunneling-facilitated photodissociation of phenol is investigated using a reduced-dimensional quantum model on two ab initio-based coupled potential energy surfaces (PESs). Although dynamics occurs largely on the lower adiabat, the proximity to a conical intersection between the S1 and S2 states requires the inclusion of both the geometric phase (GP) and diagonal Born-Oppenheimer correction (DBOC). The lifetime of the lowest-lying vibronic state is computed using the diabatic and various adiabatic models. The GP and DBOC terms are found to be essential on one set of PESs, but have a small impact on the other.

  18. Evidence for concerted ring opening and C-Br bond breaking in UV-excited bromocyclopropane.

    PubMed

    Pandit, Shubhrangshu; Preston, Thomas J; King, Simon J; Vallance, Claire; Orr-Ewing, Andrew J

    2016-06-28

    Photodissociation of gaseous bromocyclopropane via its A-band continuum has been studied at excitation wavelengths ranging from 230 nm to 267 nm. Velocity-map images of ground-state bromine atoms (Br), spin-orbit excited bromine atoms (Br(∗)), and C3H5 hydrocarbon radicals reveal the kinetic energies of these various photofragments. Both Br and Br(∗) atoms are predominantly generated via repulsive excited electronic states in a prompt photodissociation process in which the hydrocarbon co-fragment is a cyclopropyl radical. However, the images obtained at the mass of the hydrocarbon radical fragment identify a channel with total kinetic energy greater than that deduced from the Br and Br(∗) images, and with a kinetic energy distribution that exceeds the energetic limit for Br + cyclopropyl radical products. The velocity-map images of these C3H5 fragments have lower angular anisotropies than measured for Br and Br(∗), indicating molecular restructuring during dissociation. The high kinetic energy C3H5 signals are assigned to allyl radicals generated by a minor photochemical pathway which involves concerted C-Br bond dissociation and cyclopropyl ring-opening following single ultraviolet (UV)-photon absorption. Slow photofragments also contribute to the velocity map images obtained at the C3H5 radical mass, but the corresponding slow Br atoms are not observed. These features in the images are attributed to C3H5 (+) from the photodissociation of the C3H5Br(+) molecular cation following two-photon ionization of the parent compound. This assignment is confirmed by 118-nm vacuum ultraviolet ionization studies that prepare the molecular cation in its ground electronic state prior to UV photodissociation.

  19. VUV action spectroscopy of protonated leucine-enkephalin peptide in the 6-14 eV range

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ranković, M. Lj.; Canon, F.; Nahon, L.

    2015-12-28

    We have studied the Vacuum Ultraviolet (VUV) photodissociation of gas-phase protonated leucine-enkephalin peptide ion in the 5.7 to 14 eV photon energy range by coupling a linear quadrupole ion trap with a synchrotron radiation source. We report VUV activation tandem mass spectra at 6.7, 8.4, and 12.8 eV photon energies and photodissociation yields for a number of selected fragments. The obtained results provide insight into both near VUV radiation damage and electronic properties of a model peptide. We could distinguish several absorption bands and assign them to particular electronic transitions, according to previous theoretical studies. The photodissociation yields appear tomore » be very different for the various observed fragmentation channels, depending on both the types of fragments and their position along the peptide backbone. The present results are discussed in light of recent gas-phase spectroscopic data on peptides.« less

  20. Photodissociation of the carbon monoxide dication in the {sup 3}Σ{sup −} manifold: Quantum control simulation towards the C{sup 2+} + O channel

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Vranckx, S.; Laboratoire de Chimie Physique; Loreau, J.

    The photodissociation and laser assisted dissociation of the carbon monoxide dication X{sup 3}Π CO{sup 2+} into the {sup 3}Σ{sup −} states are investigated. Ab initio electronic structure calculations of the adiabatic potential energy curves, radial nonadiabatic couplings, and dipole moments for the X {sup 3}Π state are performed for 13 excited {sup 3}Σ{sup −} states of CO{sup 2+}. The photodissociation cross section, calculated by time-dependent methods, shows that the C{sup +} + O{sup +} channels dominate the process in the studied energy range. The carbon monoxide dication CO{sup 2+} is an interesting candidate for control because it can be producedmore » in a single, long lived, v = 0 vibrational state due to the instability of all the other excited vibrational states of the ground {sup 3}Π electronic state. In a spectral range of about 25 eV, perpendicular transition dipoles couple this {sup 3}Π state to a manifold of {sup 3}Σ{sup −} excited states leading to numerous C{sup +} + O{sup +} channels and a single C{sup 2+} + O channel. This unique channel is used as target for control calculations using local control theory. We illustrate the efficiency of this method in order to find a tailored electric field driving the photodissociation in a manifold of strongly interacting electronic states. The selected local pulses are then concatenated in a sequence inspired by the “laser distillation” strategy. Finally, the local pulse is compared with optimal control theory.« less

  1. Observations of the photodissociated HI region that surrounds G213.880-11.837

    NASA Astrophysics Data System (ADS)

    Rodríguez-Rico, C. A.; Gómez, Y.; Garay, G.; Neria, C.; Rodríguez, L. F.; Escalante, V.; Lizano, S.; Lebrón, M.

    2011-10-01

    New observations of the HI 21 cm line toward the cometary HII region G213.880-11.837 are presented. These observations, carried out with an angular resolution of 15'', reveal that the neutral gas in this region is part of an expanding flow. The analysis of the kinematics of the HI gas suggests that the HI gas is undergoing a champagne flow: based on the difference between the radial velocities of the neutral gas in the tail ( 4km s^{-1}) compared to the velocities of the ambient molecular gas ( 11.5 km s^{-1}) and the asymmetry of the HI emission. Besides this photodissociated region, there is only one other reported following an HI champagne flow (G111.61+0.37).

  2. 21 CFR 872.6350 - Ultraviolet detector.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ultraviolet detector. 872.6350 Section 872.6350...) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6350 Ultraviolet detector. (a) Identification. An ultraviolet detector is a device intended to provide a source of ultraviolet light which is used...

  3. 21 CFR 872.6350 - Ultraviolet detector.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Ultraviolet detector. 872.6350 Section 872.6350...) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6350 Ultraviolet detector. (a) Identification. An ultraviolet detector is a device intended to provide a source of ultraviolet light which is used...

  4. 21 CFR 872.6350 - Ultraviolet detector.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ultraviolet detector. 872.6350 Section 872.6350...) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6350 Ultraviolet detector. (a) Identification. An ultraviolet detector is a device intended to provide a source of ultraviolet light which is used...

  5. 21 CFR 872.6350 - Ultraviolet detector.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Ultraviolet detector. 872.6350 Section 872.6350...) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6350 Ultraviolet detector. (a) Identification. An ultraviolet detector is a device intended to provide a source of ultraviolet light which is used...

  6. 21 CFR 872.6350 - Ultraviolet detector.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Ultraviolet detector. 872.6350 Section 872.6350...) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6350 Ultraviolet detector. (a) Identification. An ultraviolet detector is a device intended to provide a source of ultraviolet light which is used...

  7. INFRARED MULTIPLE-PHOTON PHOTODISSOCIATION OF GAS-PHASE GROUP II METAL-NITRATE ANIONS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jos Oomens; Linda Myers; Ryan Dain

    2008-06-01

    Infrared spectra of gas-phase metal-nitrate anions M(NO3)3-, where M=Mg2+, Ca2+, Sr2+ and Ba2+, were recorded by infrared multiple photon dissociation (IRMPD) spectroscopy. Photodissociation of each of the precursors produces NO3- through the elimination of a neutral M(NO3)2 unit. An absorption pattern characteristic of metal nitrates is observed in the IRMPD spectra, including the symmetric and antisymmetric NO3 stretches. The latter is split into high and low frequency components as a result of perturbation of the nitrate symmetry by complexation to the metal ion, and the magnitude of the splitting decreases following the trend Mg2+ > Ca2+ > Sr2+ ? Ba2+.more » The experimental spectra are in good general agreement with those obtained from density functional theory calculations.« less

  8. SINGLE AND DOUBLE PHOTOIONIZATION AND PHOTODISSOCIATION OF TOLUENE BY SOFT X-RAYS IN A CIRCUMSTELLAR ENVIRONMENT

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Monfredini, T.; Boechat-Roberty, H. M.; Fantuzzi, F.

    The formation of polycyclic aromatic hydrocarbons (PAHs) and their methyl derivatives mainly occurs in the dust shells of asymptotic giant branch (AGB) stars. The bands at 3.3 and 3.4 μm, observed in infrared emission spectra of several objects, are attributed C–H vibrational modes in aromatic and aliphatic structures, respectively. In general, the feature at 3.3 μm is more intense than that at 3.4 μm. Photoionization and photodissociation processes of toluene, the precursor of methylated PAHs, were studied using synchrotron radiation at soft X-ray energies around the carbon K edge using time-of-flight mass spectrometry. Partial ion yields of a large numbermore » of ionic fragments were extracted from single and 2D-spectra, where electron-ion coincidences have revealed the doubly charged parent molecule and several doubly charged fragments containing seven carbon atoms with considerable abundance. Ab initio calculations based on density functional theory were performed in order to elucidate the chemical structure of these stable dicationic species. The survival of the dications subjected to hard inner shell ionization suggests that they could be observed in the interstellar medium, especially in regions where PAHs are detected. The ionization and destruction of toluene induced by X-rays were examined in the T Dra conditions, a carbon-rich AGB star. In this context, a minimum photodissociation radius and the half-life of toluene subjected to the incidence of the soft X-ray flux emitted from a companion white dwarf star were determined.« less

  9. Single and Double Photoionization and Photodissociation of Toluene by Soft X-Rays in a Circumstellar Environment

    NASA Astrophysics Data System (ADS)

    Monfredini, T.; Fantuzzi, F.; Nascimento, M. A. C.; Wolff, W.; Boechat-Roberty, H. M.

    2016-04-01

    The formation of polycyclic aromatic hydrocarbons (PAHs) and their methyl derivatives mainly occurs in the dust shells of asymptotic giant branch (AGB) stars. The bands at 3.3 and 3.4 μm, observed in infrared emission spectra of several objects, are attributed C-H vibrational modes in aromatic and aliphatic structures, respectively. In general, the feature at 3.3 μm is more intense than that at 3.4 μm. Photoionization and photodissociation processes of toluene, the precursor of methylated PAHs, were studied using synchrotron radiation at soft X-ray energies around the carbon K edge using time-of-flight mass spectrometry. Partial ion yields of a large number of ionic fragments were extracted from single and 2D-spectra, where electron-ion coincidences have revealed the doubly charged parent molecule and several doubly charged fragments containing seven carbon atoms with considerable abundance. Ab initio calculations based on density functional theory were performed in order to elucidate the chemical structure of these stable dicationic species. The survival of the dications subjected to hard inner shell ionization suggests that they could be observed in the interstellar medium, especially in regions where PAHs are detected. The ionization and destruction of toluene induced by X-rays were examined in the T Dra conditions, a carbon-rich AGB star. In this context, a minimum photodissociation radius and the half-life of toluene subjected to the incidence of the soft X-ray flux emitted from a companion white dwarf star were determined.

  10. Properties of Highly Rotationally Excited H2 in Photodissociation Regions

    NASA Astrophysics Data System (ADS)

    Cummings, Sally Jane; Wan, Yier; Stancil, Phillip C.; Yang, Benhui H.; Zhang, Ziwei

    2018-06-01

    H2 is the dominant molecular species in the vast majority of interstellar environments and it plays a crucial role as a radiative coolant. In photodissociation regions, it is one of the primary emitters in the near to mid-infrared which are due to lines originating from highly excited rotational levels. However, collisional data for rotational levels j>10 are sparse, particularly for H2-H2 collisions. Utilizing new calculations for para-H2 and ortho-H2 collisional rate coefficients with H2 for j as high as 30, we investigate the effects of the new results in standard PDR models with the spectral simulation package Cloudy. We also perform Cloudy models of the Orion Bar and use Radex to explore rotational line ratio diagnostics. The resulting dataset of H2 collisional data should find wide application to other molecular environments. This work was support by Hubble Space Telescope grant HST-AR-13899.001-A and NASA grants NNX15AI61G and NNX16AF09G.

  11. Far Infrared Line Profiles from Photodissociation Regions and Warm Molecular Clouds

    NASA Technical Reports Server (NTRS)

    Boreiko, R. T.; Betz, A. L.

    1998-01-01

    This report summarizes the work done under NASA Grant NAG2-1056 awarded to the University of Colorado. The aim of the project was to analyze data obtained over the past several years with the University of Colorado far-infrared heterodyne spectrometer (Betz & Boreiko 1993) aboard the Kuiper Airborne Observatory. Of particular interest were observations of CO and ionized carbon (C II) in photodissociation regions (PDRs) at the interface between UV-ionized H II regions and the neutral molecular clouds supporting star formation. These data, obtained with a heterodyne spectrometer having a resolution of 3.2 MHz, which is equivalent to a velocity resolution of 0.2 km/s at 60 microns and 1.0 km/s at 300 microns, were analyzed to obtain physical parameters such as density and temperature in the observed PDR. The publication resulting from the work reported here is appended. No inventions were made nor was any federally owned property acquired as a result of the activities under this grant.

  12. Ab initio studies of ultrafast x-ray scattering of the photodissociation of iodine

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Debnarova, Andrea; Techert, Simone; Schmatz, Stefan

    2010-09-28

    We computationally examine various aspects of the reaction dynamics of the photodissociation and recombination of molecular iodine. We use our recently proposed formalism to calculate time-dependent x-ray scattering signal changes from first principles. Different aspects of the dynamics of this prototypical reaction are studied, such as coherent and noncoherent processes, features of structural relaxation that are periodic in time versus nonperiodic dissociative processes, as well as small electron density changes caused by electronic excitation, all with respect to x-ray scattering. We can demonstrate that wide-angle x-ray scattering offers a possibility to study the changes in electron densities in nonperiodic systems,more » which render it a suitable technique for the investigation of chemical reactions from a structural dynamics point of view.« less

  13. Chlorate Formation Mechanism in the Presence of Sulfate Radical, Chloride, Bromide and Natural Organic Matter.

    PubMed

    Hou, Shaodong; Ling, Li; Dionysiou, Dionysios D; Wang, Yuru; Huang, Jiajia; Guo, Kaiheng; Li, Xuchun; Fang, Jingyun

    2018-06-05

    Halides and natural organic matter (NOM) are inevitable in aquatic environment and influence the degradation of contaminants in sulfate radical (SO 4 •- )-based advanced oxidation processes. This study investigated the formation of chlorate in the coexposure of SO 4 •- , chloride (Cl - ), bromide (Br - ) and/or NOM in UV/persulfate (UV/PDS) and cobalt(II)/peroxymonosulfate (Co/PMS) systems. The formation of chlorate increased with increasing Cl - concentration in the UV/PDS system, however, in the Co/PMS system, it initially increased and then decreased. The chlorate formation involved the formation of hypochlorous acid/hypochlorite (HOCl/OCl - ) as an intermediate in both systems. The formation was primarily attributable to SO 4 •- in the UV/PDS system, whereas Co(III) played a significant role in the oxidation of Cl - to HOCl/OCl - and SO 4 •- was important for the oxidation of HOCl/OCl - to chlorate in the Co/PMS system. The pseudo-first-order rate constants ( k') of the transformation from Cl - to HOCl/OCl - were 3.32 × 10 -6 s -1 and 9.23 × 10 -3 s -1 in UV/PDS and Co/PMS, respectively. Meanwhile, k' of HOCl/OCl - to chlorate in UV/PDS and Co/PMS were 2.43 × 10 -3 s -1 and 2.70 × 10 -4 s -1 , respectively. Br - completely inhibited the chlorate formation in UV/PDS, but inhibited it by 45.2% in Co/PMS. The k' of SO 4 •- reacting with Br - to form hypobromous acid/hypobromite (HOBr/OBr - ) was calculated to be 378 times higher than that of Cl - to HOCl/OCl - , but the k' of Co(III) reacting with Br - to form HOBr/OBr - was comparable to that of Cl - to HOCl/OCl - . NOM also significantly inhibited the chlorate formation, due to the consumption of SO 4 •- and reactive chlorine species (RCS, such as Cl·, ClO· and HOCl/OCl - ). This study demonstrated the formation of chlorate in SO 4 •- -based AOPs, which should to be considered in their application in water treatment.

  14. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pandit, Shubhrangshu; Preston, Thomas J.; Orr-Ewing, Andrew J., E-mail: a.orr-ewing@bristol.ac.uk

    Photodissociation of gaseous bromocyclopropane via its A-band continuum has been studied at excitation wavelengths ranging from 230 nm to 267 nm. Velocity-map images of ground-state bromine atoms (Br), spin-orbit excited bromine atoms (Br{sup ∗}), and C{sub 3}H{sub 5} hydrocarbon radicals reveal the kinetic energies of these various photofragments. Both Br and Br{sup ∗} atoms are predominantly generated via repulsive excited electronic states in a prompt photodissociation process in which the hydrocarbon co-fragment is a cyclopropyl radical. However, the images obtained at the mass of the hydrocarbon radical fragment identify a channel with total kinetic energy greater than that deduced frommore » the Br and Br{sup ∗} images, and with a kinetic energy distribution that exceeds the energetic limit for Br + cyclopropyl radical products. The velocity-map images of these C{sub 3}H{sub 5} fragments have lower angular anisotropies than measured for Br and Br{sup ∗}, indicating molecular restructuring during dissociation. The high kinetic energy C{sub 3}H{sub 5} signals are assigned to allyl radicals generated by a minor photochemical pathway which involves concerted C–Br bond dissociation and cyclopropyl ring-opening following single ultraviolet (UV)-photon absorption. Slow photofragments also contribute to the velocity map images obtained at the C{sub 3}H{sub 5} radical mass, but the corresponding slow Br atoms are not observed. These features in the images are attributed to C{sub 3}H{sub 5}{sup +} from the photodissociation of the C{sub 3}H{sub 5}Br{sup +} molecular cation following two-photon ionization of the parent compound. This assignment is confirmed by 118-nm vacuum ultraviolet ionization studies that prepare the molecular cation in its ground electronic state prior to UV photodissociation.« less

  15. Ab initio reaction pathways for photodissociation and isomerization of nitromethane on four singlet potential energy surfaces with three roaming paths

    NASA Astrophysics Data System (ADS)

    Isegawa, Miho; Liu, Fengyi; Maeda, Satoshi; Morokuma, Keiji

    2014-06-01

    Photodissociation pathways of nitromethane following π → π* electronic excitation are reported. The potential energy surfaces for four lowest singlet states are explored, and structures of many intermediates, dissociation limits, transition states, and minimum energy conical intersections were determined using the automated searching algorism called the global reaction route mapping strategy. Geometries are finally optimized at CASSCF(14e,11o) level and energies are computed at CAS(14o,11e)PT2 level. The calculated preferable pathways and important products qualitatively explain experimental observations. The major photodissociation product CH3 and NO2 (2B2) is formed by direct dissociation from the S1 state. Important pathways involving S1 and S0 states for production of various dissociation products CH3NO + O (1D), CH3O(X2E) + NO (X2Π), CH2NO + OH, and CH2O + HNO, as well as various isomerization pathways have been identified. Three roaming processes also have been identified: the O atom roaming in O dissociation from CH3NO2, the OH radical roaming in OH dissociation from CH2N(O)(OH), and the NO roaming in NO dissociation from CH3ONO.

  16. Ab initio reaction pathways for photodissociation and isomerization of nitromethane on four singlet potential energy surfaces with three roaming paths.

    PubMed

    Isegawa, Miho; Liu, Fengyi; Maeda, Satoshi; Morokuma, Keiji

    2014-06-28

    Photodissociation pathways of nitromethane following π → π(*) electronic excitation are reported. The potential energy surfaces for four lowest singlet states are explored, and structures of many intermediates, dissociation limits, transition states, and minimum energy conical intersections were determined using the automated searching algorism called the global reaction route mapping strategy. Geometries are finally optimized at CASSCF(14e,11o) level and energies are computed at CAS(14o,11e)PT2 level. The calculated preferable pathways and important products qualitatively explain experimental observations. The major photodissociation product CH3 and NO2 ((2)B2) is formed by direct dissociation from the S1 state. Important pathways involving S1 and S0 states for production of various dissociation products CH3NO + O ((1)D), CH3O(X(2)E) + NO (X(2)Π), CH2NO + OH, and CH2O + HNO, as well as various isomerization pathways have been identified. Three roaming processes also have been identified: the O atom roaming in O dissociation from CH3NO2, the OH radical roaming in OH dissociation from CH2N(O)(OH), and the NO roaming in NO dissociation from CH3ONO.

  17. Laser induced photoluminiscence studies of primary photochemical production processes of cometary radicals

    NASA Technical Reports Server (NTRS)

    Jackson, W. M.

    1977-01-01

    A tunable vacuum ultraviolet flash lamp was constructed. This unique flash lamp was coupled with a tunable dye laser detector and permits the experimenter to measure the production rates of ground state radicals as a function of wavelength. A new technique for producing fluorescent radicals was discovered. This technique called multiphoton ultraviolet photodissociation is currently being applied to several problems of both cometary and stratospheric interest. It was demonstrated that NO2 will dissociate to produce an excited fragment and the radiation can possibly be used for remote detection of this species.

  18. Detection of latent fingerprints by ultraviolet spectral imaging

    NASA Astrophysics Data System (ADS)

    Huang, Wei; Xu, Xiaojing; Wang, Guiqiang

    2013-12-01

    Spectral imaging technology research is becoming more popular in the field of forensic science. Ultraviolet spectral imaging technology is an especial part of the full spectrum of imaging technology. This paper finished the experiment contents of the ultraviolet spectrum imaging method and image acquisition system based on ultraviolet spectral imaging technology. Ultraviolet spectral imaging experiments explores a wide variety of ultraviolet reflectance spectra of the object material curve and its ultraviolet spectrum of imaging modalities, can not only gives a reference for choosing ultraviolet wavelength to show the object surface potential traces of substances, but also gives important data for the ultraviolet spectrum of imaging technology development.

  19. Transmitting and reflecting diffuser. [for ultraviolet light

    NASA Technical Reports Server (NTRS)

    Keafer, L. S., Jr.; Burcher, E. E.; Kopia, L. P. (Inventor)

    1973-01-01

    A near-Lambertian diffuser is described which transmits and reflects ultraviolet light. An ultraviolet grade fused silica substrate is coated with vaporized fuse silica. The coating thickness is controlled, one thickness causing ultraviolet light to diffuse and another thickness causing ultraviolet light to reflect a near Lambertian pattern.

  20. International Ultraviolet Explorer (IUE)

    NASA Technical Reports Server (NTRS)

    Boehm, Karl-Heinz

    1992-01-01

    The observation, data reduction, and interpretation of ultraviolet spectra (obtained with the International Ultraviolet Explorer) of Herbig-Haro objects, stellar jets, and (in a few cases) reflection nebulae in star-forming regions is discussed. Intermediate results have been reported in the required semi-annual reports. The observations for this research were obtained in 23 (US1) IUE shifts. The spectra were taken in the low resolution mode with the large aperture. The following topics were investigated: (1) detection of UV spectra of high excitation Herbig-Haro (HH) objects, identification of emission lines, and a preliminary study of the energy distribution of the ultraviolet continuum; (2) details of the continuum energy distribution of these spectra and their possible interpretation; (3) the properties of the reddening (extinction) of HH objects; (4) the possible time variation of strong emission lines in high excitation HH objects; (5) the ultraviolet emission of low excitation HH objects, especially in the fluorescent lines of the H2 molecule; (6) the ultraviolet emission in the peculiar object HH24; (7) the spatial emission distribution of different lines and different parts of the continuum in different HH objects; and (8) some properties of reflection nebula, in the environment of Herbig-Haro objects. Each topic is discussed.

  1. Hot Stars and Cool Clouds: The Photodissociation Region M16.

    PubMed

    Levenson; Graham; McLean; Becklin; Figer; Gilbert; Larkin; Teplitz; Wilcox

    2000-04-10

    We present high-resolution spectroscopy and images of a photodissociation region (PDR) in M16 obtained during commissioning of the near-infrared spectrometer (NIRSPEC) on the Keck II telescope. PDRs play a significant role in regulating star formation, and M16 offers the opportunity to examine the physical processes of a PDR in detail. We simultaneously observe both the molecular and ionized phases of the PDR and resolve the spatial and kinematic differences between them. The most prominent regions of the PDR are viewed edge-on. Fluorescent emission from nearby stars is the primary excitation source, although collisions also preferentially populate the lowest vibrational levels of H2. Variations in density-sensitive emission-line ratios demonstrate that the molecular cloud is clumpy, with an average density n=3x105 cm-3. We measure the kinetic temperature of the molecular region directly and find that TH2=930 K. The observed density, temperature, and UV flux imply a photoelectric heating efficiency of 4%. In the ionized region, ni=5x103 cm-3 and THii=9500 K. In the brightest regions of the PDR, the recombination line widths include a nonthermal component, which we attribute to viewing geometry.

  2. Photodissociation of anisole and absolute photoionization cross-section of the phenoxy radical.

    PubMed

    Xu, Hong; Pratt, S T

    2013-11-21

    We have studied the photodissociation dynamics of anisole (C6H5OCH3) at 193 nm and determined the absolute photoionization cross-section of the phenoxy radical at 118.2 nm (10.486 eV) relative to the known cross-section of the methyl radical. Even at this energy, there is extensive fragmentation of the phenoxy radical upon photoionization, which is attributed to ionizing transitions that populate low-lying excited electronic states of the cation. For phenoxy radicals with less than ∼1 eV of internal energy, we find a cross-section for the production of the phenoxy cation of 14.8 ± 3.8 Mb. For radicals with higher internal energy, dissociative ionization is the dominant process, and for internal energies of ∼2.7-3.7 eV, we find a total cross-section (photoionization plus dissociative ionization) of 22.3 ± 4.1 Mb. The results are discussed relative to the recently reported photoionization cross-section of phenol.

  3. HCN and HCO(+) images of the photodissociation region in the Orion Bar

    NASA Technical Reports Server (NTRS)

    Youngowl, Rolaine C.; Meixner, Margaret; Tielens, Alexander G. G. M.; Tauber, Jan A.

    1995-01-01

    We present preliminary millimeter-wavelength images of the photodissociation region (PDR) in the Orion Bar, observed with the Berkeley- Illinois-Maryland array (BIMA). These new BIMA observations have attained 5 arc sec resolution in the J=l-O emission lines of HCO+ (formyl ion) and HCN (hydrogen cyanide). The results are compared with previous observations of the J=1-0 transition lines of (13)CO. We find that the HCO+ and HCN have different spatial distributions. HCN appears to lie primarily inside dense clumps of gas, which are defined by areas of intense (13)CO emission. However, the HCO+ emission appears to be only loosely associated with the surfaces of the gas clumps. We suggest that HCO+ abundance is enhanced by the presence of vibrationally excited H2 on the surfaces of dense clumps, and that the HCN abundance is attenuated by photo destruction outside the cores of dense clumps of gas.

  4. Infrared Multiple-Photon Photodissociation of Gas-Phase Group II Metal-Nitrate Anions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    C. M. Leavitt; Jos Oomens; R. P. Dain

    2008-06-01

    Infrared spectra of gas-phase metal-nitrate anions M(NO{sub 3}){sub 3}{sup -}, where M = Mg{sup 2+}, Ca{sup 2+}, Sr{sup 2+} and Ba{sup 2+}, were recorded by infrared multiple-photon dissociation (IRMPD) spectroscopy. Photodissociation of each of the precursors produces NO{sub 3}{sup -} through the elimination of a neutral M(NO{sub 3}){sub 2} unit. An absorption pattern characteristic of metal nitrates is observed in the IRMPD spectra, including the symmetric and antisymmetric NO{sub 3} stretches. The latter is split into high-and low-frequency components as a result of perturbation of the nitrate symmetry by complexation to the metal ion, and the magnitude of the splittingmore » decreases following the trend Mg{sup 2+} > Ca{sup 2+} > Sr{sup 2+} {approx_equal} Ba{sup 2+}. The experimental spectra are in good general agreement with those obtained from density functional theory (DFT) calculations.« less

  5. UV photodissociation of proline-containing peptide ions: insights from molecular dynamics.

    PubMed

    Girod, Marion; Sanader, Zeljka; Vojkovic, Marin; Antoine, Rodolphe; MacAleese, Luke; Lemoine, Jérôme; Bonacic-Koutecky, Vlasta; Dugourd, Philippe

    2015-03-01

    UV photodissociation of proline-containing peptide ions leads to unusual product ions. In this paper, we report laser-induced dissociation of a series of proline-containing peptides at 213 nm. We observe specific fragmentation pathways corresponding to the formation of (y-2), (a + 2) and (b + 2) fragment ions. This was not observed at 266 nm or for peptides which do not contain proline residues. In order to obtain insights into the fragmentation dynamics at 213 nm, a small peptide (RPK for arginine-proline-lysine) was studied both theoretically and experimentally. Calculations of absorption spectra and non-adiabatic molecular dynamics (MD) were made. Second and third excited singlet states, S(2) and S(3), lie close to 213 nm. Non-adiabatic MD simulation starting from S(2) and S(3) shows that these transitions are followed by C-C and C-N bond activation close to the proline residue. After this first relaxation step, consecutive rearrangements and proton transfers are required to produce unusual (y-2), (a + 2) and (b + 2) fragment ions. These fragmentation mechanisms were confirmed by H/D exchange experiments.

  6. UV Photodissociation of Proline-containing Peptide Ions: Insights from Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Girod, Marion; Sanader, Zeljka; Vojkovic, Marin; Antoine, Rodolphe; MacAleese, Luke; Lemoine, Jérôme; Bonacic-Koutecky, Vlasta; Dugourd, Philippe

    2015-03-01

    UV photodissociation of proline-containing peptide ions leads to unusual product ions. In this paper, we report laser-induced dissociation of a series of proline-containing peptides at 213 nm. We observe specific fragmentation pathways corresponding to the formation of (y-2), (a + 2) and (b + 2) fragment ions. This was not observed at 266 nm or for peptides which do not contain proline residues. In order to obtain insights into the fragmentation dynamics at 213 nm, a small peptide (RPK for arginine-proline-lysine) was studied both theoretically and experimentally. Calculations of absorption spectra and non-adiabatic molecular dynamics (MD) were made. Second and third excited singlet states, S2 and S3, lie close to 213 nm. Non-adiabatic MD simulation starting from S2 and S3 shows that these transitions are followed by C-C and C-N bond activation close to the proline residue. After this first relaxation step, consecutive rearrangements and proton transfers are required to produce unusual (y-2), (a + 2) and (b + 2) fragment ions. These fragmentation mechanisms were confirmed by H/D exchange experiments.

  7. Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging

    DOE PAGES

    Makhov, Dmitry V.; Saita, Kenichiro; Martinez, Todd J.; ...

    2014-12-11

    In this study, we report a detailed computational simulation of the photodissociation of pyrrole using the ab initio Multiple Cloning (AIMC) method implemented within MOLPRO. The efficiency of the AIMC implementation, employing train basis sets, linear approximation for matrix elements, and Ehrenfest configuration cloning, allows us to accumulate significant statistics. We calculate and analyze the total kinetic energy release (TKER) spectrum and Velocity Map Imaging (VMI) of pyrrole and compare the results directly with experimental measurements. Both the TKER spectrum and the structure of the velocity map image (VMI) are well reproduced. Previously, it has been assumed that the isotropicmore » component of the VMI arises from long time statistical dissociation. Instead, our simulations suggest that ultrafast dynamics contributes significantly to both low and high energy portions of the TKER spectrum.« less

  8. Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Makhov, Dmitry V.; Saita, Kenichiro; Martinez, Todd J.

    In this study, we report a detailed computational simulation of the photodissociation of pyrrole using the ab initio Multiple Cloning (AIMC) method implemented within MOLPRO. The efficiency of the AIMC implementation, employing train basis sets, linear approximation for matrix elements, and Ehrenfest configuration cloning, allows us to accumulate significant statistics. We calculate and analyze the total kinetic energy release (TKER) spectrum and Velocity Map Imaging (VMI) of pyrrole and compare the results directly with experimental measurements. Both the TKER spectrum and the structure of the velocity map image (VMI) are well reproduced. Previously, it has been assumed that the isotropicmore » component of the VMI arises from long time statistical dissociation. Instead, our simulations suggest that ultrafast dynamics contributes significantly to both low and high energy portions of the TKER spectrum.« less

  9. Future Directions in Ultraviolet Spectroscopy

    NASA Technical Reports Server (NTRS)

    Sonneborn, George (Editor); Moos, Warren; VanSteenberg, Michael

    2009-01-01

    The 'Future Directions in Ultraviolet Spectroscopy' conference was inspired by the accomplishments of the Far Ultraviolet Spectroscopic Explorer (FUSE) Mission. The FUSE mission was launched in June 1999 and spent over eight years exploring the far-ultraviolet universe, gathering over 64 million seconds of high-resolution spectral data on nearly 3000 astronomical targets. The goal of this conference was not only to celebrate the accomplishments of FUSE, but to look toward the future and understand the major scientific drivers for the ultraviolet capabilities of the next generation fo space observatories. Invited speakers presented discussions based on measurements made by FUSE and other ultraviolet instruments, assessed their connection with measurements made with other techniques and, where appropriate, discussed the implications of low-z measurements for high-z phenomena. In addition to the oral presentations, many participants presented poster papers. The breadth of these presentation made it clear that much good science is still in progress with FUSE data and that these result will continue to have relevance in many scientific areas.

  10. Ab initio reaction pathways for photodissociation and isomerization of nitromethane on four singlet potential energy surfaces with three roaming paths

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Isegawa, Miho; Liu, Fengyi; Morokuma, Keiji

    2014-06-28

    Photodissociation pathways of nitromethane following π → π{sup *} electronic excitation are reported. The potential energy surfaces for four lowest singlet states are explored, and structures of many intermediates, dissociation limits, transition states, and minimum energy conical intersections were determined using the automated searching algorism called the global reaction route mapping strategy. Geometries are finally optimized at CASSCF(14e,11o) level and energies are computed at CAS(14o,11e)PT2 level. The calculated preferable pathways and important products qualitatively explain experimental observations. The major photodissociation product CH{sub 3} and NO{sub 2} ({sup 2}B{sub 2}) is formed by direct dissociation from the S{sub 1} state. Importantmore » pathways involving S{sub 1} and S{sub 0} states for production of various dissociation products CH{sub 3}NO + O ({sup 1}D), CH{sub 3}O(X{sup 2}E) + NO (X{sup 2}Π), CH{sub 2}NO + OH, and CH{sub 2}O + HNO, as well as various isomerization pathways have been identified. Three roaming processes also have been identified: the O atom roaming in O dissociation from CH{sub 3}NO{sub 2}, the OH radical roaming in OH dissociation from CH{sub 2}N(O)(OH), and the NO roaming in NO dissociation from CH{sub 3}ONO.« less

  11. Ultraviolet Enceladus

    NASA Image and Video Library

    2004-09-23

    Looking beyond Saturn's south pole, this was the Cassini spacecraft's view of the distant, icy moon Enceladus on July 28, 2004. The planet itself shows few obvious features at these ultraviolet wavelengths, due to scattering of light by molecules of the gases high in the atmosphere. Enceladus is 499 kilometers (310 miles) wide. The image was taken with the Cassini spacecraft narrow angle camera at a distance of 7.4 million kilometers (4.6 million miles) from Saturn through a filter sensitive to ultraviolet wavelengths of light. The image scale is 44 kilometers (27 miles) per pixel of Saturn. http://photojournal.jpl.nasa.gov/catalog/PIA06483

  12. Ultraviolet radiation induced discharge laser

    DOEpatents

    Gilson, Verle A.; Schriever, Richard L.; Shearer, James W.

    1978-01-01

    An ultraviolet radiation source associated with a suitable cathode-anode electrode structure, disposed in a gas-filled cavity of a high pressure pulsed laser, such as a transverse electric atmosphere (TEA) laser, to achieve free electron production in the gas by photoelectric interaction between ultraviolet radiation and the cathode prior to the gas-exciting cathode-to-anode electrical discharge, thereby providing volume ionization of the gas. The ultraviolet radiation is produced by a light source or by a spark discharge.

  13. Nonadiabatic effects in C-Br bond scission in the photodissociation of bromoacetyl chloride

    NASA Astrophysics Data System (ADS)

    Valero, Rosendo; Truhlar, Donald G.

    2006-11-01

    Bromoacetyl chloride photodissociation has been interpreted as a paradigmatic example of a process in which nonadiabatic effects play a major role. In molecular beam experiments by Butler and co-workers [J. Chem. Phys. 95, 3848 (1991); J. Chem. Phys. 97, 355 (1992)], BrCH2C(O )Cl was prepared in its ground electronic state (S0) and excited with a laser at 248nm to its first excited singlet state (S1). The two main ensuing photoreactions are the ruptures of the C-Cl bond and of the C-Br bond. A nonadiabatic model was proposed in which the C-Br scission is strongly suppressed due to nonadiabatic recrossing at the barrier formed by the avoided crossing between the S1 and S2 states. Recent reduced-dimensional dynamical studies lend support to this model. However, another interpretation that has been given for the experimental results is that the reduced probability of C-Br scission is a consequence of incomplete intramolecular energy redistribution. To provide further insight into this problem, we have studied the energetically lowest six singlet electronic states of bromoacetyl chloride by using an ab initio multiconfigurational perturbative electronic structure method. Stationary points (minima and saddle points) and minimum energy paths have been characterized on the S0 and S1 potential energy surfaces. The fourfold way diabatization method has been applied to transform five adiabatic excited electronic states to a diabatic representation. The diabatic potential energy matrix of the first five excited singlet states has been constructed along several cuts of the potential energy hypersurfaces. The thermochemistry of the photodissociation reactions and a comparison with experimental translational energy distributions strongly suggest that nonadiabatic effects dominate the C-Br scission, but that the reaction proceeds along the energetically allowed diabatic pathway to excited-state products instead of being nonadiabatically suppressed. This conclusion is also

  14. Oscillation of Branching Ratios Between the D(2s)+D(1s) and the D(2p)+D(1s) Channels in Direct Photodissociation of D_{2}.

    PubMed

    Wang, Jie; Meng, Qingnan; Mo, Yuxiang

    2017-08-04

    The direct photodissociation of D_{2} at excitation energies above 14.76 eV occurs via two channels, D(2s)+D(1s) and D(2p)+D(1s). The branching ratios between the two have been measured from the dissociation threshold to 3200 cm^{-1} above it, and it is found that they show cosine oscillations as a function of the fragment wave vector magnitudes. The oscillation is due to an interference effect and can be simulated using the phase difference between the wave functions of the two channels, analogous to Young's double-slit experiment. By fitting the measured branching ratios, we have determined the depths and widths of the effective spherical potential wells related to the two channels, which are in agreement with the effective depths and widths of the ab initio interaction potentials. The results of this Letter illustrate the importance of the relative phase between the fragments in controlling the branching ratios of the photodissociation channels.

  15. Oscillation of Branching Ratios Between the D (2 s )+D (1 s ) and the D (2 p )+D (1 s ) Channels in Direct Photodissociation of D2

    NASA Astrophysics Data System (ADS)

    Wang, Jie; Meng, Qingnan; Mo, Yuxiang

    2017-08-01

    The direct photodissociation of D2 at excitation energies above 14.76 eV occurs via two channels, D (2 s )+D (1 s ) and D (2 p )+D (1 s ) . The branching ratios between the two have been measured from the dissociation threshold to 3200 cm-1 above it, and it is found that they show cosine oscillations as a function of the fragment wave vector magnitudes. The oscillation is due to an interference effect and can be simulated using the phase difference between the wave functions of the two channels, analogous to Young's double-slit experiment. By fitting the measured branching ratios, we have determined the depths and widths of the effective spherical potential wells related to the two channels, which are in agreement with the effective depths and widths of the ab initio interaction potentials. The results of this Letter illustrate the importance of the relative phase between the fragments in controlling the branching ratios of the photodissociation channels.

  16. Highly Nuclear-Spin-Polarized Deuterium Atoms from the UV Photodissociation of Deuterium Iodide.

    PubMed

    Sofikitis, Dimitris; Glodic, Pavle; Koumarianou, Greta; Jiang, Hongyan; Bougas, Lykourgos; Samartzis, Peter C; Andreev, Alexander; Rakitzis, T Peter

    2017-06-09

    We report a novel highly spin-polarized deuterium (SPD) source, via the photodissociation of deuterium iodide at 270 nm. I(^{2}P_{3/2}) photofragments are ionized with m-state selectivity, and their velocity distribution measured via velocity-map slice imaging, from which the D polarization is determined. The process produces ∼100% electronically polarized D at the time of dissociation, which is then converted to ∼60% nuclear D polarization after ∼1.6  ns. These production times for SPD allow collision-limited densities of ∼10^{18}  cm^{-3} and at production rates of ∼10^{21}  s^{-1} which are 10^{6} and 10^{4} times higher than conventional (Stern-Gerlach separation) methods, respectively. We discuss the production of SPD beams, and combining high-density SPD with laser fusion, to investigate polarized D-T, D-^{3}He, and D-D fusion.

  17. Photodissociation dynamics of the 2-propyl radical, C{sub 3}H{sub 7}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Noller, Bastian; Fischer, Ingo

    2007-04-14

    The photodissociation of 2-propyl leading to propene+H was investigated with nanosecond time resolution. A supersonic beam of isolated 2-propyl radicals was produced by pyrolysis of 2-bromopopane. The kinetic energy release of the H-atom photofragment was monitored as a function of excitation wavelength by photofragment Doppler spectroscopy via the Lyman-{alpha} transition. The loss of hydrogen atoms after excitation proceeds in {alpha} position to the radical center with a rate constant of 5.8x10{sup 7} s{sup -1} at 254 nm. Approximately 20% of the excess energy is deposited as translation in the H-atom photofragment. In contrast 1-propyl does not lose H atoms tomore » a significant extent. The experimental results are compared to simple Rice-Ramsperger-Kassel-Marcus calculations. The possible reaction pathways are examined in hybrid density functional theory calculations.« less

  18. Inhibition of seagrass photosynthesis by ultraviolet-B radiation.

    PubMed

    Trocine, R P; Rice, J D; Wells, G N

    1981-07-01

    Effects of ultraviolet-B radiation on the photosynthesis of seagrasses (Halophila engelmanni Aschers, Halodule wrightii Aschers, and Syringodium filiforme Kütz) were examined. The intrinsic tolerance of each seagrass to ultraviolet-B, the presence and effectiveness of photorepair mechanisms to ultraviolet-B-induced photosynthetic inhibition, and the role of epiphytic growth as a shield from ultraviolet-B were investigated.Halodule was found to possess the greatest photosynthetic tolerance for ultraviolet-B. Photosynthesis in Syringodium was slightly more sensitive to ultraviolet-B while Halophila showed relatively little photosynthetic tolerance. Evidence for a photorepair mechanism was found only in Halodule. This mechanism effectively attenuated photosynthetic inhibition induced by ultraviolet-B dose rates and dosages in excess of natural conditions. Syringodium appeared to rely primarily on a thick epidermal cell layer to reduce photosynthetic damage. Halophila seemed to have no morphological or photorepair capabilities to deal with ultraviolet-B. This species appeared to rely on epiphytic and detrital shielding and the shade provided by other seagrasses to reduce ultraviolet-B irradiation to tolerable levels. The presence of epiphytes on leaf surfaces was found to reduce the extent of photosynthetic inhibition from ultraviolet-B exposure in all species.Observations obtained in this study seem to suggest the possibility of anthocyanin and/or other flavonoid synthesis as an adaptation to long term ultraviolet-B irradiation by these species. In addition, Halophila appears to obtain an increased photosynthetic tolerance to ultraviolet-B as an indirect benefit of chloroplast clumping to avoid photo-oxidation by intense levels of photosynthetically active radiation.

  19. Inhibition of seagrass photosynthesis by ultraviolet-B radiation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Trocine, R.P.; Rice, J.D.; Wells, G.N.

    1981-07-01

    Effects of ultraviolet-B radiation on the photosynthesis of seagrasses (Halophila engelmanni Aschers, Halodule wrightii Aschers, and Syringodium filiforme (Kuetz) were examined. The intrinsic tolerance of each seagrass to ultraviolet-B, the presence and effectiveness of photorepair mechanisms to ultraviolet-B-induced photosynthetic inhibition, and the role of epiphytic growth as a shield from ultraviolet-B were investigated. Halodule was found to possess the greatest photosynthetic tolerance for ultraviolet-B. Photosynthesis in Syringodium was slightly more sensitive to ultraviolet-B while Halophila showed relatively little photosynthetic tolerance. Evidence for a photorepair mechanism was found only in Halodule. Syringodium appeared to rely primarily on a thick epidermal cellmore » layer to reduce photosynthetic damage. Halophila seemed to have no morphological or photorepair capabilities to deal with ultraviolet-B. This species appeared to rely on epiphytic and detrital shielding and the shade provided by other seagrasses to reduce ultraviolet-B irradiation to tolerable levels. The presence of epiphytes on leaf surfaces was found to reduce the extent of photosynthetic inhibition from ultraviolet-B exposure in all species. Halophila appears to obtain an increased photosynthetic tolerance to ultraviolet-B as an indirect benefit of chloroplast clumping to avoid photo-oxidation by intense levels of photosynthetically active radiation.« less

  20. Photodegradation of sulfasalazine and its human metabolites in water by UV and UV/peroxydisulfate processes.

    PubMed

    Ji, Yuefei; Yang, Yan; Zhou, Lei; Wang, Lu; Lu, Junhe; Ferronato, Corinne; Chovelon, Jean-Marc

    2018-04-15

    The widespread occurrence of pharmaceuticals and their metabolites in natural waters has raised great concerns about their potential risks on human health and ecological systems. This study systematically investigates the degradation of sulfasalazine (SSZ) and its two human metabolites, sulfapyridine (SPD) and 5-aminosalicylic acid (5-ASA), by UV and UV/peroxydisulfate (UV/PDS) processes. Experimental results show that SPD and 5-ASA were readily degraded upon UV 254 nm direct photolysis, with quantum yields measured to be (8.6 ± 0.8) × 10 -3 and (2.4 ± 0.1) × 10 -2  mol Einstein -1 , respectively. Although SSZ was resistant to direct UV photolysis, it could be effectively removed by both UV/H 2 O 2 and UV/PDS processes, with fluence-based pseudo-first-order rate constants determined to be 0.0030 and 0.0038 cm 2  mJ -1 , respectively. Second-order rate constant between SO 4 •- and SSZ was measured as (1.33 ± 0.01) × 10 9  M -1 s -1 by competition kinetic method. A kinetic model was established for predicting the degradation rate of SSZ in the UV/PDS process. Increasing the dosage of PDS significantly enhanced the degradation of SSZ in the UV/PDS process, which can be well predicted by the developed kinetic model. Natural water constituents, such as natural organic matter (NOM) and bicarbonate (HCO 3 - ), influenced the degradation of SSZ differently. The azo functional group of SSZ molecule was predicted as the reactive site susceptible to electrophilic attack by SO 4 •- by frontier electron densities (FEDs) calculations. Four intermediate products arising from azo bond cleavage and SO 2 extrusion were identified by solid phase extraction-liquid chromatography-triple quadrupole mass spectrometry (SPE-LC-MS/MS). Based on the products identified, detailed transformation pathways for SSZ degradation in the UV/PDS system were proposed. Results reveal that UV/PDS could be an efficient approach for remediation of water

  1. Ferromagnetic spin coupling in the chromium dimer cation: Measurements by photodissociation spectroscopy combined with coupled-cluster calculations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Egashira, Kazuhiro, E-mail: egashira@clusterlab.jp; Yamada, Yurika; Kita, Yukiumi

    2015-02-07

    The magnetic coupling of the chromium dimer cation, Cr{sub 2}{sup +}, has been an outstanding problem for decades. An optical absorption spectrum of Cr{sub 2}{sup +} has been obtained by photodissociation spectroscopy in the photon-energy range from 2.0 to 5.0 eV. Besides, calculations have been performed by the equation-of-motion coupled-cluster singles and doubles method for vertical excitation of the species. Their coincidence supports our assignment that the ground electronic state exhibits a ferromagnetic spin coupling, which is contrary to those of neutral and negatively charged dimers, Cr{sub 2} and Cr{sub 2}{sup −}, in their lowest spin states.

  2. Corona And Ultraviolet Equipment For Testing Materials

    NASA Technical Reports Server (NTRS)

    Laue, Eric G.

    1993-01-01

    Two assemblies of laboratory equipment developed for use in testing abilities of polymers, paints, and other materials to withstand ultraviolet radiation and charged particles. One is vacuum ultraviolet source built around commercial deuterium lamp. Other exposes specimen in partial vacuum to both ultraviolet radiation and brush corona discharge. Either or both assemblies used separately or together to simulate approximately combination of solar radiation and charged particles encountered by materials aboard spacecraft in orbit around Earth. Also used to provide rigorous environmental tests of materials exposed to artificial ultraviolet radiation and charged particles in industrial and scientific settings or to natural ultraviolet radiation and charged particles aboard aircraft at high altitudes.

  3. Polymerizable ultraviolet stabilizers for outdoor use

    NASA Technical Reports Server (NTRS)

    Vogl, O.

    1982-01-01

    Polymeric materials that are stable enough to use outdoors without changes in excess of 20 years are investigated. Ultraviolet stabilizers or plastic materials were synthesized, polymerizable ultraviolet stabilizers, particularly of the 2(2-hydroxyphenyl)2H-benzotriazole family were prepared their polymerization, copolymerization and grafting onto other polymers were demonstrated, and ultraviolet stabilizing systems were devised. These materials were evaluated from the photophysical point of view.

  4. Mutagenesis of Trichoderma Viride by Ultraviolet and Plasma

    NASA Astrophysics Data System (ADS)

    Yao, Risheng; Li, Manman; Deng, Shengsong; Hu, Huajia; Wang, Huai; Li, Fenghe

    2012-04-01

    Considering the importance of a microbial strain capable of increased cellulase production, a mutant strain UP4 of Trichoderma viride was developed by ultraviolet (UV) and plasma mutation. The mutant produced a 21.0 IU/mL FPase which was 98.1% higher than that of the parent strain Trichoderma viride ZY-1. In addition, the effect of ultraviolet and plasma mutagenesis was not merely simple superimposition of single ultraviolet mutation and single plasma mutation. Meanwhile, there appeared a capsule around some of the spores after the ultraviolet and plasma treatment, namely, the spore surface of the strain became fuzzy after ultraviolet or ultraviolet and plasma mutagenesis.

  5. Ozone Depletion, UVB and Atmospheric Chemistry

    NASA Technical Reports Server (NTRS)

    Stolarski, Richard S.

    1999-01-01

    The primary constituents of the Earth's atmosphere are molecular nitrogen and molecular oxygen. Ozone is created when ultraviolet light from the sun photodissociates molecular oxygen into two oxygen atoms. The oxygen atoms undergo many collisions but eventually combine with a molecular oxygen to form ozone (O3). The ozone molecules absorb ultraviolet solar radiation, primarily in the wavelength region between 200 and 300 nanometers, resulting in the dissociation of ozone back into atomic oxygen and molecular oxygen. The oxygen atom reattaches to an O2 molecule, reforming ozone which can then absorb another ultraviolet photon. This sequence goes back and forth between atomic oxygen and ozone, each time absorbing a uv photon, until the oxygen atom collides with and ozone molecule to reform two oxygen molecules.

  6. Far-ultraviolet spectral changes of titanium dioxide with gold nanoparticles by ultraviolet and visible light

    NASA Astrophysics Data System (ADS)

    Tanabe, Ichiro; Kurawaki, Yuji

    2018-05-01

    Attenuated total reflectance spectra including the far-ultraviolet (FUV, ≤ 200 nm) region of titanium dioxide (TiO2) with and without gold (Au) nanoparticles were measured. A newly developed external light-irradiation system enabled to observe spectral changes of TiO2 with Au nanoparticles upon light irradiations. Absorption in the FUV region decreased and increased by the irradiation with ultraviolet and visible light, respectively. These spectral changes may reflect photo-induced electron transfer from TiO2 to Au nanoparticles under ultraviolet light and from Au nanoparticles to TiO2 under visible light, respectively.

  7. [Ultraviolet radiation and long term space flight].

    PubMed

    Wu, H B; Su, S N; Ba, F S

    2000-08-01

    With the prolongation of space flight, influences of various aerospace environmental factors on the astronauts become more and more severe, while ultraviolet radiation is lacking. Some studies indicated that low doses of ultraviolet rays are useful and essential for human body. In space flight, ultraviolet rays can improve the hygienic condition in the space cabin, enhance astronaut's working ability and resistance to unfavorable factors, prevent mineral metabolic disorders, cure purulent skin diseases and deallergize the allergens. So in long-term space flight, moderate amount of ultraviolet rays in the space cabin would be beneficial.

  8. Ultraviolet spectrophotometry of three LINERs

    NASA Technical Reports Server (NTRS)

    Goodrich, R. W.; Keel, W. C.

    1986-01-01

    Three galaxies known to be LINERs were observed spectroscopically in the ultraviolet in an attempt to detect the presumed nonthermal continuum source thought to be the source of photoionization in the nuclei. NGC 4501 was found to be too faint for study with the IUE spectrographs, while NGC 5005 had an extended ultraviolet light profile. Comparison with the optical light profile of NGC 5005 indicates that the ultraviolet source is distributed spatially in the same manner as the optical starlight, probably indicating that the ultraviolet excess is due to a component of hot stars in the nucleus. These stars contribute detectable absorption features longward of 2500 A; together with optical data, the IUE spectra suggest a burst of star formation about 1 billion yr ago, with a lower rate continuing to produce a few OB stars. In NGC 4579, a point source contributing most of the ultraviolet excess is found that is much different than the optical light distribution. Furthermore, the ultraviolet to X-ray spectral index in NGC 4579 is 1.4, compatible with the UV to X-ray indices found for samples of Seyfert galaxies. This provides compelling evidence for the detection of the photoionizing continuum in NGC 4579 and draws the research fields of normal galaxies and active galactic nuclei closer together. The emission-line spectrum of NGC 4579 is compared with calculations from a photoionization code, CLOUDY, and several shock models. The photoionization code is found to give superior results, adding to the increasing weight of evidence that the LINER phenomenon is essentially a scaled-down version of the Seyfert phenomenon.

  9. Vacuum ultraviolet imagery of the Virgo Cluster region. II - Total far-ultraviolet flux of galaxies

    NASA Astrophysics Data System (ADS)

    Kodaira, K.; Watanabe, T.; Onaka, T.; Tanaka, W.

    1990-11-01

    The total flux in the far-ultraviolet region around 150 nm was measured for more than 40 galaxies in the central region of the Virgo Cluster, using two imaging telescopes on board a sounding rocket. The observed far-ultraviolet flux shows positive correlations with the H I 21 cm flux and the far-infrared flux for spiral galaxies, and with the X-ray flux and the radio continuum flux for elliptical galaxies. The former correlations of spiral galaxies are interpreted in terms of star formation activity, which indicates substantial depletion in the Virgo galaxies in accordance with the H I stripping. The latter correlations of elliptical galaxies indicate possible far-ultraviolet sources of young population, in addition to evolved hot stars. Far-ultraviolet fluxes from two dwarf elliptical galaxies were obtained tentatively, indicating star formation activity in elliptical galaxies. A high-resolution UV imagery by HST would be effective to distinguish the young population and the old population in elliptical galaxies.

  10. Ultraviolet safety assessments of insect light traps.

    PubMed

    Sliney, David H; Gilbert, David W; Lyon, Terry

    2016-01-01

    Near-ultraviolet (UV-A: 315-400 nm), "black-light," electric lamps were invented in 1935 and ultraviolet insect light traps (ILTs) were introduced for use in agriculture around that time. Today ILTs are used indoors in several industries and in food-service as well as in outdoor settings. With recent interest in photobiological lamp safety, safety standards are being developed to test for potentially hazardous ultraviolet emissions. A variety of UV "Black-light" ILTs were measured at a range of distances to assess potential exposures. Realistic time-weighted human exposures are shown to be well below current guidelines for human exposure to ultraviolet radiation. These UV-A exposures would be far less than the typical UV-A exposure in the outdoor environment. Proposals are made for realistic ultraviolet safety standards for ILT products.

  11. Ultraviolet Extensions

    NASA Image and Video Library

    2008-04-16

    This ultraviolet image from NASA Galaxy Evolution Explorer shows the Southern Pinwheel galaxy, also know as Messier 83 or M83. It is located 15 million light-years away in the southern constellation Hydra.

  12. Control of photodissociation and photoionization of the NaI molecule by dynamic Stark effect.

    PubMed

    Han, Yong-Chang; Yuan, Kai-Jun; Hu, Wen-Hui; Cong, Shu-Lin

    2009-01-28

    The diabatic photodissociation and photoionization processes of the NaI molecule are studied theoretically using the quantum wave packet method. A pump laser pulse is used to prepare a dissociation wave packet that propagates through both the ionic channel (NaI-->Na(+)+I(-)) and the covalent channel (NaI-->Na+I). A Stark pulse is used to control the diabatic dissociation dynamics and a probe pulse is employed to ionize the products from the two channels. Based on the first order nonresonant nonperturbative dynamic Stark effect, the dissociation probabilities and the branching ratio of the products from the two channels can be controlled. Moreover the final photoelectron kinetic energy distribution can also be affected by the Stark pulse. The influences of the delay time, intensity, frequency, and carrier-envelope phase of the Stark pulse on the dissociation and ionization dynamics of the NaI molecule are discussed in detail.

  13. Photodissociation studies of the electronic and vibrational spectroscopy of Ni(+)(H2O).

    PubMed

    Daluz, Jennifer S; Kocak, Abdulkadir; Metz, Ricardo B

    2012-02-09

    The electronic spectrum of Ni⁺(H₂O) has been measured from 16200 to 18000 cm⁻¹ using photofragment spectroscopy. Transitions to two excited electronic states are observed; they are sufficiently long-lived that the spectrum is vibrationally and partially rotationally resolved. An extended progression in the metal-ligand stretch is observed, and the absolute vibrational quantum numbering is assigned by comparing isotopic shifts between ⁵⁸Ni⁺(H₂O) and ⁶⁰Ni⁺(H₂O). Time-dependent density functional calculations aid in assigning the spectrum. Two electronic transitions are observed, from the ²A₁ ground state (which correlates to the ²D, 3d⁹ ground state of Ni⁺) to the 3²A₁ and 2²A₂ excited states. These states are nearly degenerate and correlate to the ²F, 3d⁸4s excited state of Ni⁺. Both transitions are quite weak, but surprisingly, the transition to the ²A₂ state is stronger, although it is symmetry-forbidden. The 3d⁸4s states of Ni⁺ interact less strongly with water than does the ground state; therefore, the excited states observed are less tightly bound and have a longer metal-ligand bond than the ground state. Calculations at the CCSD(T)/aug-cc-pVTZ level predict that binding to Ni⁺ increases the H-O-H angle in water from 104.2 to 107.5° as the metal removes electron density from the oxygen lone pairs. The photodissociation spectrum shows well-resolved rotational structure due to rotation about the Ni-O axis. This permits determination of the spin rotation constants ε(αα)'' = -12 cm⁻¹ and ε(αα)' = -3 cm⁻¹ and the excited state rotational constant A' = 14.5 cm⁻¹. This implies a H-O-H angle of 104 ± 1° in the 2²A₂ excited state. The O-H stretching frequencies of the ground state of Ni⁺(H₂O) were measured by combining IR excitation with visible photodissociation in a double resonance experiment. The O-H symmetric stretch is ν₁'' = 3616.5 cm⁻¹; the antisymmetric stretch is ν₅'' = 3688

  14. Inhibition of Seagrass Photosynthesis by Ultraviolet-B Radiation 1

    PubMed Central

    Trocine, Robert P.; Rice, John D.; Wells, Gary N.

    1981-01-01

    Effects of ultraviolet-B radiation on the photosynthesis of seagrasses (Halophila engelmanni Aschers, Halodule wrightii Aschers, and Syringodium filiforme Kütz) were examined. The intrinsic tolerance of each seagrass to ultraviolet-B, the presence and effectiveness of photorepair mechanisms to ultraviolet-B-induced photosynthetic inhibition, and the role of epiphytic growth as a shield from ultraviolet-B were investigated. Halodule was found to possess the greatest photosynthetic tolerance for ultraviolet-B. Photosynthesis in Syringodium was slightly more sensitive to ultraviolet-B while Halophila showed relatively little photosynthetic tolerance. Evidence for a photorepair mechanism was found only in Halodule. This mechanism effectively attenuated photosynthetic inhibition induced by ultraviolet-B dose rates and dosages in excess of natural conditions. Syringodium appeared to rely primarily on a thick epidermal cell layer to reduce photosynthetic damage. Halophila seemed to have no morphological or photorepair capabilities to deal with ultraviolet-B. This species appeared to rely on epiphytic and detrital shielding and the shade provided by other seagrasses to reduce ultraviolet-B irradiation to tolerable levels. The presence of epiphytes on leaf surfaces was found to reduce the extent of photosynthetic inhibition from ultraviolet-B exposure in all species. Observations obtained in this study seem to suggest the possibility of anthocyanin and/or other flavonoid synthesis as an adaptation to long term ultraviolet-B irradiation by these species. In addition, Halophila appears to obtain an increased photosynthetic tolerance to ultraviolet-B as an indirect benefit of chloroplast clumping to avoid photo-oxidation by intense levels of photosynthetically active radiation. Images PMID:16661893

  15. Far-ultraviolet spectral changes of titanium dioxide with gold nanoparticles by ultraviolet and visible light.

    PubMed

    Tanabe, Ichiro; Kurawaki, Yuji

    2018-05-15

    Attenuated total reflectance spectra including the far-ultraviolet (FUV, ≤200nm) region of titanium dioxide (TiO 2 ) with and without gold (Au) nanoparticles were measured. A newly developed external light-irradiation system enabled to observe spectral changes of TiO 2 with Au nanoparticles upon light irradiations. Absorption in the FUV region decreased and increased by the irradiation with ultraviolet and visible light, respectively. These spectral changes may reflect photo-induced electron transfer from TiO 2 to Au nanoparticles under ultraviolet light and from Au nanoparticles to TiO 2 under visible light, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Real-time detection of S(1D2) photofragments produced from the 1B2(1Σu+) state of CS2 by vacuum ultraviolet photoelectron imaging using 133 nm probe pulses

    NASA Astrophysics Data System (ADS)

    Horio, Takuya; Spesyvtsev, Roman; Furumido, Yu; Suzuki, Toshinori

    2017-07-01

    Ultrafast photodissociation dynamics from the 1B2(1Σu+) state of CS2 are studied by time-resolved photoelectron imaging using the fourth (4ω, 198 nm) and sixth (6ω, 133 nm) harmonics of a femtosecond Ti:sapphire laser. The 1B2 state of CS2 was prepared with the 4ω pulses, and subsequent dynamics were probed using the 6ω vacuum ultraviolet (VUV) pulses. The VUV pulses enabled real-time detection of S(1D2) photofragments, produced via CS2*(1B2(1Σu+)) → CS(X 1Σ+) + S(1D2). The photoionization signal of dissociating CS2*(1B2(1Σu+)) molecules starts to decrease at about 100 fs, while the S(1D2) fragments appear with a finite (ca. 400 fs) delay time after the pump pulse. Also discussed is the configuration interaction of the 1B2(1Σu+) state based on relative photoionization cross-sections to different cationic states.

  17. Ultraviolet safety assessments of insect light traps

    PubMed Central

    Sliney, David H.; Gilbert, David W.; Lyon, Terry

    2016-01-01

    ABSTRACT Near-ultraviolet (UV-A: 315–400 nm), “black-light,” electric lamps were invented in 1935 and ultraviolet insect light traps (ILTs) were introduced for use in agriculture around that time. Today ILTs are used indoors in several industries and in food-service as well as in outdoor settings. With recent interest in photobiological lamp safety, safety standards are being developed to test for potentially hazardous ultraviolet emissions. A variety of UV “Black-light” ILTs were measured at a range of distances to assess potential exposures. Realistic time-weighted human exposures are shown to be well below current guidelines for human exposure to ultraviolet radiation. These UV-A exposures would be far less than the typical UV-A exposure in the outdoor environment. Proposals are made for realistic ultraviolet safety standards for ILT products. PMID:27043058

  18. Aqueous humour and ultraviolet radiation.

    PubMed

    Ringvold, A

    1980-01-01

    Studies on the ultraviolet ray absorption in the aqueous humour of rabbit, cat, monkey, guinea pig, and rat showed marked species differences. In the rabbit aqueous the ascorbic acid, the proteins, and some amino acids (tyrosine, phenylalanine, cystine, and tryptophane) are together responsible for the total absorption, and a very great part of it refers to the ascorbic acid content. Accordingly, species with significant amounts of ascorbic acid in the aqueous (monkey, rabbit, guinea pig) have a greater absorption capacity towards ultraviolet radiation than species (cat, rat) lacking this substance. This effect of the ascorbic acid may contribute in protecting the lens against the most biotoxic ultraviolet rays. It seems that the ascorbic acid concentration is highest in the aqueous of typical day animals and lowest in species being active in the dark, indicating a correlation between the aqueous' ascorbic acid level and the quantity of incident light on the eye. The possible significance of changed aqueous ultraviolet ray absorption in the pathogenesis of human cataract development is discussed.

  19. The ultraviolet detection component based on Te-Cs image intensifier

    NASA Astrophysics Data System (ADS)

    Qian, Yunsheng; Zhou, Xiaoyu; Wu, Yujing; Wang, Yan; Xu, Hua

    2017-05-01

    Ultraviolet detection technology has been widely focused and adopted in the fields of ultraviolet warning and corona detection for its significant value and practical meaning. The component structure of ultraviolet ICMOS, imaging driving and the photon counting algorithm are studied in this paper. Firstly, the one-inch and wide dynamic range CMOS chip with the coupling optical fiber panel is coupled to the ultraviolet image intensifier. The photocathode material in ultraviolet image intensifier is Te-Cs, which contributes to the solar blind characteristic, and the dual micro-channel plates (MCP) structure ensures the sufficient gain to achieve the single photon counting. Then, in consideration of the ultraviolet detection demand, the drive circuit of the CMOS chip is designed and the corresponding program based on Verilog language is written. According to the characteristics of ultraviolet imaging, the histogram equalization method is applied to enhance the ultraviolet image and the connected components labeling way is utilized for the ultraviolet single photon counting. Moreover, one visible light video channel is reserved in the ultraviolet ICOMS camera, which can be used for the fusion of ultraviolet and visible images. Based upon the module, the ultraviolet optical lens and the deep cut-off solar blind filter are adopted to construct the ultraviolet detector. At last, the detection experiment of the single photon signal is carried out, and the test results are given and analyzed.

  20. Theoretical analysis of the time-resolved binary (e, 2e) binding energy spectra on three-body photodissociation of acetone at 195 nm

    NASA Astrophysics Data System (ADS)

    Yamazaki, M.; Nakayama, S.; Zhu, C. Y.; Takahashi, M.

    2017-11-01

    We report on theoretical progress in time-resolved (e, 2e) electron momentum spectroscopy of photodissociation dynamics of the deuterated acetone molecule at 195 nm. We have examined the predicted minimum energy reaction path to investigate whether associated (e, 2e) calculations meet the experimental results. A noticeable difference between the experiment and calculations has been found at around binding energy of 10 eV, suggesting that the observed difference may originate, at least partly, in ever-unconsidered non-minimum energy paths.

  1. Ultraviolet Spectroscopy of Asteroid(4) Vesta

    NASA Technical Reports Server (NTRS)

    Li, Jian-Yang; Bodewits, Dennis; Feaga, Lori M.; Landsman, Wayne; A'Hearn, Michael F.; Mutchler, Max J.; Russell, Christopher T.; McFadden, Lucy A.; Raymond, Carol A.

    2011-01-01

    We report a comprehensive review of the UV-visible spectrum and rotational lightcurve of Vesta combining new observations by Hubble Space Telescope and Swift with archival International Ultraviolet Explorer observations. The geometric albedos of Vesta from 220 nm to 953 nm arc derived by carefully comparing these observations from various instruments at different times and observing geometries. Vesta has a rotationally averaged geometric albedo of 0.09 at 250 nm, 0.14 at 300 nm, 0.26 at 373 nm, 0.38 at 673 nm, and 0.30 at 950 nm. The linear spectral slope in the ultraviolet displays a sharp minimum ncar sub-Earth longitude of 20deg, and maximum in the eastern hemisphere. This is completely consistent with the distribution of the spectral slope in the visible wavelength. The uncertainty of the measurement in the ultraviolet is approx.20%, and in the visible wavelengths better than 10%. The amplitude of Vesta's rotational lightcurves is approx.10% throughout the range of wavelengths we observed, but is smaller at 950 nm (approx.6%) ncar the 1-micron mafic band center. Contrary to earlier reports, we found no evidence for any difference between the phasing of the ultraviolet and visible/ncar-infrared lightcurves with respect to sub-Earth longitude. Vesta's average spectrum between 220 and 950 nm can well be described by measured reflectance spectra of fine particle howardite-like materials of basaltic achondrite meteorites. Combining this with the in-phase behavior of the ultraviolet, visible. and ncar-infrared lightcurves, and the spectral slopes with respect to the rotational phase, we conclude that there is no global ultraviolet/visible reversal on Vesta. Consequently, this implies lack of global space weathering on Vesta. Keyword,: Asteroid Vesta; Spectrophotometry; Spectroscopy; Ultraviolet observations; Hubble Space Telescope observations

  2. Photodissociation of N2O: triplet states and triplet channel.

    PubMed

    Schinke, R; Schmidt, J A; Johnson, M S

    2011-11-21

    The role of triplet states in the UV photodissociation of N(2)O is investigated by means of quantum mechanical wave packet calculations. Global potential energy surfaces are calculated for the lowest two (3)A' and the lowest two (3)A'' states at the multi-reference configuration interaction level of electronic structure theory using the augmented valence quadruple zeta atomic basis set. Because of extremely small transition dipole moments with the ground electronic state, excitation of the triplet states has only a marginal effect on the far red tail of the absorption cross section. The calculations do not show any hint of an increased absorption around 280 nm as claimed by early experimental studies. The peak observed in several electron energy loss spectra at 5.4 eV is unambiguously attributed to the lowest triplet state 1(3)A'. Excitation of the 2(1)A' state and subsequent transition to the repulsive branch of the 2(3)A'' state at intermediate NN-O separations, promoted by spin-orbit coupling, is identified as the main pathway to the N(2)((1)Σ(g)(+))+O((3)P) triplet channel. The yield, determined in two-state wave packet calculations employing calculated spin-orbit matrix elements, is 0.002 as compared to 0.005 ± 0.002 measured by Nishida et al. [J. Phys. Chem. A 108, 2451 (2004)].

  3. Detection of OH stretching mode of CH3OH chemisorbed on Ni3+ and Ni4+ by infrared photodissociation spectroscopy.

    PubMed

    Hirabayashi, Shinichi; Okawa, Ryuji; Ichihashi, Masahiko; Kondow, Tamotsu; Kawazoe, Yoshiyuki

    2007-08-09

    Structures of nickel cluster ions adsorbed with methanol, Ni3+ (CH3OH)m (m = 1-3) and Ni4+ (CH3OH)m (m = 1-4) were investigated by using infrared photodissociation (IR-PD) spectroscopy based on a tandem-type mass spectrometer, where they were produced by passing Ni3,4+ through methanol vapor under a multiple collision condition. The IR-PD spectra were measured in the wavenumber region between 3100 and 3900 cm-1. In each IR-PD spectrum, a single peak was observed at a wavenumber lower by approximately 40 cm-1 than that of the OH stretching vibration of a free methanol molecule and was assigned to the OH stretching vibrations of the methanol molecules in Ni3,4+ (CH3OH)m. The photodissociation was analyzed by assuming that Ni3,4+ (CH3OH)m dissociate unimolecularly after the photon energy absorbed by them is statistically distributed among the accessible modes of Ni3,4+ (CH3OH)m. In comparison with the calculations performed by the density functional theory, it is concluded that (1) the oxygen atom of each methanol molecule is bound to one of the nickel atoms in Ni3,4+ (defined as molecular chemisorption), (2) the methanol molecules in Ni3,4+ (CH3OH)m do not form any hydrogen bonds, and (3) the cross section for demethanation [CH4 detachment from Nin+ (CH3OH)] is related to the electron density distribution inside the methanol molecule.

  4. Nonthermal combined ultraviolet and vacuum-ultraviolet curing process for organosilicate dielectrics

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zheng, H.; Guo, X.; Pei, D.

    2016-06-13

    Porous SiCOH films are of great interest in semiconductor fabrication due to their low-dielectric constant properties. Post-deposition treatments using ultraviolet (UV) light on organosilicate thin films are required to decompose labile pore generators (porogens) and to ensure optimum network formation to improve the electrical and mechanical properties of low-k dielectrics. The goal of this work is to choose the best vacuum-ultraviolet photon energy in conjunction with vacuum ultraviolet (VUV) photons without the need for heating the dielectric to identify those wavelengths that will have the most beneficial effect on improving the dielectric properties and minimizing damage. VUV irradiation between 8.3more » and 8.9 eV was found to increase the hardness and elastic modulus of low-k dielectrics at room temperature. Combined with UV exposures of 6.2 eV, it was found that this “UV/VUV curing” process is improved compared with current UV curing. We show that UV/VUV curing can overcome drawbacks of UV curing and improve the properties of dielectrics more efficiently without the need for high-temperature heating of the dielectric.« less

  5. Extracting Both Peptide Sequence and Glycan Structural Information by 157 nm Photodissociation of N-Linked Glycopeptides

    PubMed Central

    Zhang, Liangyi; Reilly, James P.

    2009-01-01

    157 nm photodissociation of N-linked glycopeptides was investigated in MALDI tandem time-of-flight (TOF) and linear ion trap mass spectrometers. Singly-charged glycopeptides yielded abundant peptide and glycan fragments. The peptide fragments included a series of x-, y-, v- and w- ions with the glycan remaining intact. These provide information about the peptide sequence and the glycosylation site. In addition to glycosidic fragments, abundant cross-ring glycan fragments that are not observed in low-energy CID were detected. These fragments provide insight into the glycan sequence and linkages. Doubly-charged glycopeptides generated by nanospray in the linear ion trap mass spectrometer also yielded peptide and glycan fragments. However, the former were dominated by low-energy fragments such as b- and y- type ions while glycan was primarily cleaved at glycosidic bonds. PMID:19113943

  6. Theoretical study of the photodissociation of Li(2)+ in one-color intense laser fields.

    PubMed

    Li, Yuanjun; Jiang, Wanyi; Khait, Yuriy G; Hoffmann, Mark R

    2011-05-07

    A theoretical treatment of the photodissociation of the molecular ion Li(2) (+) in one-color intense laser fields, using the time-dependent wave packet approach in a Floquet Born-Oppenheimer representation, is presented. Six electronic states 1,2 (2)Σ(g)(+), 1,2 (2)Σ(u)(+), 1 (2)Π(g), and 1 (2)Π(u) are of relevance in this simulation and have been included. The dependences of the fragmental dissociation probabilities and kinetic energy release (KER) spectra on pulse width, peak intensity, polarization angle, wavelength, and initial vibrational level are analyzed to interpret the influence of control parameters of the external field. Three main dissociation channels, 1 (2)Σ(g)(+) (m = -1), 2 (2)Σ(g)(+) (m = -2), and 2 (2)Σ(u)(+) (m = -3), are seen to dominate the dissociation processes under a wide variety of laser conditions and give rise to well separated groups of KER features. Different dissociation mechanisms for the involved Floquet channels are discussed.

  7. LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Study of photodissociation parameters of carboxyhemoglobin

    NASA Astrophysics Data System (ADS)

    Kuz'min, V. V.; Salmin, V. V.; Salmina, A. B.; Provorov, A. S.

    2008-07-01

    The general properties of photodissociation of carboxyhemoglobin (HbCO) in buffer solutions of whole human blood are studied by the flash photolysis method on a setup with intersecting beams. It is shown that the efficiency of photoinduced dissociation of the HbCO complex virtually linearly depends on the photolytic irradiation intensity for the average power density not exceeding 45 mW cm-2. The general dissociation of the HbCO complex in native conditions occurs in a narrower range of values of the saturation degree than in model experiments with the hemoglobin solution. The dependence of the pulse photolysis efficiency of HbCO on the photolytic radiation wavelength in the range from 550 to 585 nm has a broad bell shape. The efficiency maximum corresponds to the electronic Q transition (porphyrin π—π* absorption) in HbCO at a wavelength of 570 nm. No dissociation of the complex was observed under given experimental conditions upon irradiation of solutions by photolytic radiation at wavelengths above 585 nm.

  8. Near unity ultraviolet absorption in graphene without patterning

    NASA Astrophysics Data System (ADS)

    Zhu, Jinfeng; Yan, Shuang; Feng, Naixing; Ye, Longfang; Ou, Jun-Yu; Liu, Qing Huo

    2018-04-01

    Enhancing the light-matter interaction of graphene is an important issue for related photonic devices and applications. In view of its potential ultraviolet applications, we aim to achieve extremely high ultraviolet absorption in graphene without any nanostructure or microstructure patterning. By manipulating the polarization and angle of incident light, the ultraviolet power can be sufficiently coupled to the optical dissipation of graphene based on single-channel coherent perfect absorption in an optimized multilayered thin film structure. The ultraviolet absorbance ratios of single and four atomic graphene layers are enhanced up to 71.4% and 92.2%, respectively. Our research provides a simple and efficient scheme to trap ultraviolet light for developing promising photonic and optoelectronic devices based on graphene and potentially other 2D materials.

  9. International Conference on Photochemistry (15th) Abstracts of Invited Lectures and Oral and Poster Contributions Held in Paris, France on 28 July-2 August 1991 (XVeme Conference Internationale de Photochimie, Paris, France 28 Juillet-2 Aout 1991)

    DTIC Science & Technology

    1991-08-01

    pyrene-labelled palmitoyl-phosphatidylcholine (PyPPC) and DPPA the pyrene is located at the monolayer-air interface. The ad- sorption of the electron...chemical transfor- mation of many trace compounds. Photodissociation of atmospheric species occurs by ab- sorption of solar ultraviolet and visible radiation...bakable one, and its inner surface is coated with PFA . The solar simulator and the end windows to introduce UV light were modified in order to utilize

  10. STEREO's Extreme UltraViolet Imager (EUVI)

    NASA Technical Reports Server (NTRS)

    2007-01-01

    At a pixel resolution of 2048x2048, the STEREO EUVI instrument provides views of the Sun in ultraviolet light that rivals the full-disk views of SOHO/EIT. This image is through the 171 Angstrom (ultraviolet) filter which is characteristic of iron ions (missing eight and nine electrons) at 1 million degrees. There is a short data gap in the latter half of the movie that creates a freeze and then jump in the data view. This is a movie of the Sun in 171 Angstrom ultraviolet light. The time frame is late January, 2007

  11. 21 CFR 880.6710 - Medical ultraviolet water purifier.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Medical ultraviolet water purifier. 880.6710... Miscellaneous Devices § 880.6710 Medical ultraviolet water purifier. (a) Identification. A medical ultraviolet water purifier is a device intended for medical purposes that is used to destroy bacteria in water by...

  12. 21 CFR 880.6710 - Medical ultraviolet water purifier.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Medical ultraviolet water purifier. 880.6710... Miscellaneous Devices § 880.6710 Medical ultraviolet water purifier. (a) Identification. A medical ultraviolet water purifier is a device intended for medical purposes that is used to destroy bacteria in water by...

  13. 21 CFR 880.6710 - Medical ultraviolet water purifier.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Medical ultraviolet water purifier. 880.6710... Miscellaneous Devices § 880.6710 Medical ultraviolet water purifier. (a) Identification. A medical ultraviolet water purifier is a device intended for medical purposes that is used to destroy bacteria in water by...

  14. 21 CFR 880.6710 - Medical ultraviolet water purifier.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Medical ultraviolet water purifier. 880.6710... Miscellaneous Devices § 880.6710 Medical ultraviolet water purifier. (a) Identification. A medical ultraviolet water purifier is a device intended for medical purposes that is used to destroy bacteria in water by...

  15. Ultraviolet Communication for Medical Applications

    DTIC Science & Technology

    2015-06-01

    DEI procured several UVC phosphors and tested them with vacuum UV (VUV) excitation. Available emission peaks include: 226 nm, 230 nm, 234 nm, 242...SUPPLEMENTARY NOTES Report contains color. 14. ABSTRACT Under this Phase II SBIR effort, Directed Energy Inc.’s (DEI) proprietary ultraviolet ( UV ...15. SUBJECT TERMS Non-line-of-sight (NLOS), networking, optical communication, plasma-shells, short range, ultraviolet ( UV ) light 16. SECURITY

  16. Photodissociation dynamics in the first absorption band of pyrrole. I. Molecular Hamiltonian and the Herzberg-Teller absorption spectrum for the A12(π σ* ) ←X˜ 1 A1(π π ) transition

    NASA Astrophysics Data System (ADS)

    Picconi, David; Grebenshchikov, Sergy Yu.

    2018-03-01

    This paper opens a series in which the photochemistry of the two lowest πσ* states of pyrrole and their interaction with each other and with the ground electronic state X ˜ are studied using ab initio quantum mechanics. New 24-dimensional potential energy surfaces for the photodissociation of the N-H bond and the formation of the pyrrolyl radical are calculated using the multiconfigurational perturbation theory (CASPT2) for the electronic states X ˜ (π π ) , 11A2(πσ*), and 11B1(πσ*) and locally diabatized. In this paper, the ab initio calculations are described and the photodissociation in the state 11A2(πσ*) is analyzed. The excitation 11 A2←X ˜ is mediated by the coordinate dependent transition dipole moment functions constructed using the Herzberg-Teller expansion. Nuclear dynamics, including 6, 11, and 15 active degrees of freedom, are studied using the multi-configurational time-dependent Hartree method. The focus is on the frequency resolved absorption spectrum as well as on the dissociation time scales and the resonance lifetimes. Calculations are compared with available experimental data. An approximate convolution method is developed and validated, with which absorption spectra can be calculated and assigned in terms of vibrational quantum numbers. The method represents the total absorption spectrum as a convolution of the diffuse spectrum of the detaching H-atom and the Franck-Condon spectrum of the heteroaromatic ring. Convolution calculation requires a minimal quantum chemical input and is a promising tool for studying the πσ* photodissociation in model biochromophores.

  17. Ultraviolet light-an FDA approved technology

    USDA-ARS?s Scientific Manuscript database

    Ultraviolet Light (254 nm) is a U.S. Food and Drug Administration approved nonthermal intervention technology that can be used for decontamination of food and food contact surfaces. Ultraviolet light is a green technology that leaves no chemical residues. Results from our laboratory indicate that ex...

  18. 21 CFR 880.6500 - Medical ultraviolet air purifier.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Medical ultraviolet air purifier. 880.6500 Section... Miscellaneous Devices § 880.6500 Medical ultraviolet air purifier. (a) Identification. A medical ultraviolet air purifier is a device intended for medical purposes that is used to destroy bacteria in the air by exposure...

  19. 21 CFR 880.6500 - Medical ultraviolet air purifier.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Medical ultraviolet air purifier. 880.6500 Section... Miscellaneous Devices § 880.6500 Medical ultraviolet air purifier. (a) Identification. A medical ultraviolet air purifier is a device intended for medical purposes that is used to destroy bacteria in the air by exposure...

  20. 21 CFR 880.6500 - Medical ultraviolet air purifier.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Medical ultraviolet air purifier. 880.6500 Section... Miscellaneous Devices § 880.6500 Medical ultraviolet air purifier. (a) Identification. A medical ultraviolet air purifier is a device intended for medical purposes that is used to destroy bacteria in the air by exposure...

  1. The Extreme Ultraviolet Explorer

    NASA Technical Reports Server (NTRS)

    Malina, R. F.; Bowyer, S.; Lampton, M.; Finley, D.; Paresce, F.; Penegor, G.; Heetderks, H.

    1982-01-01

    The Extreme Ultraviolet Explorer Mission is described. The purpose of this mission is to search the celestial sphere for astronomical sources of extreme ultraviolet (EUV) radiation (100 to 1000 A). The search will be accomplished with the use of three EUV telescopes, each sensitive to different bands within the EUV band. A fourth telescope will perform a higher sensitivity search of a limited sample of the sky in a single EUV band. In six months, the entire sky will be scanned at a sensitivity level comparable to existing surveys in other more traditional astronomical bandpasses.

  2. Imaging charge transfer in a cation-π system: velocity-map imaging of Ag(+)(benzene) photodissociation.

    PubMed

    Maner, Jonathon A; Mauney, Daniel T; Duncan, Michael A

    2015-11-19

    Ag(+)(benzene) complexes are generated in the gas phase by laser vaporization and mass selected in a time-of-flight spectrometer. UV laser excitation at either 355 or 266 nm results in dissociative charge transfer (DCT), leading to neutral silver atom and benzene cation products. Kinetic energy release in translationally hot benzene cations is detected using a new instrument designed for photofragment imaging of mass-selected ions. Velocity-map imaging and slice imaging techniques are employed. In addition to the expected translational energy release, DCT of Ag(+)(benzene) produces a distribution of internally hot benzene cations. Compared with experiments at 355 nm, 266 nm excitation produces only slightly higher translational excitation and a much greater fraction of internally hot benzene ions. The maximum kinetic energy release in the photodissociation sets an upper limit on the Ag(+)(benzene) dissociation energy of 32.8 (+1.4/-1.5) kcal/mol.

  3. 21 CFR 878.4635 - Ultraviolet lamp for tanning.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ultraviolet lamp for tanning. 878.4635 Section 878... tanning. (a) Identification. An ultraviolet lamp for tanning is a device that is a lamp (including a fixture) intended to provide ultraviolet radiation to tan the skin. See § 1040.20 of this chapter. (b...

  4. International Ultraviolet Explorer (IUE) ultraviolet spectral atlas of selected astronomical objects

    NASA Technical Reports Server (NTRS)

    Wu, Chi-Chao; Reichert, Gail A.; Ake, Thomas B.; Boggess, Albert; Holm, Albert V.; Imhoff, Catherine L.; Kondo, Yoji; Mead, Jaylee M.; Shore, Steven N.

    1992-01-01

    The IUE Ultraviolet Spectral Atlas of Selected Astronomical Objects (or 'the Atlas'), is based on the data that were available in the IUE archive in 1986, and is intended to be a quick reference for the ultraviolet spectra of many categories of astronomical objects. It shows reflected sunlight from the Moon, planets, and asteroids, and also shows emission from comets. Comprehensive compilations of UV spectra for main sequence, subgiant, giant, bright giant, and supergiant stars are published elsewhere. This Atlas contains the spectra for objects occupying other areas of the Hertzsprung-Russell diagram: pre-main sequence stars, chemically peculiar stars, pulsating variables, subluminous stars, and Wolf-Rayet stars. This Atlas also presents phenomena such as the chromospheric and transition region emissions from late-type stars; composite spectra of stars, gas streams, accretion disks and gas envelopes of binary systems; the behavior of gas ejecta shortly after the outburst of novac and supernovac; and the H II regions, planetary nebulae, and supernova remnants. Population 2 stars, globular clusters, and luminous stars in the Magellanic Clouds, M31, and M33, are also included in this publication. Finally, the Atlas gives the ultraviolet spectra of galaxies of different Hubble types and of active galaxies.

  5. Ultraviolet Views of Enceladus, Tethys, and Dione

    NASA Technical Reports Server (NTRS)

    Hansen, C. J.; Hendrix, A. R.

    2005-01-01

    The Cassini Ultraviolet Imaging Spectrograph (UVIS) has collected ultraviolet observations of many of Saturn's icy moons since Cassini's insertion into orbit around Saturn. We will report on results from Enceladus, Tethys and Dione, orbiting in the Saturn system at distances of 3.95, 4.88 and 6.26 Saturn radii, respectively. Icy satellite science objectives of the UVIS include investigations of surface age and evolution, surface composition and chemistry, and tenuous exospheres. We address these objectives by producing albedo maps, and reflection and emission spectra, and observing stellar occultations. UVIS has four channels: EUV: Extreme Ultraviolet (55 nm to 110 nm), FUV: Far Ultraviolet (110 to 190 nm), HSP: High Speed Photometer, and HDAC: Hydrogen-Deuterium Absorption Cell. The EUV and FUV spectrographs image onto a 2-dimensional detector, with 64 spatial rows by 1024 spectral columns. To-date we have focused primarily on the far ultraviolet data acquired with the low resolution slit width (4.8 angstrom spectral resolution). Additional information is included in the original extended abstract.

  6. Thermally assisted infrared multiphoton photodissociation in a quadrupole ion trap.

    PubMed

    Payne, A H; Glish, G L

    2001-08-01

    Thermally assisted infrared multiphoton photodissociation (TA-IRMPD) provides an effective means to dissociate ions in the quadrupole ion trap mass spectrometer (QITMS) without detrimentally affecting the performance of the instrument. IRMPD can offer advantages over collision-induced dissociation (CID). However, collisions with the QITMS bath gas at the standard pressure and ambient temperature cause IR-irradiated ions to lose energy faster than photons can be absorbed to induce dissociation. The low pressure required for IRMPD (< or = 10(-5) Torr) is not that required for optimal performance of the QITMS (10(-3) Torr), and sensitivity and resolution suffer. TA-IRMPD is performed with the bath gas at an elevated temperature. The higher temperature of the bath gas results in less energy lost in collisions of the IR-excited ions with the bath gas. Thermal assistance allows IRMPD to be used at or near optimal pressures, which results in an approximately 1 order of magnitude increase in signal intensity. Unlike CID, IRMPD allows small product ions, those less than about one-third the m/z of the parent ion, to be observed. IRMPD should also be more easily paired with fluctuating ion sources, as the corresponding fluctuations in resonant frequencies do not affect IRMPD. Finally, while IR irradiation nonselectively causes dissociation of all ions, TA-IRMPD can be made selective by using axial expansion to move ions away from the path of the laser beam.

  7. Photoabsorption and photodissociation studies of dimethyl sulphoxide (DMSO) in the 35,000-80,000 cm-1 region using synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Mandal, Anuvab; Singh, Param Jeet; Shastri, Aparna; Sunanda, K.; Jagatap, B. N.

    2015-05-01

    Photoabsorption and photodissociation studies of dimethyl sulphoxide and its deuterated isotopologue (DMSO-h6 and DMSO-d6) are performed using synchrotron radiation in the 35,000-80,000 cm-1 region. In the photoabsorption spectrum, Rydberg series converging to the first three ionization potentials of DMSO at 9.1, 10.1 and 12.3 eV corresponding to removal of an electron from the highest three occupied molecular orbitals (14a‧, 7a″ and 13a‧) are observed. Based on a quantum defect analysis, Rydberg series assignments are extended to higher members as compared to earlier works and a few ambiguities in earlier assignments are clarified. Analysis is aided by quantum chemical calculations using the DFT and TDDFT methodologies. Vibronic structures observed in the spectrum of DMSO-h6 in the regions 7.7-8.1 eV and 8.1-8.8 eV are attributed to the transitions 7a″→4p at 7.862 eV and 14a‧→6s/4d at 8.182 eV, respectively. Photoabsorption spectra of DMSO-h6 and -d6 recorded using a broad band incident radiation show prominent peaks, which are identified and assigned to electronic and vibronic transitions of the SO radical. This provides a direct confirmation of the fact that DMSO preferentially dissociates into CH3 and SO upon UV-VUV excitation, as proposed in earlier photodissociation studies. An extended vibronic band system associated with the e1Π-X3Σ- transition of the SO radical is identified and assigned. The complete VUV photoabsorption spectrum of DMSO-d6 is also reported here for the first time.

  8. Photon-counting array detectors for space and ground-based studies at ultraviolet and vacuum ultraviolet /VUV/ wavelengths

    NASA Technical Reports Server (NTRS)

    Timothy, J. G.; Bybee, R. L.

    1981-01-01

    The Multi-Anode Microchannel Arrays (MAMAs) are a family of photoelectric photon-counting array detectors, with formats as large as (256 x 1024)-pixels that can be operated in a windowless configuration at vacuum ultraviolet (VUV) and soft X-ray wavelengths or in a sealed configuration at ultraviolet and visible wavelengths. This paper describes the construction and modes of operation of (1 x 1024)-pixel and (24 x 1024)-pixel MAMA detector systems that are being built and qualified for use in sounding-rocket spectrometers for solar and stellar observations at wavelengths below 1300 A. The performance characteristics of the MAMA detectors at ultraviolet and VUV wavelengths are also described.

  9. ULTRAVIOLET PROTECTIVE COMPOUNDS AS A RESPONSE TO ULTRAVIOLET RADIATION EXPOSURE

    EPA Science Inventory

    Life on Earth has evolved adaptations to many environmental stresses over the epochs. One consistent stress has been exposure to ultraviolet radiation. In response to UVR organisms have adapted myriad responses; behavioral, morphological and physiological. Behaviorally, some orga...

  10. Condenser for ring-field deep ultraviolet and extreme ultraviolet lithography

    DOEpatents

    Chapman, Henry N.; Nugent, Keith A.

    2002-01-01

    A condenser for use with a ring-field deep ultraviolet or extreme ultraviolet lithography system. A condenser includes a ripple-plate mirror which is illuminated by a collimated or converging beam at grazing incidence. The ripple plate comprises a flat or curved plate mirror into which is formed a series of channels along an axis of the mirror to produce a series of concave surfaces in an undulating pattern. Light incident along the channels of the mirror is reflected onto a series of cones. The distribution of slopes on the ripple plate leads to a distribution of angles of reflection of the incident beam. This distribution has the form of an arc, with the extremes of the arc given by the greatest slope in the ripple plate. An imaging mirror focuses this distribution to a ring-field arc at the mask plane.

  11. Condenser for ring-field deep-ultraviolet and extreme-ultraviolet lithography

    DOEpatents

    Chapman, Henry N.; Nugent, Keith A.

    2001-01-01

    A condenser for use with a ring-field deep ultraviolet or extreme ultraviolet lithography system. A condenser includes a ripple-plate mirror which is illuminated by a collimated beam at grazing incidence. The ripple plate comprises a plate mirror into which is formed a series of channels along an axis of the mirror to produce a series of concave surfaces in an undulating pattern. Light incident along the channels of the mirror is reflected onto a series of cones. The distribution of slopes on the ripple plate leads to a distribution of angles of reflection of the incident beam. This distribution has the form of an arc, with the extremes of the arc given by the greatest slope in the ripple plate. An imaging mirror focuses this distribution to a ring-field arc at the mask plane.

  12. Astro-1 Image Taken by Ultraviolet Imaging Telescope

    NASA Technical Reports Server (NTRS)

    1990-01-01

    This image shows a part of the Cygnus loop supernova remnant, taken by the Ultraviolet Imaging Telescope (UIT) on the Astro Observatory during the Astro-1 mission (STS-35) on December 5, 1990. Pictured is a portion of the huge Cygnus loop, an array of interstellar gas clouds that have been blasted by a 900,000 mile per hour shock wave from a prehistoric stellar explosion, which occurred about 20,000 years ago, known as supernova. With ultraviolet and x-rays, astronomers can see emissions from extremely hot gases, intense magnetic fields, and other high-energy phenomena that more faintly appear in visible and infrared light or in radio waves that are crucial to deepening the understanding of the universe. The Astro Observatory was designed to explore the universe by observing and measuring the ultraviolet radiation from celestial objects. Three instruments make up the Astro Observatory: The Hopkins Ultraviolet Telescope (HUT), the Ultraviolet Imaging Telescope (UIT), and the Wisconsin Ultraviolet Photo-Polarimetry Experiment (WUPPE). The Marshall Space Flight Center had managment responsibilities for the Astro-1 mission. The Astro-1 Observatory was launched aboard the Space Shuttle Orbiter Columbia (STS-35) on December 2, 1990.

  13. The Chemistry and Excitation of Water in Molecular Clouds

    NASA Technical Reports Server (NTRS)

    Hollenbach, David

    2003-01-01

    We model the chemistry and thermal balance of opaque molecular clouds exposed to an external flux of ultraviolet photons. We include the processes of gas phase and grain surface chemical reactions; in particular we examine closely the freezing of atoms and molecules onto grain surfaces and the desorption of molecules from grain surfaces as a function of depth into a molecular cloud. We find that on the surface of a molecular cloud the gas phase water abundances are low because of photodissociation, and the grain phase water (ice) abundance is low because of photodesorption of water from the grain surfaces. Deeper into the cloud, at A(sub v) less than or approximately 2-8 depending on the strength of the external ultraviolet flux, the gas phase water abundance increases with depth as the photodissociation rates decline due to dust attenuation of the ultraviolet field. However, beyond A(sub v) less than or approximately 2-8 the gas phase water abundance declines because the water freezes as water ice on the grains, and photodesorption is no longer effective in clearing the ice. A peak water abundance of about 10(exp -6) to 10(exp -7) occurs at about A(sub v) approximately 2-8, relatively independent of the gas density and the ultraviolet field. We show that such a model matches very closely the observations of the Submillimeter Wave Astronomical Satellite (SWAS), a NASA Small Explorer Mission. The model elucidates several mechanisms that have been recently invoked to understand gas phase chemistry in clouds, including-the freeze-out of molecules onto grain surface, the desorption of these molecules from the surfaces, and the abundance gradients of molecules as functions of depth into molecular clouds.

  14. Pen Ink as an Ultraviolet Dosimeter

    ERIC Educational Resources Information Center

    Downs, Nathan; Turner, Joanna; Parisi, Alfio; Spence, Jenny

    2008-01-01

    A technique for using highlighter ink as an ultraviolet dosimeter has been developed for use by secondary school students. The technique requires the students to measure the percentage of colour fading in ink drawn onto strips of paper that have been exposed to sunlight, which can be calibrated to measurements of the ultraviolet irradiance using…

  15. Ultraviolet laser beam monitor using radiation responsive crystals

    DOEpatents

    McCann, Michael P.; Chen, Chung H.

    1988-01-01

    An apparatus and method for monitoring an ultraviolet laser beam includes disposing in the path of an ultraviolet laser beam a substantially transparent crystal that will produce a color pattern in response to ultraviolet radiation. The crystal is exposed to the ultraviolet laser beam and a color pattern is produced within the crystal corresponding to the laser beam intensity distribution therein. The crystal is then exposed to visible light, and the color pattern is observed by means of the visible light to determine the characteristics of the laser beam that passed through crystal. In this manner, a perpendicular cross sectional intensity profile and a longitudinal intensity profile of the ultraviolet laser beam may be determined. The observation of the color pattern may be made with forward or back scattered light and may be made with the naked eye or with optical systems such as microscopes and television cameras.

  16. Scatter Measurements Made With Ultraviolet Light

    NASA Astrophysics Data System (ADS)

    Anthon, Erik W.

    1985-09-01

    The quality of optical surfaces is generally evaluated by how much light (normally visible light) is scattered by the surface. Most optical glasses and many coating materials are completely opaque to ultraviolet light (253.7 nm). Ultraviolet light tends to scatter much more than visible light. Scatter measurements made with ultraviolet light are therefore very sensitive and the scatter from second surfaces and from the interior (bulk) of the optical material is eliminated by the opacity. A novel scattermeter that operates with ultraviolet light has been developed. The construction and operation of this scattermeter will be described. Cleaning soon becomes the limiting factor when measuring the surfaces with very low level of scatter. Sensitivity to repeated cleaning has been investigated. Different surfaces are compared and uniformity of surfaces is measured by mapping a surface area with an x-y stage. Polished glass surfaces generally have much higher scatter than natural glass surfaces (fire polished, drawn or floated surfaces). Very low scatter levels have been found on thin drawn glass.

  17. In-orbit Calibrations of the Ultraviolet Imaging Telescope

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tandon, S. N.; Subramaniam, Annapurni; Sankarasubramanian, K.

    The Ultra-Violet Imaging Telescope (UVIT) is one of the payloads in ASTROSAT, the first Indian Space Observatory. The UVIT instrument has two 375 mm telescopes: one for the far-ultraviolet (FUV) channel (1300–1800 Å), and the other for the near-ultraviolet (NUV) channel (2000–3000 Å) and the visible (VIS) channel (3200–5500 Å). UVIT is primarily designed for simultaneous imaging in the two ultraviolet channels with spatial resolution better than 1.″8, along with provisions for slit-less spectroscopy in the NUV and FUV channels. The results of in-orbit calibrations of UVIT are presented in this paper.

  18. Infrared photodissociation spectroscopy of M(N2)n(+) (M = Y, La, Ce; n = 7-8) in the gas phase.

    PubMed

    Xie, Hua; Shi, Lei; Xing, Xiaopeng; Tang, Zichao

    2016-02-14

    M(N2)n(+) (M = Y, La, Ce; n = 7-8) complexes have been studied by infrared photodissociation (IRPD) spectroscopy and density functional theory (DFT) calculations. The experimental results indicate that the N-N stretching vibrational frequencies are red-shifted from the gas-phase N2 value. The π back-donation is found to be a main contributor in these systems. IRPD spectra and DFT calculations reveal the coexistence of two isomers in the seven-coordinate M(N2)7(+) and eight-coordinate M(N2)8(+) complexes, respectively. The present studies on these metal-nitrogen complexes shed light on the interactions and coordinations toward N2 with transition and lanthanide metals.

  19. Far ultraviolet excitation processes in comets

    NASA Technical Reports Server (NTRS)

    Feldman, P. D.; Opal, C. B.; Meier, R. R.; Nicolas, K. R.

    1976-01-01

    Recent observations of atomic oxygen and carbon in the far ultraviolet spectrum of comet Kohoutek have demonstrated the existence of these atomic species in the cometary coma. However, in order to identify the source of their origin, it is necessary to relate the observed ultraviolet flux to the atomic production rate. Analyses of observed OI wavelength 1304 and CI wavelength 1657 A multiplets have been carried out using high resolution solar spectra. Also examined is the possibility of observing ultraviolet fluorescence from molecules such as CO and H2, as well as resonance scattering either from atomic ions for which there are strong corresponding solar lines (CII) or from atoms for which there is an accidental wavelength coincidence (SI).

  20. Transport and Distribution of Hydroxyl Radicals and Oxygen Atoms from H2O Photodissociation in the Inner Coma of Comet 67P/Churyumov-Gerasimenko

    NASA Astrophysics Data System (ADS)

    Lai, Ian-Lin; Su, Cheng-Chin; Ip, Wing-Huen; Wei, Chen-En; Wu, Jong-Shinn; Lo, Ming-Chung; Liao, Ying; Thomas, Nicolas

    2016-03-01

    With a combination of the Direct Simulation Monte Carlo (DSMC) calculation and test particle computation, the ballistic transport process of the hydroxyl radicals and oxygen atoms produced by photodissociation of water molecules in the coma of comet 67P/Churyumov-Gerasimenko is modelled. We discuss the key elements and essential features of such simulations which results can be compared with the remote-sensing and in situ measurements of cometary gas coma from the Rosetta mission at different orbital phases of this comet.

  1. [Effect of long-wave ultraviolet light (UV-A) and medium-wave ultraviolet rays (UV-B) on human skin. Critical comparison].

    PubMed

    Raab, W

    1980-04-15

    When discussing the effects of ultraviolet radiation on human skin, one should carefully distinguish between the long wave ultraviolet light (UV-A) and the short wave radiations (UV-B and UV-C). Ultraviolet A induces immediate pigmentation but, if high energies are applied, a permanent pigmentation is elicited. This type of ultraviolet A-induced pigmentation has been called "spontaneous" pigmentation as no erythematous reaction is necessary to induce or accelerate melanine formation. Ultraviolet B provokes erythema and consecutive pigmentation. Upon chronic exposure, ultraviolet B causes the wellknown actinic damage of the skin and even provokes carcinoma. With exposures to the sunlight (global radiation), one should be most careful. The public must be informed extensively about the dangers of excessive sunbaths. The use of artificial "suns" with spectra between 260 and 400 nm is limited as it may cause the same type of damage as the global radiation. An exact schedule for use of artificial lamps is strongly recommended. After one cycle of exposures, an interruption is necessary until the next cycle of irradiations may start. Upon continual use for tanning of the skin, artificial lamps may provoke irreversible damage of the skin. Radiation sources with emission spectra of wavelengths between 315 and 400 nm exclusively are well suited for the induction of skin pigmentation (cosmetic use). Potent radiation such as UVASUN systems provoke a "pleasant" permanent pigmentation after exposures for less than one hour. The use of ultraviolet A (UV-A) does not carry any risk for the human skin.

  2. Investigation of ultraviolet fluxes of normal and peculiar stars

    NASA Technical Reports Server (NTRS)

    Deutschman, W. A.; Schild, R. E.

    1974-01-01

    Data from Project Celescope, a program that photographed the ultraviolet sky, in order to study several problems in current astrophysics are analyzed. Two star clusters, the Pleiades and the Hyades, reveal differences between the two that we are unable to explain simply from their differences in chemical abundance, rotation, or reddening. Data for Orion show large scatter, which appears to be in the sense that the Orion stars are too faint for their ground-based photometry. Similarly, many supergiants in the association Sco OB1 are too faint in the ultraviolet, but the ultraviolet brightness appears to be only poorly correlated with spectral type. Ultraviolet Celescope data for several groups of peculiar stars have also been analyzed. The strong He I stars are too faint in the ultraviolet, possibly owing to enhancement of O II continuous opacity due to oxygen overabundance. The Be stars appear to have ultraviolet colors normal for their MK spectral types. The P Cygni stars are considerably fainter than main-sequence stars of comparable spectral type, probably owing, at least in part, to line blocking by resonance lines of multiply ionized light metals. The Wolf-Rayet stars have ultraviolet color temperatures of O stars.

  3. Ultrastructure study of hair damage after ultraviolet irradiation.

    PubMed

    Zuel-Fakkar, Nehal Mohamed; El Khateeb, Ekramy Ahmed; Cousha, Hala Sobhi; Hamed, Dina Mohamed

    2013-12-01

    Natural ultraviolet exposure induces hair damage, which is difficult to avoid. Most of the research work is focused on the effect of ultraviolet on the epidermis, dermis as well as the immune system, whereas the long-term effect of ultraviolet on hair has not been investigated. we performed our experiment to find out the changes induced in hair follicle and shaft in those patients exposed to high doses of ultraviolet (A and B) during treatment of other skin conditions. Light and transmission electron microscopy examination of scalp hair follicles and shafts of 10 patients with vitiligo under psoralen plus ultraviolet A (group 1) and 10 patients with vitiligo under narrow band ultraviolet B (group 2) was carried out and compared with those of 10 healthy volunteers (group 3). Physical changes in the appearance of hair were more in groups 1 and 2 than control. Reduced hair follicle thickness and perifollicular infiltrate and hyaline disorganized perifollicular collagen were observed more in group 1 than in group 2 with the absence of these changes in group 3. Transmission electron microscopy showed nonspecific cell injury in hair follicles in group 1 more than the other 2 groups, while the damaging effect on hair was more in the second group than the others. Due to the damaging effect of ultraviolet on hair, patients under treatment with this modality should be cautious to protect their hair during treatment. © 2013 Wiley Periodicals, Inc.

  4. Electronic and vibrational spectroscopy and vibrationally mediated photodissociation of V+(OCO).

    PubMed

    Citir, Murat; Altinay, Gokhan; Metz, Ricardo B

    2006-04-20

    Electronic spectra of gas-phase V+(OCO) are measured in the near-infrared from 6050 to 7420 cm(-1) and in the visible from 15,500 to 16,560 cm(-1), using photofragment spectroscopy. The near-IR band is complex, with a 107 cm(-1) progression in the metal-ligand stretch. The visible band shows clearly resolved vibrational progressions in the metal-ligand stretch and rock, and in the OCO bend, as observed by Brucat and co-workers. A vibrational hot band gives the metal-ligand stretch frequency in the ground electronic state nu3'' = 210 cm(-1). The OCO antisymmetric stretch frequency in the ground electronic state (nu1'') is measured by using vibrationally mediated photodissociation. An IR laser vibrationally excites ions to nu1'' = 1. Vibrationally excited ions selectively dissociate following absorption of a second, visible photon at the nu1' = 1 <-- nu1'' = 1 transition. Rotational structure in the resulting vibrational action spectrum confirms that V+(OCO) is linear and gives nu1'' = 2392.0 cm(-1). The OCO antisymmetric stretch frequency in the excited electronic state is nu1' = 2368 cm(-1). Both show a blue shift from the value in free CO2, due to interaction with the metal. Larger blue shifts observed for complexes with fewer ligands agree with trends seen for larger V+(OCO)n clusters.

  5. Design of fire detection equipment based on ultraviolet detection technology

    NASA Astrophysics Data System (ADS)

    Liu, Zhenji; Liu, Jin; Chu, Sheng; Ping, Chao; Yuan, Xiaobing

    2015-03-01

    Utilized the feature of wide bandgap semiconductor of MgZnO, researched and developed a kind of Mid-Ultraviolet-Band(MUV) ultraviolet detector which has passed the simulation experiment in the sun circumstance. Based on the ultraviolet detector, it gives out a design scheme of gun-shot detection device, which is composed of twelve ultraviolet detectors, signal amplifier, processor, annunciator , azimuth indicator and the bracket. Through Analysing the feature of solar blind, ultraviolet responsivity, fire feature of gunshots and detection distance, the feasibility of this design scheme is proved.

  6. Ultraviolet Imaging Telescope images of the reflection nebula NGC 7023 - Derivation of ultraviolet scattering properties of dust grains

    NASA Technical Reports Server (NTRS)

    Witt, Adolf N.; Petersohn, Jens K.; Bohlin, Ralph C.; O'Connell, Robert W.; Roberts, Morton S.; Smith, Andrew M.; Stecher, Theodore P.

    1992-01-01

    The Ultraviolet Imaging Telescope as part of the Astro-1 mission, was used to obtain high-resolution surface brightness distribution data in six ultraviolet wavelength bands for the bright reflection nebula NGC 7023. From the quantitative comparison of the measured surface brightness gradients ratios of nebular to stellar flux, and detail radial surface brightness profiles with corresponding data from the visible, two major conclusions results: (1) the scattering in the near- and far-ultraviolet in this nebula is more strongly forward-directed than in the visible; (2) the dust albedo in the ultraviolet for wavelengths not less than 140 nm is identical to that in the visible, with the exception of the 220 nm bump in the extinction curve. In the wavelengths region of the bump, the albedo is reduced by 25 to 30 percent in comparison with wavelengths regions both shorter and longer. This lower albedo is expected, if the bump is a pure absorption feature.

  7. State-resolved Photodissociation and Radiative Association Data for the Molecular Hydrogen Ion

    NASA Astrophysics Data System (ADS)

    Zammit, Mark C.; Savage, Jeremy S.; Colgan, James; Fursa, Dmitry V.; Kilcrease, David P.; Bray, Igor; Fontes, Christopher J.; Hakel, Peter; Timmermans, Eddy

    2017-12-01

    We present state-resolved (electronic, vibrational, and rotational) cross sections and rate coefficients for the photodissociation (PD) of {{{H}}}2+ and radiative association (RA) of H–H+. We developed a fully quantum mechanical approach within the nonrelativistic Born–Oppenheimer approximation to describe {{{H}}}2+ and calculate the data for transitions between the ground electronic state 1s{σ }g and the 2p{σ }u, 2p{π }u, 3p{σ }u, 3p{π }u, 4p{σ }u, 4f{σ }u, 4f{π }u, and 4p{π }u electronic states (i.e., up to {{{H}}}2+ n = 4). Tables of the dipole-matrix elements and energies needed to calculate state-resolved cross sections and rate coefficients will be made publicly available. These data could be important in astrophysical models when dealing with photon wavelengths (or radiation temperature distributions that are weighted toward such wavelengths) around 100 nm. For example, at these wavelengths and a material temperature of 8400 K, the LTE-averaged PD cross section via the (second electronically excited) 2p{π }u state is over three times larger than the PD cross section via the (first electronically excited) 2p{σ }u state.

  8. Discuss the testing problems of ultraviolet irradiance meters

    NASA Astrophysics Data System (ADS)

    Ye, Jun'an; Lin, Fangsheng

    2014-09-01

    Ultraviolet irradiance meters are widely used in many areas such as medical treatment, epidemic prevention, energy conservation and environment protection, computers, manufacture, electronics, ageing of material and photo-electric effect, for testing ultraviolet irradiance intensity. So the accuracy of value directly affects the sterile control in hospital, treatment, the prevention level of CDC and the control accuracy of curing and aging in manufacturing industry etc. Because the display of ultraviolet irradiance meters is easy to change, in order to ensure the accuracy, it needs to be recalibrated after being used period of time. By the comparison with the standard ultraviolet irradiance meters, which are traceable to national benchmarks, we can acquire the correction factor to ensure that the instruments working under accurate status and giving the accurate measured data. This leads to an important question: what kind of testing device is more accurate and reliable? This article introduces the testing method and problems of the current testing device for ultraviolet irradiance meters. In order to solve these problems, we have developed a new three-dimensional automatic testing device. We introduce structure and working principle of this system and compare the advantages and disadvantages of two devices. In addition, we analyses the errors in the testing of ultraviolet irradiance meters.

  9. Stereodynamics of the photodissociation of nitromethane at 193 nm: unravelling the dissociation mechanism.

    PubMed

    Rodríguez, J D; González, M G; Rubio-Lago, L; Bañares, L; Samartzis, P C; Kitsopoulos, T N

    2013-08-29

    The photodissociation of nitromethane at 193 nm is reviewed in terms of new stereodynamical information provided by the measurement of the first four Dixon's bipolar moments, β0(2)(20), β0(0)(22), β0(2)(02), and β0(2)(22), using slice imaging. The measured speed-dependent β0(2)(20) (directly related with the spatial anisotropy parameter β) indicates that after one-photon absorption to the S3(2 (1)A″) state by an allowed perpendicular transition, two reaction pathways can compete with similar probability, a direct dissociation process yielding ground-state CH3 and NO2(1 (2)A2) radicals and a indirect dissociation through conical intersections in which NO2 radicals are formed in lower-lying electronic states. A particularly important result from our measurements is that the low recoil energy part of the methyl fragment translational energy distribution presents a contribution with parallel character, irrespective of the experimental conditions employed, that we attribute to parent cluster dissociation. Moreover, the positive values found for the β0(0)(22) bipolar moment indicates some propensity for the fragment's recoil velocity and angular momentum vectors to be parallel.

  10. Attosecond Coherent Control of the Photo-Dissociation of Oxygen Molecules

    NASA Astrophysics Data System (ADS)

    Sturm, Felix; Ray, Dipanwita; Wright, Travis; Shivaram, Niranjan; Bocharova, Irina; Slaughter, Daniel; Ranitovic, Predrag; Belkacem, Ali; Weber, Thorsten

    2016-05-01

    Attosecond Coherent Control has emerged in recent years as a technique to manipulate the absorption and ionization in atoms as well as the dissociation of molecules on an attosecond time scale. Single attosecond pulses and attosecond pulse trains (APTs) can coherently excite multiple electronic states. The electronic and nuclear wave packets can then be coupled with a second pulse forming multiple interfering quantum pathways. We have built a high flux extreme ultraviolet (XUV) light source delivering APTs based on HHG that allows to selectively excite neutral and ion states in molecules. Our beamline provides spectral selectivity and attosecond interferometric control of the pulses. In the study presented here, we use APTs, generated by High Harmonic Generation in a high flux extreme ultraviolet light source, to ionize highly excited states of oxygen molecules. We identify the ionization/dissociation pathways revealing vibrational structure with ultra-high resolution ion 3D-momentum imaging spectroscopy. Furthermore, we introduce a delay between IR pulses and XUV/IR pulses to constructively or destructively interfere the ionization and dissociation pathways, thus, enabling the manipulation of both the O2+and the O+ ion yields with attosecond precision. Supported by DOE under Contract No. DE-AC02-05CH11231.

  11. Astro-1 Image Taken by the Ultraviolet Imaging Telescope

    NASA Technical Reports Server (NTRS)

    1990-01-01

    This is a presentation of two comparison images of the Spiral Galaxy M81 in the constellation URA Major. The galaxy is about 12-million light years from Earth. The left image is the Spiral Galaxy M81 as photographed by the Ultraviolet Imaging Telescope (UIT) during the Astro-1 Mission (STS-35) on December 9, 1990. This UIT photograph, made with ultraviolet light, reveals regions where new stars are forming at a rapid rate. The right image is a photograph of the same galaxy in red light made with a 36-inch (0.9-meter) telescope at the Kitt Peak National Observatory near Tucson, Arizona. The Astro Observatory was designed to explore the universe by observing and measuring ultraviolet radiation from celestial objects. Three instruments made up the Astro Observatory: The Hopkins Ultraviolet Telescope (HUT), the Ultraviolet Imaging Telescope (UIT), and the Wisconsin Ultraviolet Photo-Polarimetry Experiment (WUPPE). The Marshall Space Flight Center had management responsibilities for the Astro-1 mission. The Astro-1 Observatory was launched aboard the Space Shuttle Orbiter Columbia (STS-35) on December 2, 1990.

  12. Ultraviolet spectrophotometer for measuring columnar atmospheric ozone from aircraft

    NASA Technical Reports Server (NTRS)

    Hanser, F. A.; Sellers, B.; Briehl, D. C.

    1978-01-01

    An ultraviolet spectrophotometer (UVS) to measure downward solar fluxes from an aircraft or other high altitude platform is described. The UVS uses an ultraviolet diffuser to obtain large angular response with no aiming requirement, a twelve-position filter wheel with narrow (2-nm) and broad (20-nm) bandpass filters, and an ultraviolet photodiode. The columnar atmospheric ozone above the UVS (aircraft) is calculated from the ratios of the measured ultraviolet fluxes. Comparison with some Dobson station measurements gives agreement to 2%. Some UVS measured ozone profiles over the Pacific Ocean for November 1976 are shown to illustrate the instrument's performance.

  13. Aluminum nanostructures for ultraviolet plasmonics

    NASA Astrophysics Data System (ADS)

    Martin, Jérôme; Khlopin, Dmitry; Zhang, Feifei; Schuermans, Silvère; Proust, Julien; Maurer, Thomas; Gérard, Davy; Plain, Jérôme

    2017-08-01

    An electromagnetic field is able to produce a collective oscillation of free electrons at a metal surface. This allows light to be concentrated in volumes smaller than its wavelength. The resulting waves, called surface plasmons can be applied in various technological applications such as ultra-sensitive sensing, Surface Enhanced Raman Spectroscopy, or metal-enhanced fluorescence, to name a few. For several decades plasmonics has been almost exclusively studied in the visible region by using nanoparticles made of gold or silver as these noble metals support plasmonic resonances in the visible and near-infrared range. Nevertheless, emerging applications will require the extension of nano-plasmonics toward higher energies, in the ultraviolet range. Aluminum is one of the most appealing metal for pushing plasmonics up to ultraviolet energies. The subsequent applications in the field of nano-optics are various. This metal is therefore a highly promising material for commercial applications in the field of ultraviolet nano-optics. As a consequence, aluminum (or ultraviolet, UV) plasmonics has emerged quite recently. Aluminium plasmonics has been demonstrated efficient for numerous potential applications including non-linear optics, enhanced fluorescence, UV-Surface Enhanced Raman Spectroscopy, optoelectronics, plasmonic assisted solid-state lasing, photocatalysis, structural colors and data storage. In this article, different preparation methods developed in the laboratory to obtain aluminum nanostructures with different geometries are presented. Their optical and morphological characterizations of the nanostructures are given and some proof of principle applications such as fluorescence enhancement are discussed.

  14. The influence of the environment and clothing on human exposure to ultraviolet light.

    PubMed

    Liu, Jin; Zhang, Wei

    2015-01-01

    The aim of this study is to determine the effect of clothing and the environment on human exposure to ultraviolet light. The ultraviolet (ultraviolet A and ultraviolet B) light intensity was measured, and air quality parameters were recorded in 2014 in Beijing, China. Three types of clothing (white polyester cloth, pure cotton white T-shirt, and pure cotton black T-shirt) were individually placed on a mannequin. The ultraviolet (ultraviolet A and ultraviolet B) light intensities were measured above and beneath each article of clothing, and the percentage of ultraviolet light transmission through the clothing was calculated. (1) The ultraviolet light transmission was significantly higher through white cloth than through black cloth; the transmission was significantly higher through polyester cloth than through cotton. (2) The weather significantly influenced ultraviolet light transmission through white polyester cloth; transmission was highest on clear days and lowest on overcast days (ultraviolet A: P=0.000; ultraviolet B: P=0.008). (3) Air quality parameters (air quality index and particulate matter 2.5 and 10) were inversely related to the ultraviolet light intensity that reached the earth's surface. Ultraviolet B transmission through white polyester cloth was greater under conditions of low air pollution compared with high air pollution. Clothing color and material and different types of weather affected ultraviolet light transmission; for one particular cloth, the transmission decreased with increasing air pollution.

  15. A novel high-performance self-powered ultraviolet photodetector: Concept, analytical modeling and analysis

    NASA Astrophysics Data System (ADS)

    Ferhati, H.; Djeffal, F.

    2017-12-01

    In this paper, a new MSM-UV-photodetector (PD) based on dual wide band-gap material (DM) engineering aspect is proposed to achieve high-performance self-powered device. Comprehensive analytical models for the proposed sensor photocurrent and the device properties are developed incorporating the impact of DM aspect on the device photoelectrical behavior. The obtained results are validated with the numerical data using commercial TCAD software. Our investigation demonstrates that the adopted design amendment modulates the electric field in the device, which provides the possibility to drive appropriate photo-generated carriers without an external applied voltage. This phenomenon suggests achieving the dual role of effective carriers' separation and an efficient reduce of the dark current. Moreover, a new hybrid approach based on analytical modeling and Particle Swarm Optimization (PSO) is proposed to achieve improved photoelectric behavior at zero bias that can ensure favorable self-powered MSM-based UV-PD. It is found that the proposed design methodology has succeeded in identifying the optimized design that offers a self-powered device with high-responsivity (98 mA/W) and superior ION/IOFF ratio (480 dB). These results make the optimized MSM-UV-DM-PD suitable for providing low cost self-powered devices for high-performance optical communication and monitoring applications.

  16. Strategies for generating peptide radical cations via ion/ion reactions.

    PubMed

    Gilbert, Joshua D; Fisher, Christine M; Bu, Jiexun; Prentice, Boone M; Redwine, James G; McLuckey, Scott A

    2015-02-01

    Several approaches for the generation of peptide radical cations using ion/ion reactions coupled with either collision induced dissociation (CID) or ultraviolet photo dissociation (UVPD) are described here. Ion/ion reactions are used to generate electrostatic or covalent complexes comprised of a peptide and a radical reagent. The radical site of the reagent can be generated multiple ways. Reagents containing a carbon-iodine (C-I) bond are subjected to UVPD with 266-nm photons, which selectively cleaves the C-I bond homolytically. Alternatively, reagents containing azo functionalities are collisionally activated to yield radical sites on either side of the azo group. Both of these methods generate an initial radical site on the reagent, which then abstracts a hydrogen from the peptide while the peptide and reagent are held together by either electrostatic interactions or a covalent linkage. These methods are demonstrated via ion/ion reactions between the model peptide RARARAA (doubly protonated) and various distonic anionic radical reagents. The radical site abstracts a hydrogen atom from the peptide, while the charge site abstracts a proton. The net result is the conversion of a doubly protonated peptide to a peptide radical cation. The peptide radical cations have been fragmented via CID and the resulting product ion mass spectra are compared to the control CID spectrum of the singly protonated, even-electron species. This work is then extended to bradykinin, a more broadly studied peptide, for comparison with other radical peptide generation methods. The work presented here provides novel methods for generating peptide radical cations in the gas phase through ion/ion reaction complexes that do not require modification of the peptide in solution or generation of non-covalent complexes in the electrospray process. Copyright © 2015 John Wiley & Sons, Ltd.

  17. Magnetic field in the NGC7023 photodissociation region

    NASA Astrophysics Data System (ADS)

    Alves, Marta

    2015-10-01

    The far-UV radiation of massive stars illuminates molecular clouds creating photodissociation regions (PDRs), the transition layers between atomic and molecular media. Recent results based on Herschel observations reveal the presence of small regions at high gas pressure in the PDRs, whose origin is still not well understood, while polarization measurements towards a few PDRs indicate that magnetic fields can play a significant role in their structure. The limited number of existing polarization observations suggest that, when subject to a high gas and radiation pressure from the stars, the magnetic field tends to align and to be compressed in the PDR. As a consequence, bright PDRs should be magnetically dominated. However, this possibility has been the subject of very few studies due to the sparsity of relevant data. We propose to map the magnetic field in a nearby bright PDR, NGC 7023, using the unique capabilities of HAWC+ onboard SOFIA. For one, we wish to test the hypothesis that the magnetic field should be parallel to this PDR, which is illuminated by a radiation field of 2600 (in Habing units). Secondly, since NGC 7023 is a well studied region, its physical conditions (density, temperature) are known and can thus be related to the magnetic field across the PDR. We can investigate the relation between the field structure and the geometry of the PDR, and aided by Herschel observations we can also explore a possible connection between the magnetic field and the existence of high density regions in the PDR. SOFIA HAWC+ is the only instrument capable of imaging the polarized emission of extended objects, with structure at arcsecond scales. Moreover, it allows us trace the magnetic field within the PDR, owing to its 63micron band that traces the warm (40K) dust present at the illuminated surface. Our observations will be complementary to those led by the instrument team, who will observe NGC 7023 using the three highest wavelength filters.

  18. Stimulation of hair cells with ultraviolet light

    NASA Astrophysics Data System (ADS)

    Azimzadeh, Julien B.; Fabella, Brian A.; Hudspeth, A. J.

    2018-05-01

    Hair bundles are specialized organelles that transduce mechanical inputs into electrical outputs. To activate hair cells, physiologists have resorted to mechanical methods of hair-bundle stimulation. Here we describe a new method of hair-bundle stimulation, irradiation with ultraviolet light. A hair bundle illuminated by ultraviolet light rapidly moves towards its tall edge, a motion typically associated with excitatory stimulation. The motion disappears upon tip-link rupture and is associated with the opening of mechanotransduction channels. Hair bundles can be induced to move sinusoidally with oscillatory modulation of the stimulation power. We discuss the implications of ultraviolet stimulation as a novel hair-bundle stimulus.

  19. Optical signatures of molecular particles via mass-selected cluster spectroscopy

    NASA Technical Reports Server (NTRS)

    Duncan, Michael A.

    1990-01-01

    A new molecular beam apparatus was developed to study optical absorption in cold (less than 100 K) atomic clusters and complexes produced by their condensation with simple molecular gases. In this instrument, ionized clusters produced in a laser vaporization nozzle source are mass selected and studied with photodissociation spectroscopy at visible and ultraviolet wavelengths. This new approach can be applied to synthesize and characterize numerous particulates and weakly bound complexes expected in planetary atmospheres and in comets.

  20. Extreme Ultraviolet Explorer Bright Source List

    NASA Technical Reports Server (NTRS)

    Malina, Roger F.; Marshall, Herman L.; Antia, Behram; Christian, Carol A.; Dobson, Carl A.; Finley, David S.; Fruscione, Antonella; Girouard, Forrest R.; Hawkins, Isabel; Jelinsky, Patrick

    1994-01-01

    Initial results from the analysis of the Extreme Ultraviolet Explorer (EUVE) all-sky survey (58-740 A) and deep survey (67-364 A) are presented through the EUVE Bright Source List (BSL). The BSL contains 356 confirmed extreme ultraviolet (EUV) point sources with supporting information, including positions, observed EUV count rates, and the identification of possible optical counterparts. One-hundred twenty-six sources have been detected longward of 200 A.

  1. Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent.

    PubMed

    Liu, Yong-Qiang; Yu, Hong

    2016-08-01

    Indirect ultraviolet detection was conducted in ultraviolet-absorption-agent-added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li(+) , Na(+) , K(+) , and NH4 (+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography-indirect ultraviolet detection. The successful separation and detection of Li(+) , Na(+) , K(+) , and NH4 (+) within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. The Influence of the Environment and Clothing on Human Exposure to Ultraviolet Light

    PubMed Central

    Liu, Jin; Zhang, Wei

    2015-01-01

    Objection The aim of this study is to determine the effect of clothing and the environment on human exposure to ultraviolet light. Methods The ultraviolet (ultraviolet A and ultraviolet B) light intensity was measured, and air quality parameters were recorded in 2014 in Beijing, China. Three types of clothing (white polyester cloth, pure cotton white T-shirt, and pure cotton black T-shirt) were individually placed on a mannequin. The ultraviolet (ultraviolet A and ultraviolet B) light intensities were measured above and beneath each article of clothing, and the percentage of ultraviolet light transmission through the clothing was calculated. Results (1) The ultraviolet light transmission was significantly higher through white cloth than through black cloth; the transmission was significantly higher through polyester cloth than through cotton. (2) The weather significantly influenced ultraviolet light transmission through white polyester cloth; transmission was highest on clear days and lowest on overcast days (ultraviolet A: P=0.000; ultraviolet B: P=0.008). (3) Air quality parameters (air quality index and particulate matter 2.5 and 10) were inversely related to the ultraviolet light intensity that reached the earth’s surface. Ultraviolet B transmission through white polyester cloth was greater under conditions of low air pollution compared with high air pollution. Conclusion Clothing color and material and different types of weather affected ultraviolet light transmission; for one particular cloth, the transmission decreased with increasing air pollution. PMID:25923778

  3. A novel UV-photolysis approach with acetone and isopropyl alcohol for the rapid determination of fluoride in organofluorine-containing drugs by spectrophotometry.

    PubMed

    Mullapudi, Venkata Balarama Krishna; Dheram, Karunasagar

    2018-01-01

    A UV photolysis decomposition (UVPD) method for the determination of fluoride in fluorine containing pharmaceuticals by spectrophotometry is reported. It is based on the use of high intensity UV-irradiation in the presence of a digesting solution comprising a mixture of acetone and isopropanol. For the optimization of the UVPD procedure, three bulk drugs (levofloxacin, nebivolol and efavirenz) were chosen as representatives of three diverse compounds containing a single fluorine atom, two fluorine atoms, and trifluoromethyl groups respectively. Operational conditions of the UVPD method, such as concentration and volume of reagents (acetone and isopropyl alcohol), and UV irradiation time (1-6 minutes) were optimized. The efficiency of digestion was evaluated by the determination of fluoride in sample digests. Using the developed method, it was possible for complete conversion of the organofluoride to free fluoride ion for its subsequent determination by spectrophotometry based on bleaching of Zr-xylenol orange-color complex. Quantitative recovery (>98%) of the fluorine in the drug samples could be achieved using a mixture of 2% acetone + 2% isopropyl alcohol + 0.003% Na 2 CO 3 in just 5 minutes of UV irradiation, which can be considered an important aspect considering the difficulties involved in the cleavage of the CF bond. Accuracy was evaluated by comparison of results obtained by the UVPD method with the values estimated using formula weight of the compound and no statistical difference was observed between the results. Therefore, the proposed method is suitable for application in routine analysis of fluoride in organofluorine-containing drugs. Copyright © 2016. Published by Elsevier B.V.

  4. Fluorescence of molecular hydrogen excited by solar extreme-ultraviolet radiation

    NASA Technical Reports Server (NTRS)

    Feldman, P. D.; Fastie, W. G.

    1973-01-01

    During trans-earth coast, the Apollo 17 ultraviolet spectrometer was scheduled to make observations of the far ultraviolet background in selected regions of the sky. In the course of one of these observations, the spacecraft fuel cells were routinely purged of excess hydrogen and water vapor. The ultraviolet fluorescence spectrum of the purged molecular hydrogen excited by solar extreme ultraviolet radiation is interpreted by absorption of solar L-beta and L-gamma radiation in the nearly resonant (6, 0) and (11, 0) Lyman bands. The results are deemed significant for ultraviolet spectroscopic investigations of the atmospheres of the moon and planets since Lyman-band fluorescence provides an unambiguous means of identification of molecular hydrogen in upper atmospheres.

  5. Prediction of skin cancer occurrence by ultraviolet solar index

    PubMed Central

    Rivas, Miguel; Rojas, Elisa; Calaf, Gloria M.

    2012-01-01

    An increase in the amount of solar ultraviolet light that reaches the Earth is considered to be responsible for the worldwide increase in skin cancer. It has been reported that exposure to excessive levels of solar ultraviolet light has multiple effects, which can be harmful to humans. Experimental ultraviolet light measurements were obtained in several locations in Chile between 2006 and 2009 using wide-band solar light Biometer YES, calibrated according to World Meteorological Organization (WMO) criteria and integrated into the National Meteorological Center of Chile ultraviolet network (DMC). The aim of this study was to determine skin cancer rates in relation to experimental data accumulated during one year of studying the solar ultraviolet index in Chile, in order to explain the possible effect of radiation on skin cancer. The rate of skin cancer per 100,000 persons was considered in Arica, Santiago, Concepción and Valdivia and extrapolated to other cities. Results of the present study showed that the incidence of skin cancer was markedly correlated with accumulative ultraviolet radiation, and rates of skin cancer could be extrapolated to other locations in Chile. There is a steady increase in the rate of skin cancer in cities located nearest to the equator (low latitude) that receive greater accumulated solar ultraviolet radiation, due to the accumulative effects of this type of radiation on the skin. It can be concluded that Arica is a city at sea level that receives higher levels of ultraviolet solar radiation than other locations, which may explain the higher prevalence of skin cancer in the population of this location, compared with other cities in Chile. PMID:22741013

  6. Photoresist composition for extreme ultraviolet lithography

    DOEpatents

    Felter, T. E.; Kubiak, G. D.

    1999-01-01

    A method of producing a patterned array of features, in particular, gate apertures, in the size range 0.4-0.05 .mu.m using projection lithography and extreme ultraviolet (EUV) radiation. A high energy laser beam is used to vaporize a target material in order to produce a plasma which in turn, produces extreme ultraviolet radiation of a characteristic wavelength of about 13 nm for lithographic applications. The radiation is transmitted by a series of reflective mirrors to a mask which bears the pattern to be printed. The demagnified focused mask pattern is, in turn, transmitted by means of appropriate optics and in a single exposure, to a substrate coated with photoresists designed to be transparent to EUV radiation and also satisfy conventional processing methods. A photoresist composition for extreme ultraviolet radiation of boron carbide polymers, hydrochlorocarbons and mixtures thereof.

  7. Photodissociation dynamics of propanal and isobutanal: The Norrish Type I pathway

    NASA Astrophysics Data System (ADS)

    Harrison, Aaron W.; Kable, Scott H.

    2018-04-01

    The Norrish Type I photodissociation of two aliphatic aldehydes, propanal and isobutanal, has been investigated using velocity-map imaging. The HCO photoproduct of this reaction was probed using a 1+1 resonance-enhanced multiphoton ionization scheme via the 3p2Π Rydberg state. The velocity map images of HCO+ were collected across a range of photolysis energies for both species from 30 500 to 33 000 cm-1 (λ = 312-327 nm). The corresponding translational energy distributions show that the majority of the available energy goes into the translational motion of the products (55%-68%) with this fraction increasing as the T1 barrier is approached. Analysis of the translational energy distributions was also used to determine the aldehyde α C-C bond dissociation energies which were found to be 339.8 ± 2.5 and 331.2 ± 2.5 kJ/mol for propanal and isobutanal, respectively. These values were also found to be in good agreement with the computed dissociation energies using G4 and CCSD(T)/aug-cc-pVTZ//M062X/aug-cc-pVTZ levels of theory. Furthermore, these dissociation energies, combined with the known ΔfH (0 K) of the reaction products, provided the ΔfH (0 K) of propanal and isobutanal which were calculated to be -167.3 ± 2.5 and -184.0 ± 2.5 kJ/mol, respectively.

  8. Modelling and Display of the Ultraviolet Sky

    NASA Astrophysics Data System (ADS)

    Daniels, J.; Henry, R.; Murthy, J.; Allen, M.; McGlynn, T. A.; Scollick, K.

    1994-12-01

    A computer program is currently under development to model in 3D - one dimension of which is wavelength - all the known and major speculated sources of ultraviolet (900 A - 3100 A ) radiation over the celestial sphere. The software is being written in Fortran 77 and IDL and currently operates under IRIX (the operating system of the Silicon Graphics Iris Machine); all output models are in FITS format. Models along with display software will become available to the astronomical community. The Ultraviolet Sky Model currently includes the Zodiacal Light, Point Sources of Emission, and the Diffuse Galactic Light. The Ultraviolet Sky Model is currently displayed using SkyView: a package under development at NASA/ GSFC, which allows users to retrieve and display publically available all-sky astronomical survey data (covering many wavebands) over the Internet. We present a demonstration of the SkyView display of the Ultraviolet Model. The modelling is a five year development project: the work illustrated here represents product output at the end of year one. Future work includes enhancements to the current models and incorporation of the following models: Galactic Molecular Hydrogen Fluorescence; Galactic Highly Ionized Atomic Line Emission; Integrated Extragalactic Light; and speculated sources in the intergalactic medium such as Ionized Plasma and radiation from Non-Baryonic Particle Decay. We also present a poster which summarizes the components of the Ultraviolet Sky Model and outlines a further package that will be used to display the Ultraviolet Model. This work is supported by United States Air Force Contract F19628-93-K-0004. Dr J. Daniels is supported with a post-doctoral Fellowship from the Leverhulme Foundation, London, United Kingdom. We are also grateful for the encouragement of Dr Stephen Price (Phillips Laboratory, Hanscomb Air Force Base, MA)

  9. The difficulty of ultraviolet emssion from supernovae

    NASA Technical Reports Server (NTRS)

    Colgate, S. A.

    1971-01-01

    There are certain conceptual difficulties in the theory of the generation of ultraviolet radiation which is presumed for the creation of the optical fluorescence mechanism of supernova light emission and ionization of a nebula as large as the Gum nebula. Requirements concerning the energy distribution of the ultraviolet photons are: 1) The energy of the greater part of the photons must be sufficient to cause both helium fluorescence and hydrogen ionization. 2) If the photons are emitted in an approximate black body spectrum, the fraction of energy emitted in the optical must be no more than what is already observed. Ultraviolet black body emission depends primarily on the energy source. The probability that the wide mixture of elements present in the interstellar medium and supernova ejecta results in an emission localized in a limited region with less than 0.001 emission in the visible, for either ionization or fluorescence ultraviolet, is remote. Therefore transparent emission must be excluded as unlikely, and black body or at least quasi-black-body emission is more probable.

  10. Occupational Skin Hazards From Ultraviolet (UV) Exposures

    NASA Astrophysics Data System (ADS)

    Urbach, F.; Wolbarsht, M. L.

    1980-10-01

    The various types of UV effects on the skin are classified according to the part of the spectrum and their beneficial or deleterious nature. Some hazardous ultraviolet sources used in industrial processes are described, and examples of photoallergy, phototoxicity, and photosensitization resulting from UV exposures are given. The incidence of skin cancer as a function of geographical location and exposure to sunlight is discussed in relation to natural and artificial exposures to long and short wavelength UV, especially in connection with tanning booths. The conclusion is reached that there is enough ultraviolet in a normal environment to propose a hazard, and additional ultraviolet exposure from industrial or consumer sources is not necessary, and should be eliminated wherever possible.

  11. Occupational Skin Hazards From Ultraviolet (UV) Exposures

    NASA Astrophysics Data System (ADS)

    Urbach, F.; Wolbarsht, M. L.

    1981-11-01

    The various types of UV effects on the skin are classified according to the part of the spectrum and their beneficial or deleterious nature. Some hazardous ultraviolet sources used in industrial processes are described, and examples of photoallergy, phototoxicity, and photosensitization resulting from UV exposures are given. The incidence of skin cancer as a function of geographical location and exposure to sunlight is discussed in relation to natural and artificial exposures to long and short wavelength UV, especially in connection with tanning booths. The conclusion is reached that there is enough ultraviolet in a normal environment to propose a hazard, and additional ultraviolet exposure from industrial or consumer sources is not necessary, and should be eliminated wherever possible.

  12. Far-ultraviolet imagery of the Barnard Loop Nebula

    NASA Technical Reports Server (NTRS)

    Carruthers, G. R.; Opal, C. B.

    1977-01-01

    An electrographic Schmidt camera carried on a sounding rocket has yielded far-ultraviolet (1050-2000 A and 1230-2000 A) images of the Barnard Loop Nebula and of the general background in the Orion region due to scattering of ultraviolet starlight by interstellar dust particles. The total intensity in the Barnard Loop region agrees well with OAO-2 measurements, but the discrete Loop structure contributes only some 15% of the total. The measurements are consistent with a relatively high albedo for the dust grains in the far-ultraviolet.

  13. Ultraviolet microscopy aids in cytological and biomedical research

    NASA Technical Reports Server (NTRS)

    Schlenk, F.; Svihla, B.

    1967-01-01

    Ultraviolet microscopy is used by cytologists and biochemists to study the morphological and physiological changes in the living cell under varied culture conditions. The yeast cell is used because of its content of ultraviolet absorbing materials and its lack of motility.

  14. The ultraviolet variations of iota Cas

    NASA Technical Reports Server (NTRS)

    Molnar, M. R.; Mallama, A. D.; Soskey, D. G.; Holm, A. V.

    1976-01-01

    The Ap variable star iota Cas was observed with the photometers on OAO-2 covering the spectral range 1430-4250 A. The ultraviolet light curves show a double wave with primary minimum and maximum at phase ? 0.00 and 0.35, respectively. Secondary minimum light is at phase ? 0.65 with secondary maximum at phase ? 0.85. The light curves longward of 3150 A vary in opposition to those shortward of this 'null region'. Ground-based coude spectra show that the Fe II and Cr II line strengths have a double-wave variation such that maximum strength occurs at minimum ultraviolet light. We suggest that the strong ultraviolet opacities due to photoionization and line blanketing by these metals may cause the observed photometric variations. We have also constructed an oblique-rotator model which shows iron and chromium lying in a great circle band rather than in circular spots.

  15. Ultraviolet reflective coating

    NASA Technical Reports Server (NTRS)

    Schutt, J. B.

    1974-01-01

    Composition consists of dispersion of barium sulphate in aqueous solution of water-soluble inorganic binder. Binder is selected from group consisting of alkali metal sulphates. Coating exhibits high reflectance of ultraviolet light to wavelengths of approximately 200.0 nm, which compares favorably with high reflectance of virgin barium sulphate power.

  16. Method for generating extreme ultraviolet with mather-type plasma accelerators for use in Extreme Ultraviolet Lithography

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hassanein, Ahmed; Konkashbaev, Isak

    A device and method for generating extremely short-wave ultraviolet electromagnetic wave uses two intersecting plasma beams generated by two plasma accelerators. The intersection of the two plasma beams emits electromagnetic radiation and in particular radiation in the extreme ultraviolet wavelength. In the preferred orientation two axially aligned counter streaming plasmas collide to produce an intense source of electromagnetic radiation at the 13.5 nm wavelength. The Mather type plasma accelerators can utilize tin, or lithium covered electrodes. Tin, lithium or xenon can be used as the photon emitting gas source.

  17. Extended atmospheres of outer planet satellites and comets

    NASA Technical Reports Server (NTRS)

    Smyth, W. H.; Combi, M. R.

    1984-01-01

    The cometary hydrogen particle-trajectory model was used successfully to analyze observations of Comet P/Encke. The Pioneer Venus Orbiter Ultraviolet Spectrometer observed the comet at 1216A (hydrogen Lyman-alpha) on 15 April 1984, when the comet was .58 AU from the Sun and 1.02 AU from Venus. The analysis implies a production rate at .58 AU of 3.3 x 10 to the 28th power/sec of the water molecules which photodissociate to produce the observed hydrogen.

  18. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ultraviolet activator for polymerization. 872.6070 Section 872.6070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... polymerization. (a) Identification. An ultraviolet activator for polymerization is a device that produces...

  19. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ultraviolet activator for polymerization. 872.6070 Section 872.6070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... polymerization. (a) Identification. An ultraviolet activator for polymerization is a device that produces...

  20. JUDE: An Ultraviolet Imaging Telescope pipeline

    NASA Astrophysics Data System (ADS)

    Murthy, J.; Rahna, P. T.; Sutaria, F.; Safonova, M.; Gudennavar, S. B.; Bubbly, S. G.

    2017-07-01

    The Ultraviolet Imaging Telescope (UVIT) was launched as part of the multi-wavelength Indian AstroSat mission on 28 September, 2015 into a low Earth orbit. A 6-month performance verification (PV) phase ended in March 2016, and the instrument is now in the general observing phase. UVIT operates in three channels: visible, near-ultraviolet (NUV) and far-ultraviolet (FUV), each with a choice of broad and narrow band filters, and has NUV and FUV gratings for low-resolution spectroscopy. We have written a software package (JUDE) to convert the Level 1 data from UVIT into scientifically useful photon lists and images. The routines are written in the GNU Data Language (GDL) and are compatible with the IDL software package. We use these programs in our own scientific work, and will continue to update the programs as we gain better understanding of the UVIT instrument and its performance. We have released JUDE under an Apache License.

  1. Ultraviolet corona detection sensor study

    NASA Technical Reports Server (NTRS)

    Schmitt, R. J.; MATHERN

    1976-01-01

    The feasibility of detecting electrical corona discharge phenomena in a space simulation chamber via emission of ultraviolet light was evaluated. A corona simulator, with a hemispherically capped point to plane electrode geometry, was used to generate corona glows over a wide range of pressure, voltage, current, electrode gap length and electrode point radius. Several ultraviolet detectors, including a copper cathode gas discharge tube and a UV enhanced silicon photodiode detector, were evaluated in the course of the spectral intensity measurements. The performance of both silicon target vidicons and silicon intensified target vidicons was evaluated analytically using the data generated by the spectroradiometer scans and the performance data supplied by the manufacturers.

  2. Photodissociation of van der Waals clusters of isoprene with oxygen, C{sub 5}H{sub 8}-O{sub 2}, in the wavelength range 213-277 nm

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Vidma, Konstantin V.; Frederix, Pim W. J. M.; Parker, David H.

    2012-08-07

    The speed and angular distribution of O atoms arising from the photofragmentation of C{sub 5}H{sub 8}-O{sub 2}, the isoprene-oxygen van der Waals complex, in the wavelength region of 213-277 nm has been studied with the use of a two-color dissociation-probe method and the velocity map imaging technique. Dramatic enhancement in the O atoms photo-generation cross section in comparison with the photodissociation of individual O{sub 2} molecules has been observed. Velocity map images of these 'enhanced' O atoms consisted of five channels, different in their kinetic energy, angular distribution, and wavelength dependence. Three channels are deduced to be due to themore » one-quantum excitation of the C{sub 5}H{sub 8}-O{sub 2} complex into the perturbed Herzberg III state ({sup 3}{Delta}{sub u}) of O{sub 2}. This excitation results in the prompt dissociation of the complex giving rise to products C{sub 5}H{sub 8}+O+O when the energy of exciting quantum is higher than the complex photodissociation threshold, which is found to be 41740 {+-} 200 cm{sup -1} (239.6{+-}1.2 nm). This last threshold corresponds to the photodissociation giving rise to an unexcited isoprene molecule. The second channel, with threshold shifted to the blue by 1480 {+-} 280 cm{sup -1}, corresponds to dissociation with formation of rovibrationally excited isoprene. A third channel was observed at wavelengths up to 243 nm with excitation below the upper photodissociation threshold. This channel is attributed to dissociation with the formation of a bound O atom C{sub 5}H{sub 8}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}O + O and/or to dissociation of O{sub 2} with borrowing of the lacking energy from incompletely cooled complex internal degrees of freedom C{sub 5}H{sub 8}{sup *}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}{sup *}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}+ O + O. The kinetic energy of the O atoms arising in two other observed

  3. Implementation of UV-based advanced oxidation processes in algal medium recycling.

    PubMed

    Wang, Wenxuan; Sha, Jun; Lu, Zhiying; Shao, Senlin; Sun, Peizhe; Hu, Qiang; Zhang, Xuezhi

    2018-09-01

    Algae show great potential as sustainable feedstock for numerous bioproducts. However, large volume of water consumption during algal biomass production makes that the culture media recycling is a necessity due to economic and environmental concern. To avoid the negative effect of enriched organic matters in the harvested culture media, pre-treatment prior to medium replenishment and reuse is required. In this study, degradation of algenitic organic matters (AOM) in the culture media by UV-based photolysis processes (i.e., direct UV, UV/peroxydisulfate (PDS), UV/H 2 O 2 , and UV/NH 2 Cl) was explored. The results showed that UV, UV/PDS, UV/H 2 O 2 and UV/NH 2 Cl caused a decrease of SUVA for 29.9%, 35.4%, 40.45%, and 22.6%, respectively, though the organic matter was almost not mineralized. Fluorescence excitation-emission matrix combined with parallel factor analysis indicated that UV/PDS and UV/H 2 O 2 degraded 47.26%-56.31% of the fulvic-like and humic-like fractions in AOM. Powder activated carbon absorption and growth evaluation for the AOPs-treated media indicated that UV/PDS and UV/H 2 O 2 processes not only could remove the growth inhibitors in the media, but were also beneficial to the algae growth. These results suggested that UV/PDS and UV/H 2 O 2 could effectively degrade the hydrophobic components in AOM and converted the growth inhibition fraction of AOM in the recycled media into nutrient source for algal growth. Different from the general application of UV-based AOP in the wastewater treatment, this study provided an innovative idea about how to pre-treat AOM in the media recycling: utilization rather than removal, which was a more sustainable and environment-friendly technology. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. SR-71 Ship #1 - Ultraviolet Experiment

    NASA Technical Reports Server (NTRS)

    1994-01-01

    NASA's SR-71 streaks into the twilight on a night/science flight from the Dryden Flight Research Center, Edwards, California. Mounted in the nose of the SR-71 was an ultraviolet video camera aimed skyward to capture images of stars, asteroids and comets. The science portion of the flight is a project of the Jet Propulsion Laboratory, Pasadena, California. Two SR-71 aircraft have been used by NASA as test beds for high-speed and high-altitude aeronautical research. One early research project flown on one of Dryden's SR-71s consisted of a proposal for a series of flights using the SR-71 as a science camera platform for the Jet Propulsion Laboratory (JPL) of the California Institute of Technology, which operates under contract to NASA in much the way that NASA centers do. In March 1993, an upward-looking ultraviolet (UV) video camera placed in the SR-71's nosebay studied a variety of celestial objects in the ultraviolet light spectrum. The SR-71 was proposed as a test bed for the experiment because it is capable of flying at altitudes above 80,000 feet for an extended length of time. Observation of ultraviolet radiation is not possible from the Earth's surface because the atmosphere's ozone layer absorbs UV rays. Study of UV radiation is important because it is known to cause skin cancer with prolonged exposure. UV radiation is also valuable to study from an astronomical perspective. Satellite study of ultraviolet radiation is very expensive. As a result, the South West Research Institute (SWRI) in Texas developed the hypothesis of using a high-flying aircraft such as the SR-71 to conduct UV observations. The SR-71 is capable of flying above 90 percent of the Earth's atmosphere. The flight program was also designed to test the stability of the aircraft as a test bed for UV observation. A joint flight program was developed between the JPL and NASA's Ames-Dryden Flight Research Facility (redesignated the Dryden Flight Research Center, Edwards, California, in 1994) in

  5. 21 CFR 878.4635 - Ultraviolet lamp for tanning.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ultraviolet lamp for tanning. 878.4635 Section 878.4635 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES GENERAL AND PLASTIC SURGERY DEVICES Surgical Devices § 878.4635 Ultraviolet lamp for...

  6. 21 CFR 878.4635 - Ultraviolet lamp for tanning.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Ultraviolet lamp for tanning. 878.4635 Section 878.4635 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES GENERAL AND PLASTIC SURGERY DEVICES Surgical Devices § 878.4635 Ultraviolet lamp for...

  7. 21 CFR 878.4635 - Ultraviolet lamp for tanning.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Ultraviolet lamp for tanning. 878.4635 Section 878.4635 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES GENERAL AND PLASTIC SURGERY DEVICES Surgical Devices § 878.4635 Ultraviolet lamp for...

  8. 21 CFR 878.4635 - Ultraviolet lamp for tanning.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Ultraviolet lamp for tanning. 878.4635 Section 878.4635 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES GENERAL AND PLASTIC SURGERY DEVICES Surgical Devices § 878.4635 Ultraviolet lamp for...

  9. ULTRAVIOLET PROTECTIVE PIGMENTS AND DNA DIMER INDUCTION AS RESPONSES TO ULTRAVIOLET RADIATION

    EPA Science Inventory

    Life on Earth has evolved adaptations to many environmental stresses over the epochs. One consistent stress has been exposure to ultraviolet (UV) radiation. The most basic effect of UV radiation on biological systems is damage to DNA. In response to UV radiation organisms have ad...

  10. Inactivation of Pseudomonas aeruginosa biofilm after ultraviolet light-emitting diode treatment: a comparative study between ultraviolet C and ultraviolet B

    NASA Astrophysics Data System (ADS)

    Argyraki, Aikaterini; Markvart, Merete; Bjørndal, Lars; Bjarnsholt, Thomas; Petersen, Paul Michael

    2017-06-01

    The objective of this study was to test the inactivation efficiency of two different light-based treatments, namely ultraviolet B (UVB) and ultraviolet C (UVC) irradiation, on Pseudomonas aeruginosa biofilms at different growth stages (24, 48, and 72 h grown). In our experiments, a type of AlGaN light-emitting diodes (LEDs) was used to deliver UV irradiation on the biofilms. The effectiveness of the UVB at 296 nm and UVC at 266 nm irradiations was quantified by counting colony-forming units. The survival of less mature biofilms (24 h grown) was studied as a function of UV-radiant exposure. All treatments were performed on three different biological replicates to test reproducibility. It was shown that UVB irradiation was significantly more effective than UVC irradiation in inactivating P. aeruginosa biofilms. UVC irradiation induced insignificant inactivation on mature biofilms. The fact that the UVB at 296 nm exists in daylight and has such disinfection ability on biofilms provides perspectives for the treatment of infectious diseases.

  11. Line Tunable Ultraviolet Laser

    NASA Technical Reports Server (NTRS)

    Walsh, Brian M.; Barnes, Norman P.

    2004-01-01

    An ultraviolet laser is demonstrated using a dual wavelength Nd:YAG oscillator, sum frequency and second harmonic process. Synchronous pulses at 1.052 and 1.319 micrometers are amplified, mixed and subsequently doubled, producing pulses at 0.293 micrometers.

  12. Anatomy of a Photodissociation Region: High angular resolution images of molecular emission in the Orion Bar

    NASA Technical Reports Server (NTRS)

    Tauber, Jan A.; Tielens, A. G. G. M.; Meixner, Margaret; Foldsmith, Paul F.

    1994-01-01

    We present observations of the molecular component of the Orion Bar, a prototypical Photodissociation Region (PDR) illuminated by the Trapezium cluster. The high angular resolution (6 sec-10 sec) that we have achieved by combining single-dish and interferometric observations has allowed us to examine in detail the spatial and kinematic morphology of this region and to estimate the physical characteristics of the molecular gas it contains. Our observations indicate that this PDR can be essentially described as a homogeneously distributed slab of moderately dense material (approximately 5 x 10(exp 4)/cu cm), in which are embedded a small number of dense (greater than 10(exp 6)/cu cm) clumps. The latter play little or no role in determining the thickness and kinetic temperature structure of this PDR. This observational picture is largely supported by PDR model calculations for this region, which we describe in detail in this work. We also find our model predictions of the intensities of a variety of atomic and molecular lines to be in good general agreement with a number of previous observations.

  13. Exploring Mercury's Surface in UltraViolet from Orbit

    NASA Astrophysics Data System (ADS)

    Izenberg, N.

    2017-12-01

    The MESSENGER Mission's Ultraviolet and Visible Spectrometer (UVVS) component of its Mercury Atmosphere and Surface Composition Spectrometer (MASCS) instrument obtained approximately 4600 point observations of Mercury's surface in middle ultraviolet (MUV; 210 nm - 300 nm) and far ultraviolet (FUV; 119.1 - 122.5 nm and 129.2 - 131.5 nm) wavelengths over the course of its orbital mission, mostly in Mercury's southern hemisphere. Given the very low (<1 to 2 wt %) average abundance of iron in the silicates of Mercury observed by multiple MESSENGER instruments, the near- to middle-ultraviolet wavelengths encompassing the oxygen metal charge transfer band (<400 nm), which is more sensitive to the presence of iron than the classic 1 micron absorption band, provides potentially useful additional compositional insight into the top layer of Mercury's regolith. The presence of nano- and microphase carbon also has potentially significant expression in the ultraviolet, and the interplay and variation between carbon and iron in mercury surface materials is an active area of investigation. Analysis of middle-UV surface reflectance and parameters appear to support the presence of varying amounts of carbon in different spectral or geologic units on Mercury. Far-UV reflectance data is currently under-utilized, but analysis of lunar surface by the Lunar Reconnaissance Orbiter (LRO) Lyman Alpha Mapping Project (LAMP) indicate that the data are sensitive to both composition and space weathering. The far-UV reflectance from MASCS may provide similar information for the Mercury surface, complementing results from longer wavelengths. MESSENGER data products for surface reflectance include middle-UV reflectance spectra, ultraviolet far-UV reflectance values, combined middle-UV through near-infrared spectra (210 nm - 1450 nm), a global `spectral cube' of near-UV to near-IR, and an upcoming UV spectral cube.

  14. Ultraviolet Spectrum And Chemical Reactivity Of CIO Dimer

    NASA Technical Reports Server (NTRS)

    Demore, William B.; Tschuikow-Roux, E.

    1992-01-01

    Report describes experimental study of ultraviolet spectrum and chemical reactivity of dimer of chlorine monoxide (CIO). Objectives are to measure absorption cross sections of dimer at near-ultraviolet wavelengths; determine whether asymmetrical isomer (CIOCIO) exists at temperatures relevant to Antarctic stratosphere; and test for certain chemical reactions of dimer. Important in photochemistry of Antarctic stratosphere.

  15. Analysis and design of the ultraviolet warning optical system based on interference imaging

    NASA Astrophysics Data System (ADS)

    Wang, Wen-cong; Hu, Hui-jun; Jin, Dong-dong; Chu, Xin-bo; Shi, Yu-feng; Song, Juan; Liu, Jin-sheng; Xiao, Ting; Shao, Si-pei

    2017-10-01

    Ultraviolet warning technology is one of the important methods for missile warning. It provides a very effective way to detect the target for missile approaching alarm. With the development of modern technology, especially the development of information technology at high speed, the ultraviolet early warning system plays an increasingly important role. Compared to infrared warning, the ultraviolet warning has high efficiency and low false alarm rate. In the modern warfare, how to detect the threats earlier, prevent and reduce the attack of precision-guided missile has become a new challenge of missile warning technology. Because the ultraviolet warning technology has high environmental adaptability, the low false alarm rate, small volume and other advantages, in the military field applications it has been developed rapidly. For the ultraviolet warning system, the optimal working waveband is 250 nm 280 nm (Solar Blind UV) due to the strong absorption of ozone layer. According to current application demands for solar blind ultraviolet detection and warning, this paper proposes ultraviolet warning optical system based on interference imaging, which covers solar blind ultraviolet (250nm-280nm) and dual field. This structure includes a primary optical system, an ultraviolet reflector array, an ultraviolet imaging system and an ultraviolet interference imaging system. It makes use of an ultraviolet beam-splitter to achieve the separation of two optical systems. According to the detector and the corresponding application needs of two visual field of the optical system, the calculation and optical system design were completed. After the design, the MTF of the two optical system is more than 0.8@39lp/mm.A single pixel energy concentration is greater than 80%.

  16. Luminosity function of faint galaxies with ultraviolet continuum

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Stepanyan, D.A.

    1985-05-01

    The spatial density of faint galaxies with ultraviolet continuum in the Second Survey of the Byurakan Astrophysical Observatory is determined. The luminosity function of galaxies with ultraviolet continuum can be extended to objects fainter by 1-1.5 magnitudes. The spatial density of such galaxies in the interval of luminosities -16 /sup m/ .5 to -21 /sup m/ .5 is on the average 0.08 of the total density of field galaxies in the same interval of absolute magnitudes. The spatial density of low-luminosity galaxies with ultraviolet continuum is very high. In the interval from -12 /sup m/ .5 to -15 /sup m/more » .5 it is 0.23 Mpc/sup -3/.« less

  17. Web-Resources for Astronomical Data in the Ultraviolet

    NASA Astrophysics Data System (ADS)

    Sachkov, M. E.; Malkov, O. Yu.

    2017-12-01

    In this paper we describe databases of space projects that are operating or have operated in the ultraviolet spectral region. We give brief descriptions and links to major sources for UV data on the web: archives, space mission sites, databases, catalogues. We pay special attention to the World Space Observatory—Ultraviolet mission that will be launched in 2021.

  18. Metallicity and the level of the ultraviolet rising branch in elliptical galaxies

    NASA Technical Reports Server (NTRS)

    Faber, S. M.

    1986-01-01

    This final report concerns a project to study the systematics of the ultraviolet flux level in elliptical galaxies. Prior to the inception of this work, the systematic behavior of the ultraviolet flux level was basically unknown and ultraviolet fluxes were observed to vary greatly from galaxy to galaxy. There was a suggestion, however, that there might be a dependence of ultraviolet flux on galaxy metallicity, but the correlation was based on just six galaxies. IUE spectra of elliptical galaxies have been reanalyzed and placed on a consistent, homogenous flux system. The major conclusion is a confirmation of the original hypothesis: galaxies with stronger Mg2 lines show enhanced ultraviolet flux.

  19. Galileo Ultraviolet Spectrometer experiment

    NASA Technical Reports Server (NTRS)

    Hord, C. W.; Mcclintock, W. E.; Stewart, A. I. F.; Barth, C. A.; Esposito, L. W.; Thomas, G. E.; Sandel, B. R.; Hunten, D. M.; Broadfoot, A. L.; Shemansky, D. E.

    1992-01-01

    The Galileo ultraviolet spectrometer experiment uses data obtained by the Ultraviolet Spectrometer (UVS) mounted on the pointed orbiter scan platform and from the Extreme Ultraviolet Spectrometer (EUVS) mounted on the spinning part of the orbiter with the field of view perpendicular to the spin axis. The UVS is a Ebert-Fastie design that covers the range 113-432 nm with a wavelength resolution of 0.7 nm below 190 and 1.3 nm at longer wavelengths. The UVS spatial resolution is 0.4 deg x 0.1 deg for illuminated disk observations and 1 deg x 0.1 deg for limb geometries. The EUVS is a Voyager design objective grating spectrometer, modified to cover the wavelength range from 54 to 128 nm with wavelength resolution 3.5 nm for extended sources and 1.5 nm for point sources and spatial resolution of 0.87 deg x 0.17 deg. The EUVS instrument will follow up on the many Voyager UVS discoveries, particularly the sulfur and oxygen ion emissions in the Io torus and molecular and atomic hydrogen auroral and airglow emissions from Jupiter. The UVS will obtain spectra of emission, absorption, and scattering features in the unexplored, by spacecraft, 170-432 nm wavelength region. The UVS and EUVS instruments will provide a powerful instrument complement to investigate volatile escape and surface composition of the Galilean satellites, the Io plasma torus, micro- and macro-properties of the Jupiter clouds, and the composition structure and evolution of the Jupiter upper atmosphere.

  20. Ultraviolet radiation changes

    NASA Technical Reports Server (NTRS)

    Mckenzie, Richard L.; Frederick, John E.; Ilyas, Mohammad; Filyushkin, V.; Wahner, Andreas; Stamnes, K.; Muthusubramanian, P.; Blumthaler, M.; Roy, Colin E.; Madronich, Sasha

    1991-01-01

    A major consequence of ozone depletion is an increase in solar ultraviolet (UV) radiation received at the Earth's surface. This chapter discusses advances that were made since the previous assessment (World Meteorological Organization (WMO)) to our understanding of UV radiation. The impacts of these changes in UV on the biosphere are not included, because they are discussed in the effects assessment.

  1. Psoriasis and ultraviolet radiation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Farber, E.M.; Nall, L.

    1993-09-01

    Prevention and detection screening programs as a public health service in curtailing the ever-increasing incidence of all forms of skin cancer are reviewed. The effect of solar and artificial ultraviolet radiation on the general population and persons with psoriasis is examined. 54 refs.

  2. Photosynthetic carbon reduction by seagrasses exposed to ultraviolet A radiation

    NASA Technical Reports Server (NTRS)

    1979-01-01

    The seagrasses Halophila engelmannii, Halodule wrightii, and Syringodium filiforme were examined for their intrinsic sensitivity to ultraviolet-A-UV-A and ultraviolet-B-UV-B radiation. The effect of UV-A on photosynthetically active radiation (PAR) was also determined. Ultraviolet-A and ultraviolet-B were studied with emphasis on the greater respective environmental consequence in terms of seagrass distribution and abundance. Results indicate that an intrinsic sensitivity to UV-A alone is apparent only in Halophila, while net photosynthesis in Halodule and Syringodium seems unaffected by the level of UV-A provided. The sensitivity of Halophila to UV-A in the absense of (PAR) indicates that the photosynthetic reaction does not need to be in operation for damage to occur. Other significant results are reported.

  3. Method for extreme ultraviolet lithography

    DOEpatents

    Felter, T. E.; Kubiak, Glenn D.

    1999-01-01

    A method of producing a patterned array of features, in particular, gate apertures, in the size range 0.4-0.05 .mu.m using projection lithography and extreme ultraviolet (EUV) radiation. A high energy laser beam is used to vaporize a target material in order to produce a plasma which in turn, produces extreme ultraviolet radiation of a characteristic wavelength of about 13 nm for lithographic applications. The radiation is transmitted by a series of reflective mirrors to a mask which bears the pattern to be printed. The demagnified focused mask pattern is, in turn, transmitted by means of appropriate optics and in a single exposure, to a substrate coated with photoresists designed to be transparent to EUV radiation and also satisfy conventional processing methods.

  4. Method for extreme ultraviolet lithography

    DOEpatents

    Felter, T. E.; Kubiak, G. D.

    2000-01-01

    A method of producing a patterned array of features, in particular, gate apertures, in the size range 0.4-0.05 .mu.m using projection lithography and extreme ultraviolet (EUV) radiation. A high energy laser beam is used to vaporize a target material in order to produce a plasma which in turn, produces extreme ultraviolet radiation of a characteristic wavelength of about 13 nm for lithographic applications. The radiation is transmitted by a series of reflective mirrors to a mask which bears the pattern to be printed. The demagnified focused mask pattern is, in turn, transmitted by means of appropriate optics and in a single exposure, to a substrate coated with photoresists designed to be transparent to EUV radiation and also satisfy conventional processing methods.

  5. ULTRAVIOLET RADIATION DOWN-REGULATES ALLERGY IN BALB/C MICE

    EPA Science Inventory

    ULTRAVIOLET RADIATION SUPPRESSES ALLERGY IN BALB/C MICE
    Marsha D.W. Ward+ *, Denise M. Sailstad+, Debora L. Andrews, Elizabeth H. Boykin, and MaryJane K. Selgrade

    ABSTRACT
    The immunosuppressive effects of exposure to ultraviolet radiation (UVR) are well known and the...

  6. Photodissociation of aligned CH3I and C6H3F2I molecules probed with time-resolved Coulomb explosion imaging by site-selective extreme ultraviolet ionization

    PubMed Central

    Amini, Kasra; Savelyev, Evgeny; Brauße, Felix; Berrah, Nora; Bomme, Cédric; Brouard, Mark; Burt, Michael; Christensen, Lauge; Düsterer, Stefan; Erk, Benjamin; Höppner, Hauke; Kierspel, Thomas; Krecinic, Faruk; Lauer, Alexandra; Lee, Jason W. L.; Müller, Maria; Müller, Erland; Mullins, Terence; Redlin, Harald; Schirmel, Nora; Thøgersen, Jan; Techert, Simone; Toleikis, Sven; Treusch, Rolf; Trippel, Sebastian; Ulmer, Anatoli; Vallance, Claire; Wiese, Joss; Johnsson, Per; Küpper, Jochen; Rudenko, Artem; Rouzée, Arnaud; Stapelfeldt, Henrik; Rolles, Daniel; Boll, Rebecca

    2018-01-01

    We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon–iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules. PMID:29430482

  7. Photodissociation of aligned CH3I and C6H3F2I molecules probed with time-resolved Coulomb explosion imaging by site-selective extreme ultraviolet ionization.

    PubMed

    Amini, Kasra; Savelyev, Evgeny; Brauße, Felix; Berrah, Nora; Bomme, Cédric; Brouard, Mark; Burt, Michael; Christensen, Lauge; Düsterer, Stefan; Erk, Benjamin; Höppner, Hauke; Kierspel, Thomas; Krecinic, Faruk; Lauer, Alexandra; Lee, Jason W L; Müller, Maria; Müller, Erland; Mullins, Terence; Redlin, Harald; Schirmel, Nora; Thøgersen, Jan; Techert, Simone; Toleikis, Sven; Treusch, Rolf; Trippel, Sebastian; Ulmer, Anatoli; Vallance, Claire; Wiese, Joss; Johnsson, Per; Küpper, Jochen; Rudenko, Artem; Rouzée, Arnaud; Stapelfeldt, Henrik; Rolles, Daniel; Boll, Rebecca

    2018-01-01

    We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon-iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.

  8. Ultraviolet radiation, human health, and the urban forest

    Treesearch

    Gordon M. Heisler; Richard H. Grant

    2000-01-01

    Excess exposure to ultraviolet (UV) radiation from the sun, particularly the ultraviolet B (UVB) portion, has been linked with adverse effects on human health ranging from skin cancers to eye diseases such as cataracts. Trees may prevent even greater disease rates in humans by reducing UV exposure. Tree shade greatly reduces UV irradiance when both the sun and sky are...

  9. The Ratio of Ortho- to Para-H2 in Photodissociation Regions

    NASA Technical Reports Server (NTRS)

    Sternberg, Amiel; Neufeld, David A.

    1999-01-01

    We discuss the ratio of ortho- to para-H2 in photodissociation regions (PDRs). We draw attention to an apparent confusion in the literature between the ortho-to-para ratio of molecules in FUV-pumped vibrationally excited states and the total H2 ortho-to-para abundance ratio. These ratios are not the same because the process of FUV pumping of fluorescent H2 emission in PDRs occurs via optically thick absorption lines. Thus gas with an equilibrium ratio of ortho- to para-H2 equal to 3 will yield FUV-pumped vibrationally excited ortho-to-para ratios smaller than 3, because the ortho-H2 pumping rates are preferentially reduced by optical depth effects. Indeed, if the ortho and para pumping lines are on the "square root" part of the curve of growth, then the expected ratio of ortho and para vibrational line strengths is 3(sup 1/2) approximately 1.7, close to the typically observed value. Thus, contrary to what has sometimes been stated in the literature, most previous measurements of the ratio of ortho- to para-H2 in vibrationally excited states are entirely consistent with a total ortho-to-para ratio of 3, the equilibrium value for temperatures greater than 200 K. We present an analysis and several detailed models that illustrate the relationship between the total ratios of ortho- to para-H2 and the vibrationally excited ortho-to-para ratios in PDRs. Recent Infrared Space Observatory measurements of pure rotational and vibrational H2 emissions from the PDR in the star-forming region S140 provide strong observational support for our conclusions.

  10. The extreme ultraviolet explorer

    NASA Technical Reports Server (NTRS)

    Bowyer, Stuart; Malina, Roger F.

    1990-01-01

    The Extreme Ultraviolet Explorer (EUVE) mission, currently scheduled for launch in September 1991, is described. The primary purpose of the mission is to survey the celestial sphere for astronomical sources of Extreme Ultraviolet (EUV) radiation. The survey will be accomplished with the use of three EUV telescopes, each sensitive to a different segment of the EUV band. A fourth telescope will perform a high sensitivity search of a limited sample of the sky in the shortest wavelength bands. The all sky survey will be carried out in the first six months of the mission and will be made in four bands, or colors. The second phase of the mission, conducted entirely by guest observers selected by NASA, will be devoted to spectroscopic observations of EUV sources. The performance of the instrument components is described. An end to end model of the mission, from a stellar source to the resulting scientific data, was constructed. Hypothetical data from astronomical sources processed through this model are shown.

  11. Effect of ultraviolet light on mood, depressive disorders and well-being.

    PubMed

    Veleva, Bistra I; van Bezooijen, Rutger L; Chel, Victor G M; Numans, Mattijs E; Caljouw, Monique A A

    2018-06-01

    Human and animal studies have shown that exposure to ultraviolet light can incite a chain of endocrine, immunologic, and neurohumoral reactions that might affect mood. This review focuses on the evidence from clinical trials and observational studies on the effect of ultraviolet light on mood, depressive disorders, and well-being. A search was made in PubMed, Embase, Web of Science, Cochrane, Psychinfo, CINAHL, Academic Search Premier and Science Direct, and the references of key papers, for clinical trials and observational studies describing the effect of ultraviolet light applied to skin or eyes on mood, depressive disorders, and well-being. Of the seven studies eligible for this review, the effect of ultraviolet light on mood, depressive symptoms and seasonal affective disorders was positive in six of them. Of the seven studies, six demonstrated benefit of exposure to ultraviolet radiation and improvement in mood which supports a positive effect of ultraviolet light on mood. Because of the small number of the studies and their heterogeneity, more research is warranted to confirm and document this correlation. © 2018 The Authors. Photodermatology, Photoimmunology & Photomedicine Published by John Wiley & Sons Ltd.

  12. Ultraviolet Ring Around the Galaxies

    NASA Image and Video Library

    2010-08-11

    Astronomers have found unexpected rings and arcs of ultraviolet light around a selection of galaxies, four of which are shown here as viewed by NASA and the European Space Agency Hubble Space Telescope.

  13. Observations of the Ultraviolet Spectra of Carbon White Dwarfs

    NASA Technical Reports Server (NTRS)

    Wagner, G. A.

    1982-01-01

    Strong ultraviolet carbon lines were detected in additional white DC (continuous visual spectra) dwarfs using the IUE. These lines are not seen in the ultraviolet spectrum of the cool DC star Stein 2051 B. The bright DA white dwarf LB 3303 has a strong unidentified absorption near lambda 1400.

  14. Complex refractive index of Martian dust - Mariner 9 ultraviolet observations

    NASA Technical Reports Server (NTRS)

    Pang, K.; Ajello, J. M.; Hord, C. W.; Egan, W. G.

    1976-01-01

    Mariner 9 ultraviolet spectrometer observations of the 1971 dust clouds obscuring the surface of Mars have been analyzed by matching the observed dust phase function with Mie scattering calculations for size distributions of homogeneous and isotropic material. Preliminary results indicate an effective particle radius of not less than 0.2. The real component of the index of refraction is not less than 1.8 at both 268 and 305 nm; corresponding values for the imagery component are 0.02 and 0.01. These values are consistent with those found by Mead (1970) for the visible and near-visible wavelengths. The refractive index and the absorption coefficient increase rapidly with decreasing wavelength in going from the visible to the ultraviolet, indicating the presence of an ultraviolet absorption band which may shield organisms from ultraviolet irradiation.

  15. Fluoride coatings for vacuum ultraviolet reflection filters.

    PubMed

    Guo, Chun; Kong, Mingdong; Lin, Dawei; Li, Bincheng

    2015-12-10

    LaF3/MgF2 reflection filters with a high spectral-discrimination capacity of the atomic-oxygen lines at 130.4 and 135.6 nm, which were employed in vacuum ultraviolet imagers, were prepared by molybdenum-boat thermal evaporation. The optical properties of reflection filters were characterized by a high-precision vacuum ultraviolet spectrophotometer. The vulnerability of the filter's microstructures to environmental contamination and the recovery of the optical properties of the stored filter samples with ultraviolet ozone cleaning were experimentally demonstrated. For reflection filters with the optimized nonquarter-wave multilayer structures, the reflectance ratios R135.6 nm/R130.4 nm of 92.7 and 20.6 were achieved for 7° and 45° angles of incidence, respectively. On the contrary, R135.6 nm/R130.4 nm ratio of 12.4 was obtained for a reflection filter with a standard π-stack multilayer structure with H/L=1/4 at 7° AOI.

  16. A far-ultraviolet contamination-irradiation facility for in situ reflectance measurements

    NASA Astrophysics Data System (ADS)

    Meier, Steven R.; Tveekrem, June L.; Keski-Kuha, Ritva A. M.

    1998-10-01

    In this article, a contamination-irradiation facility designed to measure contamination effects on far-ultraviolet optical surfaces is described. An innovative feature of the facility is the capability of depositing a contaminant, photopolymerizing the contaminant with far-ultraviolet light, and measuring the reflectance of the contaminated sample, all in situ. In addition to describing the facility, we present far-ultraviolet reflectance measurements for a contaminated mirror.

  17. Development of ultraviolet lasers

    NASA Technical Reports Server (NTRS)

    Walters, G. K.

    1974-01-01

    The pulsed electron accelerator selected for use in the development of ultraviolet laser capability suitable for use in photoexcitation and photoionization studies of the upper atmosphere is reported. Performance figures, installation specifications, and total cost of the equipment are briefly shown, and plans for further studies are outlined.

  18. Ultraviolet Patterns on Rear of Flowers: Basis of Disparity of Buds and Blossoms

    PubMed Central

    Eisner, Thomas; Eisner, Maria; Aneshansley, D.

    1973-01-01

    Flowers of Jasminium primulinum and Hypericum spp. have ultraviolet patterns on the reverse surface of the corolla. Those areas of the surface that are exposed to the outside in the bud are ultraviolet absorbent, whereas the portions that come into view at maturity in the open blossom are ultraviolet reflectant. Buds and blossoms, as a result, appear different in color to insects sensitive to ultraviolet light. Experimental evidence indicates that the ultraviolet-absorbent quality of the outer surface of the bud is a consequence of exposure itself, attributable possibly to a “sun tanning” effect. Images PMID:16592074

  19. Interstellar extinction in the ultraviolet

    NASA Technical Reports Server (NTRS)

    Bless, R. C.; Savage, B. D.

    1972-01-01

    Interstellar extinction curves over the region 3600-1100 A for 17 stars are presented. The observations were made by the two Wisconsin spectrometers onboard the OAO-2 with spectral resolutions of 10 A and 20 A. The extinction curves generally show a pronounced maximum at 2175 plus or minus 25 A, a broad minimum in the region 1800-1350 A, and finally a rapid rise to the far ultraviolet. Large extinction variations from star to star are found, especially in the far ultraviolet; however, with only two possible exceptions in this sample, the wavelength at the maximum of the extinction bump is essentially constant. These data are combined with visual and infrared observations to display the extinction behavior over a range in wavelength of about a factor of 20.

  20. Ultraviolet Microscopy of Candida albicans

    PubMed Central

    Balish, Edward; Svihla, George

    1966-01-01

    Balish, Edward (Argonne National Laboratory, Argonne, Ill.), and George Svihla. Ultraviolet microscopy of Candida albicans. J. Bacteriol. 92:1812–1820. 1966.—Yeast and mycelial strains of Candida albicans were grown in medium supplemented with sulfur amino acids in an effort to determine factors that control the morphology and pathogenicity of the organism. Ultraviolet microscopy revealed a greater concentration of S-adenosylmethionine in the vacuoles of the mycelial phase than in those of yeast phases. Supplementation with amino acids greatly increased the concentration of S-adenosylmethionine in the mycelial phase, and made these cells more sensitive to the lytic action of snail gut enzymes than two yeast phase strains. This indicates a difference in cell wall structure that may be related to the pathogenicity of the mycelial phase. Images PMID:5958110

  1. Far-ultraviolet imagery of the Orion Nebula

    NASA Technical Reports Server (NTRS)

    Carruthers, G. R.; Opal, C. B.

    1977-01-01

    Two electrographic cameras carried on a sounding rocket have yielded useful-resolution far-ultraviolet (1000-2000 A) imagery of the Orion Nebula. The brightness distribution in the images is consistent with a primary source which is due to scattering of starlight by dust grains, although an emission-line contribution, particularly in the fainter outer regions, is not ruled out. The results are consistent with an albedo of the dust grains that is high in the far-ultraviolet and which increases toward shorter wavelengths below 1230 A.

  2. Pluto's Far Ultraviolet Spectrum and Airglow Emissions

    NASA Astrophysics Data System (ADS)

    Steffl, A.; Schindhelm, E.; Kammer, J.; Gladstone, R.; Greathouse, T. K.; Parker, J. W.; Strobel, D. F.; Summers, M. E.; Versteeg, M. H.; Ennico Smith, K.; Hinson, D. P.; Linscott, I.; Olkin, C.; Parker, A. H.; Retherford, K. D.; Singer, K. N.; Tsang, C.; Tyler, G. L.; Weaver, H. A., Jr.; Woods, W. W.; Young, L. A.; Stern, A.

    2015-12-01

    The Alice far ultraviolet spectrograph on the New Horizons spacecraft is the second in a family of six instruments in flight on, or under development for, NASA and ESA missions. Here, we present initial results from the Alice observations of Pluto during the historic flyby. Pluto's far ultraviolet spectrum is dominated by sunlight reflected from the surface with absorption by atmospehric constituents. We tentatively identify C2H2 and C2H4 in Pluto's atmosphere. We also present evidence for weak airglow emissions.

  3. Ultraviolet Source For Testing Hydrogen-Fire Detectors

    NASA Technical Reports Server (NTRS)

    Hall, Gregory A.; Larson, William E.; Youngquist, Robert C.; Moerk, John S.; Haskell, William D.; Cox, Robert B.; Polk, Jimmy D.; Stout, Stephen J.; Strobel, James P.

    1995-01-01

    Hand-held portable unit emits ultraviolet light similar to that emitted by hydrogen burning in air. Developed for use in testing optoelectronic hydrogen-fire detectors, which respond to ultraviolet light at wavelengths from 180 to 240 nanometers. Wavelength range unique in that within it, hydrogen fires emit small but detectable amounts of radiation, light from incandescent lamps and Sun almost completely absent, and air sufficiently transmissive to enable detection of hydrogen fire from distance. Consequently, this spectral region favorable for detecting hydrogen fires while minimizing false alarms.

  4. The mirrors for the Extreme Ultraviolet Explorer

    NASA Technical Reports Server (NTRS)

    Finley, David S.; Green, James C.; Bowyer, Stuart; Malina, Roger F.

    1986-01-01

    Flight mirrors for the Extreme Ultraviolet Explorer satellite are currently under fabrication. The grazing incidence metal mirrors are Wolter-Schwarzschild Type I and II and are figured by diamond turning. Imaging performance is excellent, with the figure after polishing for the best mirror being such that the full width-half maximum is 1.0 arc seconds and the half energy width is 8 arc seconds measured at visible wavelengths. Surface finish, as determined from scattering measurements in the extreme ultraviolet, is about 20 A rms.

  5. Improving Assessment of Lifetime Solar Ultraviolet Radiation Exposure in Epidemiologic Studies: Comparison of Ultraviolet Exposure Assessment Methods in a Nationwide United States Occupational Cohort.

    PubMed

    Little, Mark P; Tatalovich, Zaria; Linet, Martha S; Fang, Michelle; Kendall, Gerald M; Kimlin, Michael G

    2018-06-13

    Solar ultraviolet radiation is the primary risk factor for skin cancers and sun-related eye disorders. Estimates of individual ambient ultraviolet irradiance derived from ground-based solar measurements and from satellite measurements have rarely been compared. Using self-reported residential history from 67,189 persons in a nationwide occupational US radiologic technologists cohort, we estimated ambient solar irradiance using data from ground-based meters and noontime satellite measurements. The mean distance-moved from city of longest residence in childhood increased from 137.6 km at ages 13-19 to 870.3 km at ages ≥65, with corresponding increases in absolute latitude-difference moved. At ages 20/40/60/80, the Pearson/Spearman correlation coefficients of ground-based and satellite-derived solar potential ultraviolet exposure, using irradiance and cumulative radiant-exposure metrics, were high (=0.87-0.92). There was also moderate correlation (Pearson/Spearman correlation coefficients=0.51-0.60) between irradiance at birth and at last-known address, for ground-based and satellite data. Satellite-based lifetime estimates of ultraviolet radiation were generally 14-15% lower than ground-based estimates, albeit with substantial uncertainties, possibly because ground-based estimates incorporate fluctuations in cloud and ozone, which are incompletely incorporated in the single noontime satellite-overpass ultraviolet value. If confirmed elsewhere, the findings suggest that ground-based estimates may improve exposure-assessment accuracy and potentially provide new insights into ultraviolet-radiation-disease relationships in epidemiologic studies. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  6. Novel Ultraviolet Light Absorbing Polymers For Optical Applications

    NASA Astrophysics Data System (ADS)

    Doddi, Namassivaya; Yamada, Akira; Dunks, Gary B.

    1988-07-01

    Ultraviolet light absorbing monomers have been developed that can be copolymerized with acrylates. The composition of the resultant stable copolymers can be adjusted to totally block the transmission of light below about 430 nm. Fabrication of lenses from the materials is accomplished by lathe cutting and injection molding procedures. These ultraviolet light absorbing materials are non-mutagenic and non-toxic and are currently being used in intraocular lenses.

  7. Ultraviolet Polariton Laser

    DTIC Science & Technology

    2015-09-17

    Ultraviolet Polariton Laser Significant progress was achieved in the epitaxy of deep UV AlN/ AlGaN Bragg mirrors and microcavity structures paving...the way to the successful fabrication of vertical cavity emitting laser structures and polariton lasers. For the first time DBRs providing sufficient...high reflectivity for polariton emission were demonstrated. Thanks to a developed strain balanced Al0.85Ga0.15N template, the critical thickness

  8. Can the circadian system of a diurnal and a nocturnal rodent entrain to ultraviolet light?

    PubMed

    Hut, R A; Scheper, A; Daan, S

    2000-01-01

    Spectral measurements of sunlight throughout the day show close correspondence between the timing of above ground activity of the European ground squirrel and the presence of ultraviolet light in the solar spectrum. However, in a standard entrainment experiment ground squirrels show no entrainment to ultraviolet light, while Syrian hamsters do entrain under the same protocol. Presented transmittance spectra for lenses, corneas, and vitreous bodies may explain the different results of the entrainment experiment. We found ultraviolet light transmittance in the colourless hamster lens (50% cut-off at 341 nm), but not in the yellow ground squirrel lens (50% cut-off around 493 nm). Ultraviolet sensitivity in the ground squirrels based upon possible fluorescence mechanisms was not evident. Possible functions of ultraviolet lens filters in diurnal mammals are discussed, and compared with nocturnal mammals and diurnal birds. Species of the latter two groups lack ultraviolet filtering properties of their lenses and their circadian system is known to respond to ultraviolet light, a feature that does not necessarily has to depend on ultraviolet photoreceptors. Although the circadian system of several species responds to ultraviolet light, we argue that the role of ultraviolet light as a natural Zeitgeber is probably limited.

  9. Onboard Photo:Astro-1 Ultraviolet Telescope in Cargo Bay

    NASA Technical Reports Server (NTRS)

    1990-01-01

    Onboard the Space Shuttle Orbiter Columbia (STS-35), the various components of the Astro-1 payload are seen backdropped against a blue and white Earth. Parts of the Hopkins Ultraviolet Telescope (HUT), the Ultraviolet Imaging Telescope (UIT), and the Wisconsin Ultraviolet Photo-Polarimetry Experiment (WUPPE) are visible on the Spacelab pallet. The Broad-Band X-Ray Telescope (BBXRT) is behind the pallet and is not visible in this scene. The smaller cylinder in the foreground is the igloo. The igloo was a pressurized container housing the Command Data Management System, that interfaced with the in-cabin controllers to control the Instrument Pointing System (IPS) and the telescopes. The Astro Observatory was designed to explore the universe by observing and measuring the ultraviolet radiation from celestial objects. Astronomical targets of observation selected for Astro missions included planets, stars, star clusters, galaxies, clusters of galaxies, quasars, remnants of exploded stars (supernovae), clouds of gas and dust (nebulae), and the interstellar medium. Managed by the Marshall Space Flight Center, the Astro-1 was launched aboard the Space Shuttle Orbiter Columbia (STS-35) on December 2, 1990.

  10. Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole

    NASA Astrophysics Data System (ADS)

    Li, Shaohong L.; Truhlar, Donald G.

    2017-02-01

    Analytic potential energy surfaces (PESs) and state couplings of the ground and two lowest singlet excited states of thioanisole (C6H5SCH3) are constructed in a diabatic representation based on electronic structure calculations including dynamic correlation. They cover all 42 internal degrees of freedom and a wide range of geometries including the Franck-Condon region and the reaction valley along the breaking S-CH3 bond with the full ranges of the torsion angles. The parameters in the PESs and couplings are fitted to the results of smooth diabatic electronic structure calculations including dynamic electron correlation by the extended multi-configurational quasi-degenerate perturbation theory method for the adiabatic state energies followed by diabatization by the fourfold way. The fit is accomplished by the anchor points reactive potential method with two reactive coordinates and 40 nonreactive degrees of freedom, where the anchor-point force fields are obtained with a locally modified version of the QuickFF package. The PESs and couplings are suitable for study of the topography of the trilayer potential energy landscape and for electronically nonadiabatic molecular dynamics simulations of the photodissociation of the S-CH3 bond.

  11. Temperature dependence of the photodissociation of CO2 from high vibrational levels: 205-230 nm imaging studies of CO(X1Σ+) and O(3P, 1D) products

    NASA Astrophysics Data System (ADS)

    Sutradhar, S.; Samanta, B. R.; Samanta, A. K.; Reisler, H.

    2017-07-01

    The 205-230 nm photodissociation of vibrationally excited CO2 at temperatures up to 1800 K was studied using Resonance Enhanced Multiphoton Ionization (REMPI) and time-sliced Velocity Map Imaging (VMI). CO2 molecules seeded in He were heated in an SiC tube attached to a pulsed valve and supersonically expanded to create a molecular beam of rotationally cooled but vibrationally hot CO2. Photodissociation was observed from vibrationally excited CO2 with internal energies up to about 20 000 cm-1, and CO(X1Σ+), O(3P), and O(1D) products were detected by REMPI. The large enhancement in the absorption cross section with increasing CO2 vibrational excitation made this investigation feasible. The internal energies of heated CO2 molecules that absorbed 230 nm radiation were estimated from the kinetic energy release (KER) distributions of CO(X1Σ+) products in v″ = 0. At 230 nm, CO2 needs to have at least 4000 cm-1 of rovibrational energy to absorb the UV radiation and produce CO(X1Σ+) + O(3P). CO2 internal energies in excess of 16 000 cm-1 were confirmed by observing O(1D) products. It is likely that initial absorption from levels with high bending excitation accesses both the A1B2 and B1A2 states, explaining the nearly isotropic angular distributions of the products. CO(X1Σ+) product internal energies were estimated from REMPI spectroscopy, and the KER distributions of the CO(X1Σ+), O(3P), and O(1D) products were obtained by VMI. The CO product internal energy distributions change with increasing CO2 temperature, suggesting that more than one dynamical pathway is involved when the internal energy of CO2 (and the corresponding available energy) increases. The KER distributions of O(1D) and O(3P) show broad internal energy distributions in the CO(X1Σ+) cofragment, extending up to the maximum allowed by energy but peaking at low KER values. Although not all the observations can be explained at this time, with the aid of available theoretical studies of CO2 VUV

  12. An upper limit on ultraviolet shot noise from Cygnus X-1

    NASA Technical Reports Server (NTRS)

    Duthie, J. G.; Mcmillan, R. S.

    1979-01-01

    Rapid photometry of Cygnus X-1 through an ultraviolet filter centered on 0.35 micron has been obtained at 100-ms sampling intervals. The autocorrelation function of these data has been examined for shot noise analogous to the behavior of the X-ray light curve. The ultraviolet data are entirely consistent with white noise. Considering randomly occurring ultraviolet shots with the same duration (0.5 s) and average rate (1 per sec) as the X-ray shots, a 3-sigma upper limit on the ratio of optical to X-ray energies per shot is estimated to be 0.13, before the ultraviolet light is attenuated by interstellar dust. This limit is then generalized for shots of arbitrary duration and rate.

  13. Direct evidence for the ring opening of monosaccharide anions in the gas phase: photodissociation of aldohexoses and aldohexoses derived from disaccharides using variable-wavelength infrared irradiation in the carbonyl stretch region.

    PubMed

    Brown, Darin J; Stefan, Sarah E; Berden, Giel; Steill, Jeffrey D; Oomens, Jos; Eyler, John R; Bendiak, Brad

    2011-11-08

    All eight D-aldohexoses and aldohexoses derived from the non-reducing end of disaccharides were investigated by variable-wavelength infrared multiple-photon dissociation (IRMPD) as anions in the negative-ion mode. Spectroscopic evidence supports the existence of a relatively abundant open-chain configuration of the anions in the gas phase, based on the observation of a significant carbonyl absorption band near 1710 cm(-1). The abundance of the open-chain configuration of the aldohexose anions was approximately 1000-fold or greater than that of the neutral sugars in aqueous solution. This provides an explanation as to why it has not been possible to discriminate the anomeric configuration of aldohexose anions in the gas phase when derived from the non-reducing sugar of a disaccharide. Evidence from photodissociation spectra also indicates that the different aldohexoses yield product ions with maximal abundances at different wavelengths, and that the carbonyl stretch region is useful for differentiation of sugar stereochemistries. Quantum-chemical calculations indicate relatively low energy barriers to intramolecular proton transfer between hydroxyl groups and adjacent alkoxy sites located on open-chain sugar anions, suggesting that an ensemble of alkoxy charge locations contributes to their observed photodissociation spectra. Ring opening of monosaccharide anions and interconversion among configurations is an inherent property of the ions themselves and occurs in vacuo independent of solvent participation. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Time-Dependent Photodissociation Regions

    NASA Technical Reports Server (NTRS)

    Hollenbach, David; Natta, Antonella

    1995-01-01

    We present theoretical models of the time-dependent thermal and chemical structure of molecular gas suddenly exposed to far-ultraviolet (FUV) (6 eV less than hv less than 13.6 eV) radiation fields and the consequent time- dependent infrared emission of the gas. We focus on the response of molecular hydrogen for cloud densities ranging from n = 10(exp 3) to 10(exp 6)/cu cm and FUV fluxes G(sub 0) = 10(exp 3)-10(exp 6) times the local FUV interstellar flux. For G(sub 0)/n greater than 10(exp -2) cu cm, the emergent H(sub 2) vibrational line intensities are initially larger than the final equilibrium values. The H(sub 2) lines are excited by FUV fluorescence and by collisional excitation in warm gas. Most of the H(sub 2) intensity is generated at a characteristic hydrogen column density of N approximately 10(exp 21)/sq cm, which corresponds to an FUV optical depth of unity caused by dust opacity. The time dependence of the H(sub 2) intensities arises because the initial abundances of H(sub 2) at these depths is much higher than the equilibrium values, so that H(sub 2) initially competes more effectively with dust in absorbing FUV photons. Considerable column densities of warm (T approximately 1000) K H(sub 2) gas can be produced by the FUV pumping of H(sub 2) vibrational levels followed by collisional de-excitation, which transfers the energy to heat. In dense (n greater than or approximately 10(exp 5)/cu cm) gas exposed to high (G(sub 0) greater than or approximately 10(exp 4)) fluxes, this warm gas produces a 2-1 S(1)/1-0 S(l) H(sub 2) line ratio of approximately 0.1, which mimics the ratio found in shocked gas. In lower density regions, the FUV pumping produces a pure-fluorescent ratio of approximately 0.5. We also present calculations of the time dependence of the atomic hydrogen column densities and of the intensities of 0 I 6300 A, S II 6730 A, Fe II 1.64 microns, and rotational OH and H20 emission. Potential applications include star-forming regions, clouds

  15. Microwave-driven ultraviolet light sources

    DOEpatents

    Manos, Dennis M.; Diggs, Jessie; Ametepe, Joseph D.

    2002-01-29

    A microwave-driven ultraviolet (UV) light source is provided. The light source comprises an over-moded microwave cavity having at least one discharge bulb disposed within the microwave cavity. At least one magnetron probe is coupled directly to the microwave cavity.

  16. The Onset of H + Ketene Products from Vinoxy Radicals Prepared by Photodissociation of Chloroacetaldehyde at 157 nm

    DOE PAGES

    Lam, Chow-Shing; Adams, Jonathan D.; Butler, Laurie J.

    2016-04-19

    We investigate the unimolecular dissociation of the vinoxy radical (CH 2CHO) prepared with high internal energy imparted from the photodissociation of chloroacetaldehyde (CH 2ClCHO) at 157 nm. Using a velocity map imaging apparatus, we measured the speed distribution of the recoiling chlorine atoms, Cl( 2P 3/2) and Cl( 2P 1/2), and derived from this the resulting distribution of kinetic energy, P(ET), imparted to the Cl + vinoxy fragments upon dissociation. Using conservation of energy, the distribution of kinetic energy was used to determine the total internal energy distribution in the radical. The P(ET) derived for the C–Cl bond fission presentedmore » in this work suggests the vinoxy radicals are mostly formed in the à state. We also took ion images at m/z = 42 and m/z = 15 to characterize the branching between the unimolecular dissociation channels of the vinoxy radical to H + ketene and methyl + CO products. Our results show a marked change in the branching ratio between the two channels from the previous study on the photodissociation of chloroacetaldehyde at 193 nm by Miller et al. (J. Chem. Phys., 2004, 121, 1830) in that the production of ketene is now favored over the production of methyl. To help analyze the data, we developed a model for the branching between the two channels that takes into account how the change in rotational energy en route to the products affects the vibrational energy available to surmount the barriers to the channels. The model predicts the portion of the C–Cl bond fission P(ET) that produces dissociative vinoxy radicals, then predicts the branching ratio between the H + ketene and CH 3 + CO product channels at each ET. The model uses Rice–Ramsperger–Kassel–Marcus rate constants at the correct sums and densities of vibrational states while accounting for angular momentum conservation. We find that the predicted portion of the P(ET) that produces H + ketene products best fits the experimental portion (that we derive

  17. Optimum spectral resolution for computing atmospheric heating and photodissociation rates

    NASA Astrophysics Data System (ADS)

    Stamnes, K.; Tsay, S.-C.

    1990-06-01

    Rapid, reliable and accurate computations of atmospheric heating rates are needed in climate models aimed at predicting the impact of greenhouse gases on the surface temperature. Photolysis rates play a major role in photochemical models used to assess potential changes in atmospheric ozone abundance due to man's release of chlorofluorocarbons. Both rates depend directly on the amount of solar radiation available at any level in the atmosphere. We present a very efficient method of computing these rates in which integration over the solar spectrum is reduced to a minimum number of monochromatic (or pseudogray) problems by appealing to the continuum features of the ozone absorption cross-sections. To explore the resolutions needed to obtain adequate results we have divided the spectral range between 175 and 700 nm into four regions. Within each of these regions we may vary the resolution as we wish. Accurate results are obtained for very coarse spectral resolution provided all cross-sections are averaged by weighting them with the solar flux across any bin. By using this procedure we find that heating rate errors are less than 20% for all altitudes when only four spectral bands across the entire wavelength region from 175 to 700 nm are used to compute the heating rate profile. Similarly, we find that the error in the photodissociation of ozone is less than a few percent when 10 nm resolution is used in the Hartley and Huggins bands (below 330 nm), while an average over the entire wavelength region from 400 to 700 nm yields similar accuracy for the Chappuis band. For integrated u.v. dose estimates a resolution slightly better than 10 nm is required in the u.v.B region (290-315 nm) to yield an accuracy better than 10%, but we may treat the u.v.A region (315-400 nm) as a single band and yet have an accuracy better than 2%.

  18. The Production of Titan's Ultraviolet Nitrogen Airglow

    NASA Astrophysics Data System (ADS)

    Stevens, Michael H.; Gustin, J.; Ajello, J. M.; Evans, J. S.; Meier, R. R.; Stewart, A. I. F.; Esposito, L. W.; McClintock, W. E.; Stephan, A. W.

    2010-10-01

    The Cassini Ultraviolet Imaging Spectrograph (UVIS) observed Titan's dayside limb on 22 June, 2009, obtaining high quality extreme ultraviolet (EUV) and far ultraviolet (FUV) spectra from a distance of only 60,000 km (23 Titan radii). The observations reveal the same EUV and FUV emissions arising from photoelectron excitation and photofragmentation of molecular nitrogen (N2) on Earth but with the altitude of peak emission much higher on Titan near 1000 km altitude. In the EUV, emission bands from the photoelectron excited N2 Carroll-Yoshino c4'-X system and N I and N II multiplets arising from photofragmentation of N2 dominate, with no detectable c4'(0,0) emission near 958 Å, contrary to many interpretations of the lower resolution Voyager 1 Ultraviolet Spectrometer data. The FUV is dominated by emission bands from the N2 Lyman-Birge-Hopfield a-X system and additional N I multiplets. We also identify several N2 Vegard-Kaplan A-X bands between 1500-1900 Å, two of which are located near 1561 and 1657 Å where C I multiplets were previously identified from a separate UVIS disk observation. We compare these limb emissions to predictions from a terrestrial airglow model adapted to Titan that uses a solar spectrum appropriate for these June, 2009 observations. Volume production rates and limb radiances are calculated, including extinction by methane and allowance for multiple scattering within the readily excited c4'(0,v') system, and compared to UVIS observations. We find that for these airglow data only emissions arising from processes involving N2 are present.

  19. Light-induced pyroelectric effect as an effective approach for ultrafast ultraviolet nanosensing

    NASA Astrophysics Data System (ADS)

    Wang, Zhaona; Yu, Ruomeng; Pan, Caofeng; Li, Zhaoling; Yang, Jin; Yi, Fang; Wang, Zhong Lin

    2015-09-01

    Zinc oxide is potentially a useful material for ultraviolet detectors; however, a relatively long response time hinders practical implementation. Here by designing and fabricating a self-powered ZnO/perovskite-heterostructured ultraviolet photodetector, the pyroelectric effect, induced in wurtzite ZnO nanowires on ultraviolet illumination, has been utilized as an effective approach for high-performance photon sensing. The response time is improved from 5.4 s to 53 μs at the rising edge, and 8.9 s to 63 μs at the falling edge, with an enhancement of five orders in magnitudes. The specific detectivity and the responsivity are both enhanced by 322%. This work provides a novel design to achieve ultrafast ultraviolet sensing at room temperature via light-self-induced pyroelectric effect. The newly designed ultrafast self-powered ultraviolet nanosensors may find promising applications in ultrafast optics, nonlinear optics, optothermal detections, computational memories and biocompatible optoelectronic probes.

  20. Selected highlights from the Extreme Ultraviolet Explorer

    NASA Technical Reports Server (NTRS)

    Bowyer, S.; Malina, R. F.

    1995-01-01

    We present a few scientific highlights from the Extreme Ultraviolet Explorer (EUVE) all-sky and deep surveys, from the EUVE Righ Angle Program, and from the EUVE Guest Observer Program. The First EUVE Source Catalog includes 410 extreme ultraviolet (EUV) sources detected in the initial processing of the EUVE all-sky data. A program of optical identification indicates that counterparts include cool star coronae, flare stars, hot white dwarfs, central stars of planetary nebulae, B star photospheres and winds, an X-ray binary, extragalactic objects (active galactic nuclei, BL Lacertae), solar system objects (Moon, Mars, Io,), supernova remnants, and two novae.

  1. Ultraviolet, visible, and infrared rays

    NASA Technical Reports Server (NTRS)

    Taylor, J. H.; Letavet, A. A.

    1975-01-01

    Sources of infrared, visible and ultraviolet radiation are discussed, and important associated biological and psychophysiological effects are described. The problem of protection from excessively high or low levels of radiant energy in these spectral regions is considered and optimal levels are suggested.

  2. DDT: participation in ultraviolet-detectable, charge-transfer complexation.

    PubMed

    Wilson, W E; Fishbein, L; Clements, S T

    1971-01-15

    The chlorophenyl groups of DDT and several of its metabolites are capable of participating in a charge-transfer interaction with tetracyanoethylene detectable in the ultraviolet region of the spectrum. In addition, during a change of state DDT undergoes ultraviolet spectral alterations that closely resemble those previously claimed to support the hypothesis suggesting charge-transfer interaction between this pesticide and a component of insect nerve tissue. The pesticide DDT possesses structural characteristics that would permit it to participate in several types of molecular association.

  3. Toward quantifying the abuse liability of ultraviolet tanning: A behavioral economic approach to tanning addiction.

    PubMed

    Reed, Derek D; Kaplan, Brent A; Becirevic, Amel; Roma, Peter G; Hursh, Steven R

    2016-07-01

    Many adults engage in ultraviolet indoor tanning despite evidence of its association with skin cancer. The constellation of behaviors associated with ultraviolet indoor tanning is analogous to that in other behavioral addictions. Despite a growing literature on ultraviolet indoor tanning as an addiction, there remains no consensus on how to identify ultraviolet indoor tanning addictive tendencies. The purpose of the present study was to translate a behavioral economic task more commonly used in substance abuse to quantify the "abuse liability" of ultraviolet indoor tanning, establish construct validity, and determine convergent validity with the most commonly used diagnostic tools for ultraviolet indoor tanning addiction (i.e., mCAGE and mDSM-IV-TR). We conducted a between-groups study using a novel hypothetical Tanning Purchase Task to quantify intensity and elasticity of ultraviolet indoor tanning demand and permit statistical comparisons with the mCAGE and mDSM-IV-TR. Results suggest that behavioral economic demand is related to ultraviolet indoor tanning addiction status and adequately discriminates between potential addicted individuals from nonaddicted individuals. Moreover, we provide evidence that the Tanning Purchase Task renders behavioral economic indicators that are relevant to public health research. The present findings are limited to two ultraviolet indoor tanning addiction tools and a relatively small sample of high-risk ultraviolet indoor tanning users; however, these pilot data demonstrate the potential for behavioral economic assessment tools as diagnostic and research aids in ultraviolet indoor tanning addiction studies. © 2016 Society for the Experimental Analysis of Behavior.

  4. Apollo-16 far-ultraviolet spectra in the Large Magellanic Cloud

    NASA Technical Reports Server (NTRS)

    Carruthers, G. R.; Page, T.

    1977-01-01

    Spectra in the wavelength ranges from 900 to 1600 A and 1050 to 1600 A of some OB associations in the Large Magellanic Cloud were obtained from the lunar surface by the Apollo-16 far-ultraviolet camera/spectrograph on April 22, 1972. The observed spectral distributions appear consistent with a stellar model having an effective temperature of 30,000 K, reddened by E(B-V) = 0.3, and characterized by the average far-ultraviolet extinction curve of Bless and Savage (1972). However, the absolute intensity of the far-ultraviolet spectrum of the associations NGC 2050 and 2055 seems somewhat too bright in comparison with ground-based photometry.

  5. Influence of light-induced conical intersection on the photodissociation dynamics of D2(+) starting from individual vibrational levels.

    PubMed

    Halász, Gábor J; Csehi, András; Vibók, Ágnes; Cederbaum, Lorenz S

    2014-12-26

    Previous works have shown that dressing of diatomic molecules by standing or by running laser waves gives rise to the appearance of so-called light-induced conical intersections (LICIs). Because of the strong nonadiabatic couplings, the existence of such LICIs may significantly change the dynamical properties of a molecular system. In our former paper (J. Phys. Chem. A 2013, 117, 8528), the photodissociation dynamics of the D(2)(+) molecule were studied in the LICI framework starting the initial vibrational nuclear wave packet from the superposition of all the vibrational states initially produced by ionizing D(2). The present work complements our previous investigation by letting the initial nuclear wave packets start from different individual vibrational levels of D(2)(+), in particular, above the energy of the LICI. The kinetic energy release spectra, the total dissociation probabilities, and the angular distributions of the photofragments are calculated and discussed. An interesting phenomenon has been found in the spectra of the photofragments. Applying the light-induced adiabatic picture supported by LICI, explanations are given for the unexpected structure of the spectra.

  6. Far-ultraviolet stellar photometry: A field in Orion

    NASA Astrophysics Data System (ADS)

    Schmidt, Edward G.; Carruthers, George R.

    1993-12-01

    Far-ultraviolet photometry for 625 objects in Orion is presented. These data were extracted from electrographic camera images obtained during sounding rocket flights in 1975 and 1982. The 1975 images were centered close to the belt of Orion while the 1982 images were centered approximately 9 deg further north. One hundred and fifty stars fell in the overlapping region and were observed with both cameras. Sixty-eight percent of the objects were tentatively identified with known stars using the SIMBAD database while another 24% are blends of objects too close together to separate with our resolution. As in previous studies, the majority of the identified ultraviolet sources are early-type stars. However, there are a significant number for which no such identification was possible, and we suggest that these are interesting objects which should be further investigated. Seven stars were found which were bright in the ultraviolet but faint in the visible. We suggest that some of these are nearby white dwarfs.

  7. The interaction of ultraviolet light with Arctic sea ice during SHEBA

    NASA Astrophysics Data System (ADS)

    Perovich, Donald K.

    The reflection, absorption and transmission of ultraviolet light by a sea-ice cover strongly impacts primary productivity, higher trophic components of the food web, and humans. Measurements of the incident irradiance at 305, 320, 340 and 380 nm and of the photosynthetically active radiation were made from April through September 1998 as part of the SHEBA (Surface Heat Budget of the Arctic Ocean program) field experiment in the Arctic Ocean. In addition, observations of snow depth and ice thickness were made at more than 100 sites encompassing a comprehensive range of conditions. The thickness observations were combined with a radiative transfer model to compute a time series of the ultraviolet light transmitted by the ice cover from April through September. Peak values of incident ultraviolet irradiance occurred in mid-June. Peak transmittance was later in the summer at the end of the melt season when the snow cover had completely melted, the ice had thinned and pond coverage was extensive. The fraction of the incident ultraviolet irradiance transmitted through the ice increased by several orders of magnitude as the melt season progressed. Ultraviolet transmittance was approximately a factor of ten greater for melt ponds than bare ice. Climate change has the potential to alter the amplitude and timing of the annual albedo cycle of sea ice. If the onset of melt occurs at increasingly earlier dates, ultraviolet transmittance will be significantly enhanced, with potentially deleterious biological impacts.

  8. Ultraviolet photometry from the Orbiting Astronomical Observatory. XXVIII - Ultraviolet light curves for Alpha Lupi and BW Vulpeculae

    NASA Technical Reports Server (NTRS)

    Lesh, J. R.

    1978-01-01

    Photometric data from the Wisconsin Experiment Package on OAO-2 have been used to construct light curves at three ultraviolet wavelengths for Alpha Lup and at seven wavelengths for BW Vul. Both stars are well-known variables of the Beta Cephei (Beta Canis Majoris) type. The light curves for Alpha Lup are in good agreement with the radial-velocity period. A temperature variation of 400-500 K is derived. The BW Vul light curves confirm recent ephemerides based on a secularly varying period and show a stillstand near light maximum at some wavelengths. Both stars exhibit increasing light amplitude at the shortest ultraviolet wavelengths. There is little evidence for cycle-to-cycle variations on a time scale of the order of 1 day.

  9. The effect of prescription eyewear on ocular exposure to ultraviolet radiation.

    PubMed Central

    Rosenthal, F S; Bakalian, A E; Taylor, H R

    1986-01-01

    Several studies have suggested that ultraviolet radiation in sunlight may cause cataracts and other eye disease. We evaluated the effect of prescription eyewear in attenuating ocular exposure to ultraviolet radiation (UVR) in the sunlight portions of the ultraviolet spectrum (295-350 nm). Using natural sunlight as the source, the attenuation was measured with two ultraviolet detectors, one sensitive to only UVB (295-315 nm) and one sensitive to both UVA and UVB (295-350 nm). A random sample of spectacles, spectacle lenses, and contact lenses was examined. The average transmission, as measured with either detector, was highest for soft contact lenses, followed by glass spectacle lenses, untinted hard contact lenses, and plastic spectacle lenses. Measurements performed with mannikins wearing spectacles showed that an average of 6.6 per cent of incident radiation reached the eye even when the lenses were covered with black opaque tape. The amount of exposure was increased substantially when the spectacles were moved 0.6 cm away from the forehead. The results show that the protection against ultraviolet exposure provided by prescription eyewear is highly variable and depends largely on its composition, size, and wearing position. PMID:3752323

  10. Design Considerations for a Water Treatment System Utilizing Ultra-Violet Light Emitting Diodes

    DTIC Science & Technology

    2014-03-27

    DESIGN CONSIDERATIONS FOR A WATER TREATMENT SYSTEM UTILIZING ULTRA-VIOLET LIGHT EMITTING DIODES...the United States. ii AFIT-ENV-14-M-58 DESIGN CONSIDERATIONS FOR A WATER TREATMENT SYSTEM UTILIZING ULTRA-VIOLET LIGHT EMITTING DIODES...DISTRIBUTION UNLIMITED. iii AFIT-ENV-14-M-58 DESIGN CONSIDERATIONS FOR A WATER TREATMENT SYSTEM UTILIZING ULTRA-VIOLET LIGHT EMITTING

  11. A search for far-ultraviolet emissions from the lunar atmosphere.

    PubMed

    Fastie, W G; Feldman, P D; Henry, R C; Moos, H W; Barth, C A; Thomas, G E; Donahue, T M

    1973-11-16

    An ultraviolet spectrometer aboard the Apollo 17 orbiting spacecraft attempted to measure ultraviolet emissions from the lunar atmosphere. The only emissions observed were from a transient atmosphere introduced by the lunar landing engine. The absence of atomic hydrogen implies that solar wind protons are converted to hydrogen molecules at the lunar surface.

  12. The first Extreme Ultraviolet Explorer source catalog

    NASA Technical Reports Server (NTRS)

    Bowyer, S.; Lieu, R.; Lampton, M.; Lewis, J.; Wu, X.; Drake, J. J.; Malina, R. F.

    1994-01-01

    The Extreme Ultraviolet Explorer (EUVE) has conducted an all-sky survey to locate and identify point sources of emission in four extreme ultraviolet wavelength bands centered at approximately 100, 200, 400, and 600 A. A companion deep survey of a strip along half the ecliptic plane was simultaneously conducted. In this catalog we report the sources found in these surveys using rigorously defined criteria uniformly applied to the data set. These are the first surveys to be made in the three longer wavelength bands, and a substantial number of sources were detected in these bands. We present a number of statistical diagnostics of the surveys, including their source counts, their sensitivites, and their positional error distributions. We provide a separate list of those sources reported in the EUVE Bright Source List which did not meet our criteria for inclusion in our primary list. We also provide improved count rate and position estimates for a majority of these sources based on the improved methodology used in this paper. In total, this catalog lists a total of 410 point sources, of which 372 have plausible optical ultraviolet, or X-ray identifications, which are also listed.

  13. International Ultraviolet Explorer Observatory operations

    NASA Technical Reports Server (NTRS)

    1985-01-01

    This volume contains the final report for the International Ultraviolet Explorer IUE Observatory Operations contract. The fundamental operational objective of the International Ultraviolet Explorer (IUE) program is to translate competitively selected observing programs into IUE observations, to reduce these observations into meaningful scientific data, and then to present these data to the Guest Observer in a form amenable to the pursuit of scientific research. The IUE Observatory is the key to this objective since it is the central control and support facility for all science operations functions within the IUE Project. In carrying out the operation of this facility, a number of complex functions were provided beginning with telescope scheduling and operation, proceeding to data processing, and ending with data distribution and scientific data analysis. In support of these critical-path functions, a number of other significant activities were also provided, including scientific instrument calibration, systems analysis, and software support. Routine activities have been summarized briefly whenever possible.

  14. Development of deep-ultraviolet metal vapor lasers

    NASA Astrophysics Data System (ADS)

    Sabotinov, Nikola V.

    2004-06-01

    Deep ultraviolet laser generation is of great interest in connection with both the development of new industrial technologies and applications in medicine, biology, chemistry, etc. The development of metal vapor UV lasers oscillating in the pulsed mode with high pulse repetition frequencies and producing high average output powers is of particular interest for microprocessing of polymers, photolithography and fluorescence applications. At present, metal vapor lasers generate deep-UV radiation on the base of two methods. The first method is non-linear conversion of powerful laser generation from the visible region into the deep ultraviolet region. The second method is direct UV laser action on ion and atomic transitions of different metals.

  15. Photoluminescence emission spectra of Makrofol® DE 1-1 upon irradiation with ultraviolet radiation

    NASA Astrophysics Data System (ADS)

    El Ghazaly, M.; Aydarous, Abdulkadir

    Photoluminescence (PL) emission spectra of Makrofol® DE 1-1 (bisphenol-A based polycarbonate) upon irradiation with ultraviolet radiation of different wavelengths were investigated. The absorption-and attenuation coefficient measurements revealed that the Makrofol® DE 1-1 is characterized by high absorbance in the energy range 6.53-4.43 eV but for a lower energy than 4.43 eV, it is approximately transparent. Makrofol® DE 1-1 samples were irradiated with ultraviolet radiation of wavelength in the range from 250 (4.28 eV) to 400 (3.10 eV) nm in step of 10 nm and the corresponding photoluminescence (PL) emission spectra were measured with a spectrofluorometer. It is found that the integrated counts and the peak height of the photoluminescence emission (PL) bands are strongly correlated with the ultraviolet radiation wavelength. They are increased at the ultraviolet radiation wavelength 280 nm and have maximum at 290 nm, thereafter they decrease and diminish at 360 nm of ultraviolet wavelength. The position of the PL emission band peak was red shifted starting from 300 nm, which increased with the increase the ultraviolet radiation wavelength. The PL bandwidth increases linearly with the increase of the ultraviolet radiation wavelength. When Makrofol® DE 1-1 is irradiated with ultraviolet radiation of short wavelength (UVC), the photoluminescence emission spectra peaks also occur in the UVC but of a relatively longer wavelength. The current new findings should be considered carefully when using Makrofol® DE 1-1 in medical applications related to ultraviolet radiation.

  16. Interband Tunneling for Hole Injection in III-Nitride Ultraviolet Emitters

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, Yuewei; Krishnamoorthy, Sriram; Johnson, Jared M.

    Low p-type conductivity and high contact resistance remain a critical problem in wide band gap AlGaN-based ultraviolet light emitters due to the high acceptor ionization energy. In this work, interband tunneling is demonstrated for non-equilibrium injection of holes through the use of ultra-thin polarization-engineered layers that enhance tunneling probability by several orders of magnitude over a PN homojunction. Al 0.3Ga 0.7N interband tunnel junctions with a lowresistance of 5.6 × 10 -4 Ω cm 2 were obtained and integrated on ultraviolet light emitting diodes.Tunnel injection of holes was used to realize GaN-free ultraviolet light emitters with bottom and top n-typemore » Al 0.3Ga 0.7N contacts. At an emission wavelength of 327 nm, stable output power of 6 W/cm 2 at a current density of 120 A/cm 2 with a forward voltage of 5.9 V was achieved. Our demonstration of efficient interband tunneling could enable device designs for higher efficiency ultraviolet emitters.« less

  17. The Physics and Diagnostic Potential of Ultraviolet Spectropolarimetry

    NASA Astrophysics Data System (ADS)

    Trujillo Bueno, Javier; Landi Degl'Innocenti, Egidio; Belluzzi, Luca

    2017-09-01

    The empirical investigation of the magnetic field in the outer solar atmosphere is a very important challenge in astrophysics. To this end, we need to identify, measure and interpret observable quantities sensitive to the magnetism of the upper chromosphere, transition region and corona. This paper provides an overview of the physics and diagnostic potential of spectropolarimetry in permitted spectral lines of the ultraviolet solar spectrum, such as the Mg ii h and k lines around 2800 Å, the hydrogen Lyman-α line at 1216 Å, and the Lyman-α line of He ii at 304 Å. The outer solar atmosphere is an optically pumped vapor and the linear polarization of such spectral lines is dominated by the atomic level polarization produced by the absorption and scattering of anisotropic radiation. Its modification by the action of the Hanle and Zeeman effects in the inhomogeneous and dynamic solar atmosphere needs to be carefully understood because it encodes the magnetic field information. The circular polarization induced by the Zeeman effect in some ultraviolet lines (e.g., Mg ii h & k) is also of diagnostic interest, especially for probing the outer solar atmosphere in plages and more active regions. The few (pioneering) observational attempts carried out so far to measure the ultraviolet spectral line polarization produced by optically pumped atoms in the upper chromosphere, transition region and corona are also discussed. We emphasize that ultraviolet spectropolarimetry is a key gateway to the outer atmosphere of the Sun and of other stars.

  18. Directional properties in photodissociation: a probe for the symmetry and geometry of excited states of dimethylnitrosamine and tert-butyl nitrite

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lavi, R.; Schwartz-Lavi, I.B.; Rosenwaks, S.

    1987-10-08

    The rotational alignment, ..lambda..-doubling, and spin-orbit populations of the NO fragment following the photodissociation of (CH/sub 3/)/sub 2/NNO and (CH/sub 3/)/sub 3/CONO in different absorption bands are determined. The results for the S/sub 1/(n..pi..*) withdraws S/sub 0/ and S/sub 2/(..pi pi..*) withdraws S/sub 0/ transitions in both molecules indicate planarity of the fragmentation processes and an A'' symmetry of the S/sub 1/ state. For the S/sub 2/(..pi pi..*) withdraws S/sub 0/ transition in (CH/sub 3/)/sub 2/NNO the results imply an A' symmetry of the S/sub 2/ state. The values obtained for the alignment are indicative of the difference between themore » directions of the transition dipole moment for the S/sub 1/(n..pi..*) withdraws S/sub 0/ and the S/sub 2/(..pi pi..*) withdraws S/sub 0/ transitions.« less

  19. IUE's treasure-chest of the ultraviolet Universe

    NASA Astrophysics Data System (ADS)

    1997-11-01

    IUE was the most long-lived and (by a wide margin) the most productive satellite so far, in the history of space astronomy. After going into orbit on 26 January 1978, as a NASA-ESA-UK project, IUE was meant to operate for three years. More than eighteen years later, IUE still worked 24 hours a day, harvesting new knowledge for astronomers. The last observations were made from ESA's ground station at Villafranca, Spain, on 26 September 1996, and IUE was switched off four days later. Since then, team members at Villafranca and at NASAs Goddard Space Flight Center have used modern data-processing and information technology to recycle 100,000 ultraviolet spectra of comets, planets, stars, galaxies and quasars, acquired by IUE during its 18.5 years of operations. As a result, the IUE Final Archive is already available on-line via the Internet to hundreds of users who have registered to work with the data. The last few items (about 2 per cent of the total) will be added before the end of November. Also to be presented at the Sevilla conference is ESA's system called INES ("IUE Newly Extracted Spectra") which offers access, selection and distribution of data products, in a thoroughly user-friendly fashion. The IUE Final Archive is the third massive compendium made available to the worlds astronomers by ESA in 1997. The Hipparcos and Tycho Catalogues, released earlier in the year, give the positions of stars with unprecedented accuracy, thanks to ESA's Hipparcos satellite. "Space astronomy has set the example in providing a high standard of data quality and making the data accessible to the scientific community through archives", says Roger Bonnet, ESA's Scientific Director. "Now, ground-based observatories are following suit. The data legacy of IUE will be distributed to he community so that research on IUE data can continue long after the end of IUE's lifetime in space". Wonders of ultraviolet spectroscopy IUE analysed ultraviolet light, in a wavelength range from 1150

  20. Ultraviolet photorefractive effect in Mg-doped near-stoichiometric LiNbO 3

    NASA Astrophysics Data System (ADS)

    Zhu, Dengsong; Xu, Jingjun; Qiao, Haijun; Shi, Yanli; Gao, Feng; Li, Wei; Fu, Bo; Zhang, Guaquan; Zheng, Ke

    2006-10-01

    The ultraviolet photorefractive effect of Mg-doped near-stoichiometric LiNbO3 crystals prepared by vapor transport equilibration (VTE) technique was studied at 351 nm. It was found in the near-stoichiometric LiNbO3 crystals that the ultraviolet photorefractive effect could be enhanced greatly with the increase of Mg concentration. Based on the activation energy of dark decay of the photorefractive grating, possible centers responsible for the ultraviolet photorefractive effect were also discussed.

  1. MAHLI Calibration Target in Ultraviolet Light

    NASA Image and Video Library

    2012-02-07

    During pre-flight testing in March 2011, the Mars Hand Lens Imager MAHLI camera on NASA Mars rover Curiosity took this image of the MAHLI calibration target under illumination from MAHLI two ultraviolet LEDs light emitting diodes.

  2. Measurements of HO2 chemical kinetics with a new detection method

    NASA Technical Reports Server (NTRS)

    Lee, L. C.; Suto, M.

    1986-01-01

    Research for the period from December 1, 1985 to May 31, 1986 is discussed, i.e., the reaction rate constant of HO2+O3 has been measured with a discharge-flow-tube apparatus. The HO2 radical was detected by the OH(A-X) photofragment emission produced from photodissociative excitation of HO2 at 147 nm. In the meantime, the optical emissions produced by the vacuum ultraviolet excitation of chemical species in the flow tube were investigated and used to examine the possibility for their interference with the HO2 detection. The research results are summarized below.

  3. Gas-phase conformation-specific photofragmentation of proline-containing peptide ions.

    PubMed

    Kim, Tae-Young; Valentine, Stephen J; Clemmer, David E; Reilly, James P

    2010-08-01

    Singly-protonated proline-containing peptides with N-terminal arginine are photodissociated with vacuum ultraviolet (VUV) light in an ESI linear ion trap/orthogonal-TOF (LIT/o-TOF). When proline is the nth residue from the N-terminus, unusual b(n) + 2 and a(n) + 2 ions are observed. Their formation is explained by homolytic cleavage of the C(alpha)-C bond in conjunction with a rearrangement of electrons and an amide hydrogen. The latter is facilitated by a proline-stabilized gas-phase peptide conformation. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

  4. Ultraviolet spectrometer experiment for the Voyager mission

    NASA Technical Reports Server (NTRS)

    Broadfoot, A. L.; Sandel, B. R.; Shemansky, D. E.; Atreya, S. K.; Donahue, T. M.; Moos, H. W.; Bertaux, J. L.; Blamont, J. E.; Ajello, J. M.; Strobel, D. F.

    1977-01-01

    An objective grating spectrometer covering the wavelength range of 500 to 1700 A with a 10-A resolution is employed for the Voyager ultraviolet spectrometer experiment. In determining the composition and structure of the atmospheres of Saturn, Jupiter and several satellites, the ultraviolet spectrometer will rely on airglow mode observations to measure radiation from the atmospheres due to resonant scattering of solar flux, and the occultation mode for assessments of the atmospheric extinction of solar or stellar radiation as the spacecraft enters shadow zones. Since it is capable of prolonged stellar observations in the 500 to 1000 A wavelength range, the spectrometer is expected to make important contributions to exploratory studies of UV sources.

  5. GALEX 1st Light Far Ultraviolet

    NASA Technical Reports Server (NTRS)

    2003-01-01

    This image was taken May 21 and 22 by NASA's Galaxy Evolution Explorer. The image was made from data gathered by the far ultraviolet channel of the spacecraft camera during the mission's 'first light' milestone. It shows about 400 celestial objects, appearing in blue, detected over a 3-minute, 20-second period in the constellation Hercules.

    The Galaxy Evolution Explorer's first light images are dedicated to the crew of the Space Shuttle Columbia. The Hercules region was directly above Columbia when it made its last contact with NASA Mission Control on February 1, over the skies of Texas.

    The Galaxy Evolution Explorer launched on April 28 on a mission to map the celestial sky in the ultraviolet and determine the history of star formation in the universe over the last 10 billion years.

  6. Balloon Borne Ultraviolet Spectrometer.

    DTIC Science & Technology

    1978-12-28

    n.c.aaary ond lden lfy by block numb.r) ultraviolet ground support equipment (GSE) spectrometers flight electronics instrumentation balloons \\ solar ...Assembly 4 Fig. 3 Solar Balloon Experiment Ass ’y 7 Fig. 4 Mechanical Interface , UV Spectrometer 8 Fig . 5 Spectrometer Body Assemb ly 10 Fig. 6...Diagram, GSE )bnitor 48 Selector and Battery Charger Fig. 25 Schematic Diagram, GSE Serial to 49 Parallel Data Converter Fig. 26 Schematic Diagram

  7. Ultraviolet Imaging Telescope (UIT) observations of galaxies

    NASA Technical Reports Server (NTRS)

    Neff, S. G.

    1993-01-01

    Ultraviolet images of several galaxies were obtained during the ASTRO-1 shuttle mission in December, 1990. The images have a FWHM angular resolution of approximately 3 arcsecond and are of circular fields approximately 40 arcminutes in diameter. Most galaxies were observed in at least two and sometimes as many as four broad bands. A very few fields were observed with narrower band filters. The most basic result of these observations is that most systems look dramatically different in the UV from their well-known optical appearances. Preliminary results of these studies will be presented. Information will be available on fields observed by the UTI during the ASTRO 1 mission; when that data becomes public it can be obtained from the NSSDC. The ASTRO observatory is expected to fly again in 1994 with approximately half of the observing time from that mission devoted to guest observers. The Ultraviolet Imaging telescope is extremely well suited for galaxy studies, and the UIT term is interested in encouraging a wide range of scientific studies by guest observers. Ultraviolet Imaging telescope is extremely well suited for galaxy studies, and the UIT team is interested in encouraging a wide range of scientific studies by guest observers.

  8. Photoprotection of human skin beyond ultraviolet radiation.

    PubMed

    Grether-Beck, Susanne; Marini, Alessandra; Jaenicke, Thomas; Krutmann, Jean

    2014-01-01

    Photoprotection of human skin by means of sunscreens or daily skin-care products is traditionally centered around the prevention of acute (e.g. sunburn) and chronic (e.g. skin cancer and photoaging) skin damage that may result from exposure to ultraviolet rays (UVB and UVA). Within the last decade, however, it has been appreciated that wavelengths beyond the ultraviolet spectrum, in particular visible light and infrared radiation, contribute to skin damage in general and photoaging of human skin in particular. As a consequence, attempts have been made to develop skin care/sunscreen products that not only protect against UVB or UVA radiation but provide photoprotection against visible light and infrared radiation as well. In this article, we will briefly review the current knowledge about the mechanisms responsible for visible light/infrared radiation-induced skin damage and then, based on this information, discuss strategies that have been successfully used or may be employed in the future to achieve photoprotection of human skin beyond ultraviolet radiation. In this regard we will particularly focus on the use of topical antioxidants and the challenges that result from the task of showing their efficacy. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  9. High precision optical spectroscopy and quantum state selected photodissociation of ultracold 88Sr2 molecules in an optical lattice

    NASA Astrophysics Data System (ADS)

    McDonald, Mickey

    2017-04-01

    Over the past several decades, rapid progress has been made toward the accurate characterization and control of atoms, epitomized by the ever-increasing accuracy and precision of optical atomic lattice clocks. Extending this progress to molecules will have exciting implications for chemistry, condensed matter physics, and precision tests of physics beyond the Standard Model. My thesis describes work performed over the past six years to establish the state of the art in manipulation and quantum control of ultracold molecules. We describe a thorough set of measurements characterizing the rovibrational structure of weakly bound 88Sr2 molecules from several different perspectives, including determinations of binding energies; linear, quadratic, and higher order Zeeman shifts; transition strengths between bound states; and lifetimes of narrow subradiant states. Finally, we discuss measurements of photofragment angular distributions produced by photodissociation of molecules in single quantum states, leading to an exploration of quantum-state-resolved ultracold chemistry. The images of exploding photofragments produced in these studies exhibit dramatic interference effects and strongly violate semiclassical predictions, instead requiring a fully quantum mechanical description.

  10. REMPI detection of singlet oxygen 1O2 arising from UV-photodissociation of van der Waals complex isoprene-oxygen C5H8-O2

    NASA Astrophysics Data System (ADS)

    Bogomolov, Alexandr S.; Dozmorov, Nikolay V.; Kochubei, Sergei A.; Baklanov, Alexey V.

    2018-01-01

    The one-laser two-color resonance enhanced multiphoton ionization REMPI [(1 + 1‧) + 1] and velocity map imaging have been applied to investigate formation of molecular oxygen in excited singlet O2(a1Δg) and ground O2(X3Σg-) states in the photodissociation of van der Waals complex isoprene-oxygen C5H8-O2. These molecules were found to appear in the different rotational states with translational energy varied from a value as low as ∼1 meV to a distribution with temperature of about 940 K. The observed traces of electron recoil in the images of photoions reveal participation of several ionization pathways of the resonantly excited intermediate states of O2.

  11. Near-ultraviolet laser diodes for brilliant ultraviolet fluorophore excitation.

    PubMed

    Telford, William G

    2015-12-01

    Although multiple lasers are now standard equipment on most modern flow cytometers, ultraviolet (UV) lasers (325-365 nm) remain an uncommon excitation source for cytometry. Nd:YVO4 frequency-tripled diode pumped solid-state lasers emitting at 355 nm are now the primary means of providing UV excitation on multilaser flow cytometers. Although a number of UV excited fluorochromes are available for flow cytometry, the cost of solid-state UV lasers remains prohibitively high, limiting their use to all but the most sophisticated multilaser instruments. The recent introduction of the brilliant ultraviolet (BUV) series of fluorochromes for cell surface marker detection and their importance in increasing the number of simultaneous parameters for high-dimensional analysis has increased the urgency of including UV sources in cytometer designs; however, these lasers remain expensive. Near-UV laser diodes (NUVLDs), a direct diode laser source emitting in the 370-380 nm range, have been previously validated for flow cytometric analysis of most UV-excited probes, including quantum nanocrystals, the Hoechst dyes, and 4',6-diamidino-2-phenylindole. However, they remain a little-used laser source for cytometry, despite their significantly lower cost. In this study, the ability of NUVLDs to excite the BUV dyes was assessed, along with their compatibility with simultaneous brilliant violet (BV) labeling. A NUVLD emitting at 375 nm was found to excite most of the available BUV dyes at least as well as a UV 355 nm source. This slightly longer wavelength did produce some unwanted excitation of BV dyes, but at sufficiently low levels to require minimal additional compensation. NUVLDs are compact, relatively inexpensive lasers that have higher power levels than the newest generation of small 355 nm lasers. They can, therefore, make a useful, cost-effective substitute for traditional UV lasers in multicolor analysis involving the BUV and BV dyes. Published 2015 Wiley Periodicals Inc. on

  12. Ultraviolet Imaging Telescope observations of the Crab Nebula

    NASA Technical Reports Server (NTRS)

    Hennessy, Gregory S.; O'Connell, Robert W.; Cheng, Kwang P.; Bohlin, Ralph C.; Collins, Nicholas R.; Gull, Theodore P.; Hintzen, Paul; Isensee, Joan E.; Landsman, Wayne B.; Roberts, Morton S.

    1992-01-01

    We obtained ultraviolet images of the Crab Nebula with the Ultraviolet Imaging Telescope during the Astro-1 Space Shuttle mission in 1990 December. The UV continuum morphology of the Crab is generally similar to that in the optical region, but the wispy structures are less conspicuous in the UV and X-ray. UV line emission from the thermal filaments is not strong. UV spectral index maps with a resolution of 10 arcsecs show a significant gradient across the nebula, with the outer parts being redder, as expected from synchrotron losses. The location of the bluest synchrotron continuum does not coincide with the pulsar.

  13. ASASSN-15LH: A SUPERLUMINOUS ULTRAVIOLET REBRIGHTENING OBSERVED BY SWIFT AND HUBBLE

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Brown, Peter J.; Yang, Yi; Wang, Lifan

    2016-09-01

    We present and discuss ultraviolet and optical photometry from the Ultraviolet/Optical Telescope, X-ray limits from the X-Ray Telescope on Swift, and imaging polarimetry and ultraviolet/optical spectroscopy with the Hubble Space Telescope , all from observations of ASASSN-15lh. It has been classified as a hydrogen-poor superluminous supernova (SLSN I), making it more luminous than any other supernova observed. ASASSN-15lh is not detected in the X-rays in individual or co-added observations. From the polarimetry we determine that the explosion was only mildly asymmetric. We find the flux of ASASSN-15lh to increase strongly into the ultraviolet, with an ultraviolet luminosity 100 times greatermore » than the hydrogen-rich, ultraviolet-bright SLSN II SN 2008es. We find that objects as bright as ASASSN-15lh are easily detectable beyond redshifts of ∼4 with the single-visit depths planned for the Large Synoptic Survey Telescope. Deep near-infrared surveys could detect such objects past a redshift of ∼20, enabling a probe of the earliest star formation. A late rebrightening—most prominent at shorter wavelengths—is seen about two months after the peak brightness, which is itself as bright as an SLSN. The ultraviolet spectra during the rebrightening are dominated by the continuum without the broad absorption or emission lines seen in SLSNe or tidal disruption events (TDEs) and the early optical spectra of ASASSN-15lh. Our spectra show no strong hydrogen emission, showing only Ly α absorption near the redshift previously found by optical absorption lines of the presumed host. The properties of ASASSN-15lh are extreme when compared to either SLSNe or TDEs.« less

  14. The Extreme Ultraviolet Explorer Mission

    NASA Technical Reports Server (NTRS)

    Bowyer, S.; Malina, R. F.

    1991-01-01

    The Extreme Ultraviolet Explorer (EUVE) mission, currently scheduled from launch in September 1991, is described. The primary purpose of the mission is to survey the celestial sphere for astronomical sources of extreme ultraviolet (EUV) radiation with the use of three EUV telescope, each sensitive to a different segment of the EUV band. A fourth telescope is planned to perform a high-sensitivity search of a limited sample of the sky in the shortest wavelength bands. The all-sky survey is planned to be carried out in the first six months of the mission in four bands, or colors, 70-180 A, 170-250 A, 400-600 A, and 500-700 A. The second phase of the mission is devoted to spectroscopic observations of EUV sources. A high-efficiency grazing-incidence spectrometer using variable line-space gratings is planned to provide spectral data with about 1-A resolution. An end-to-end model of the mission, from a stellar source to the resulting scientific data, is presented. Hypothetical data from astronomical sources were processed through this model and are shown.

  15. Effects of exposure to ultraviolet light on the development of Rana pipiens, the northern leopard frog

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Williams, J.J.; Wofford, H.W.

    1996-10-01

    The increase in ultraviolet light intensity levels due to ozone depletion recently has been linked to the decline in amphibian population. In this experiment, eggs and larvae of Rana pipiens were subjected to differing amounts of ultraviolet radiation to determine the effects of ultraviolet light on the development of amphibian tadpoles. The total length, length of body without tail, and maximum width of each specimen was recorded for a month of the tadpoles` development, including several measurements after the ultraviolet exposures were concluded. It was found that ultraviolet exposure significantly reduced the size of the organisms in comparison with themore » control group in all three measured areas. Ultraviolet radiation altered the health and appearance of the exposed organisms and was lethal at large amounts. This experiment showed that ultraviolet radiation could cause many problems in developing amphibians. By slowing their development and physically weakening predation, thus contributing to a decline in overall population levels.« less

  16. GALEX 1st Light Near and Far Ultraviolet -100

    NASA Image and Video Library

    2003-05-28

    NASA's Galaxy Evolution Explorer took this image on May 21 and 22, 2003. The image was made from data gathered by the two channels of the spacecraft camera during the mission's "first light" milestone. It shows about 100 celestial objects in the constellation Hercules. The reddish objects represent those detected by the camera's near ultraviolet channel over a 5-minute period, while bluish objects were detected over a 3-minute period by the camera's far ultraviolet channel. The Galaxy Evolution Explorer's first light images are dedicated to the crew of the Space Shuttle Columbia. The Hercules region was directly above Columbia when it made its last contact with NASA Mission Control on February 1, over the skies of Texas. The Galaxy Evolution Explorer launched on April 28 on a mission to map the celestial sky in the ultraviolet and determine the history of star formation in the universe over the last 10 billion years. http://photojournal.jpl.nasa.gov/catalog/PIA04281

  17. Coordinated ultraviolet and radio observations of selected nearby stars

    NASA Technical Reports Server (NTRS)

    Lang, Kenneth R.

    1987-01-01

    All of the US2 shifts assigned were successfully completed with simultaneous International Ultraviolet Explorer (IUE) and the Very Large Array (VLA) observations of the proposed target stars. The target stars included dwarf M flare stars and RS CVn stars. The combined ultraviolet (IUE) and microwave (VLA) observations have provided important new insights to the radiation mechanisms at these two widely-separated regions of the electromagnetic spectrum. The VLA results included the discovery of narrow-band microwave radiation and rapid time variations in the microwave radiation of dwarf M flare stars. The results indicate that conventional radiation mechanisms cannot explain the microwave emission from these stars. In general, ultraviolet variations and bursts occur when no similar variations are detected at microwave wavelengths and vice versa. Although these is some overlap, the variations in these two spectral regions are usually uncorrelated, suggesting that there is little interaction between the activity centers at the two associated atmospheric levels.

  18. GALEX 1st Light Far Ultraviolet

    NASA Image and Video Library

    2003-05-28

    This image was taken May 21 and 22, 2003 by NASA Galaxy Evolution Explorer. The image was made from data gathered by the far ultraviolet channel of the spacecraft camera during the mission first light milestone. It shows about 400 celestial objects

  19. Lunar Ultraviolet Telescope Experiment (LUTE), phase A

    NASA Technical Reports Server (NTRS)

    Mcbrayer, Robert O.

    1994-01-01

    The Lunar Ultraviolet Telescope Experiment (LUTE) is a 1-meter telescope for imaging from the lunar surface the ultraviolet spectrum between 1,000 and 3,500 angstroms. There have been several endorsements of the scientific value of a LUTE. In addition to the scientific value of LUTE, its educational value and the information it can provide on the design of operating hardware for long-term exposure in the lunar environment are important considerations. This report provides the results of the LUTE phase A activity begun at the George C. Marshall Space Flight Center in early 1992. It describes the objective of LUTE (science, engineering, and education), a feasible reference design concept that has evolved, and the subsystem trades that were accomplished during the phase A.

  20. Shuttle-based measurements: GLO ultraviolet earthlimb view

    NASA Astrophysics Data System (ADS)

    Gardner, James A.; Murad, Edmond; Viereck, Rodney A.; Knecht, David J.; Pike, Charles P.; Broadfoot, A. Lyle

    1996-11-01

    The GLO experiment is an on-going shuttle-based spectrograph/imager project that has returned ultraviolet (100 - 400 nm) limb views. High spectral (0.35 nm FWHM) and temporal (4 s) resolution spectra include simultaneous altitude profiles (in the range of 80 - 400 km tangent height with 10 km resolution) of dayglow and nightglow features. Measured emissions include the NO gamma, N2 Vegard-Kaplan and second positive, N2+ first negative, and O2 Herzberg I band systems and both atomic and cation lines of N, O, and Mg. This data represents a low solar activity benchmark for future observations. We report on the status of the GLO project, which included three space flights in 1995, and present spectral data on important ultraviolet band systems.

  1. Helium Tagging Infrared Photodissociation Spectroscopy of Reactive Ions.

    PubMed

    Roithová, Jana; Gray, Andrew; Andris, Erik; Jašík, Juraj; Gerlich, Dieter

    2016-02-16

    The interrogation of reaction intermediates is key for understanding chemical reactions; however their direct observation and study remains a considerable challenge. Mass spectrometry is one of the most sensitive analytical techniques, and its use to study reaction mixtures is now an established practice. However, the information that can be obtained is limited to elemental analysis and possibly to fragmentation behavior, which is often challenging to analyze. In order to extend the available experimental information, different types of spectroscopy in the infrared and visible region have been combined with mass spectrometry. Spectroscopy of mass selected ions usually utilizes the powerful sensitivity of mass spectrometers, and the absorption of photons is not detected as such but rather translated to mass changes. One approach to accomplish such spectroscopy involves loosely binding a tag to an ion that will be removed by absorption of one photon. We have constructed an ion trapping instrument capable of reaching temperatures that are sufficiently low to enable tagging by helium atoms in situ, thus permitting infrared photodissociation spectroscopy (IRPD) to be carried out. While tagging by larger rare gas atoms, such as neon or argon is also possible, these may cause significant structural changes to small and reactive species, making the use of helium highly beneficial. We discuss the "innocence" of helium as a tag in ion spectroscopy using several case studies. It is shown that helium tagging is effectively innocent when used with benzene dications, not interfering with their structure or IRPD spectrum. We have also provided a case study where we can see that despite its minimal size there are systems where He has a huge effect. A strong influence of the He tagging was shown in the IRPD spectra of HCCl(2+) where large spectral shifts were observed. While the presented systems are rather small, they involve the formation of mixtures of isomers. We have therefore

  2. ULTRAVIOLET SPECTROSCOPY OF BL Hyi AND EF Eri IN HIGH AND INTERMEDIATE STATES

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sanad, M. R.; Abdel-Sabour, M. A.

    2016-08-01

    We present the first phase-resolved ultraviolet spectroscopy of two polar systems, BL Hyi and EF Eri, in high and intermediate states from the International Ultraviolet Explorer ( IUE ) during the periods between 1982–1995 and 1979–1991, respectively. The flux curves for the C iv and He ii emission lines for both systems showing variations in their fluxes at different orbital phases are presented. The emission lines are produced in the accretion stream. The reddening for the two polars is found to be 0.00. Our results show that there are variations of the line fluxes with time, similar to the lightmore » curves found for both BL Hyi and EF Eri in the optical, infrared, ultraviolet, and X-ray bands. IUE observations support a radiative shock model of BL Hyi with the heating of matter by radiation from the accretion shock and cooling by the electrons scattering off ultraviolet photons from the surface of the white dwarf. EF Eri observations support a two-temperature white dwarf model producing sufficient ultraviolet flux for orbital modulations.« less

  3. Filtering and polychromatic vision in mantis shrimps: themes in visible and ultraviolet vision.

    PubMed

    Cronin, Thomas W; Bok, Michael J; Marshall, N Justin; Caldwell, Roy L

    2014-01-01

    Stomatopod crustaceans have the most complex and diverse assortment of retinal photoreceptors of any animals, with 16 functional classes. The receptor classes are subdivided into sets responsible for ultraviolet vision, spatial vision, colour vision and polarization vision. Many of these receptor classes are spectrally tuned by filtering pigments located in photoreceptors or overlying optical elements. At visible wavelengths, carotenoproteins or similar substances are packed into vesicles used either as serial, intrarhabdomal filters or lateral filters. A single retina may contain a diversity of these filtering pigments paired with specific photoreceptors, and the pigments used vary between and within species both taxonomically and ecologically. Ultraviolet-filtering pigments in the crystalline cones serve to tune ultraviolet vision in these animals as well, and some ultraviolet receptors themselves act as birefringent filters to enable circular polarization vision. Stomatopods have reached an evolutionary extreme in their use of filter mechanisms to tune photoreception to habitat and behaviour, allowing them to extend the spectral range of their vision both deeper into the ultraviolet and further into the red.

  4. Ionospheric Profiles from Ultraviolet Remote Sensing

    DTIC Science & Technology

    1997-09-30

    The long-term goal of this project is to obtain ionospheric profiles from ultraviolet remote sensing of the ionosphere from orbiting space platforms... Remote sensing of the nighttime ionosphere is a more straightforward process because of the absence of the complications brought about by daytime

  5. Protection from visible light by commonly used textiles is not predicted by ultraviolet protection.

    PubMed

    Van den Keybus, Caroline; Laperre, Jan; Roelandts, Rik

    2006-01-01

    Interest is increasing in the prevention of acute and chronic actinic damage provided by clothing. This interest has focused mainly on protection against ultraviolet irradiation, but it has now also turned to protection against visible light. This change is mainly due to the action spectrum in the visible light range of some photodermatoses and the increasing interest in photodynamic therapy. The ultraviolet protection provided by commercially available textiles can be graded by determining an ultraviolet protection factor. Several methods have already been used to determine the ultraviolet protection factor. The fact that protection from visible light by textiles cannot be predicted by their ultraviolet protection makes the situation more complicated. This study attempts to determine whether or not the ultraviolet protection factor value of a particular textile is a good parameter for gauging its protection in the visible light range and concludes that a protection factor of textile materials against visible light needs to be developed. This development should go beyond the protection factor definition used in this article, which has some limitations, and should take into account the exact action spectrum for which the protection is needed.

  6. Single-crystalline aluminum film for ultraviolet plasmonic nanolasers

    PubMed Central

    Chou, Bo-Tsun; Chou, Yu-Hsun; Wu, Yen-Mo; Chung, Yi-Cheng; Hsueh, Wei-Jen; Lin, Shih-Wei; Lu, Tien-Chang; Lin, Tzy-Rong; Lin, Sheng-Di

    2016-01-01

    Significant advances have been made in the development of plasmonic devices in the past decade. Plasmonic nanolasers, which display interesting properties, have come to play an important role in biomedicine, chemical sensors, information technology, and optical integrated circuits. However, nanoscale plasmonic devices, particularly those operating in the ultraviolet regime, are extremely sensitive to the metal and interface quality. Thus, these factors have a significant bearing on the development of ultraviolet plasmonic devices. Here, by addressing these material-related issues, we demonstrate a low-threshold, high-characteristic-temperature metal-oxide-semiconductor ZnO nanolaser that operates at room temperature. The template for the ZnO nanowires consists of a flat single-crystalline Al film grown by molecular beam epitaxy and an ultrasmooth Al2O3 spacer layer synthesized by atomic layer deposition. By effectively reducing the surface plasmon scattering and metal intrinsic absorption losses, the high-quality metal film and the sharp interfaces formed between the layers boost the device performance. This work should pave the way for the use of ultraviolet plasmonic nanolasers and related devices in a wider range of applications. PMID:26814581

  7. Observations of the sun, an ultraviolet variable star

    NASA Technical Reports Server (NTRS)

    Heath, D. F.

    1972-01-01

    The uncertainty as to whether or not the sun is a variable star in that region of the ultraviolet which is absorbed in the mesosphere and stratosphere led to an experiment with acronym MUSE, Monitor of Ultraviolet Solar Energy. The experiment was first flown on an Aerobee rocket in August 1966 and subsequently on Nimbus 3 and 4 in April 1969 and April 1970 respectively. The basic philosophy behind the design of the experiment was to provide an instrument which would not require a solar pointing mechanism and at the same time would be capable of high radiometric accuracy for long periods in space.

  8. Pollen and spores as biological recorders of past ultraviolet irradiance

    NASA Astrophysics Data System (ADS)

    Jardine, Phillip E.; Fraser, Wesley T.; Lomax, Barry H.; Sephton, Mark A.; Shanahan, Timothy M.; Miller, Charlotte S.; Gosling, William D.

    2016-12-01

    Solar ultraviolet (UV) irradiance is a key driver of climatic and biotic change. Ultraviolet irradiance modulates stratospheric warming and ozone production, and influences the biosphere from ecosystem-level processes through to the largest scale patterns of diversification and extinction. Yet our understanding of ultraviolet irradiance is limited because no method has been validated to reconstruct its flux over timescales relevant to climatic or biotic processes. Here, we show that a recently developed proxy for ultraviolet irradiance based on spore and pollen chemistry can be used over long (105 years) timescales. Firstly we demonstrate that spatial variations in spore and pollen chemistry correlate with known latitudinal solar irradiance gradients. Using this relationship we provide a reconstruction of past changes in solar irradiance based on the pollen record from Lake Bosumtwi in Ghana. As anticipated, variations in the chemistry of grass pollen from the Lake Bosumtwi record show a link to multiple orbital precessional cycles (19-21 thousand years). By providing a unique, local proxy for broad spectrum solar irradiance, the chemical analysis of spores and pollen offers unprecedented opportunities to decouple solar variability, climate and vegetation change through geologic time and a new proxy with which to probe the Earth system.

  9. Absolute vacuum ultraviolet photoabsorption cross section studies of atomic and molecular species: Techniques and observational data

    NASA Technical Reports Server (NTRS)

    Judge, D. L.; Wu, C. Y. R.

    1990-01-01

    Absorption of a high energy photon (greater than 6 eV) by an isolated molecule results in the formation of highly excited quasi-discrete or continuum states which evolve through a wide range of direct and indirect photochemical processes. These are: photoionization and autoionization, photodissociation and predissociation, and fluorescence. The ultimate goal is to understand the dynamics of the excitation and decay processes and to quantitatively measure the absolute partial cross sections for all processes which occur in photoabsorption. Typical experimental techniques and the status of observational results of particular interest to solar system observations are presented.

  10. The MUSCLES Treasury Survey. III. X-Ray to Infrared Spectra of 11 M and K Stars Hosting Planets

    NASA Astrophysics Data System (ADS)

    Loyd, R. O. P.; France, Kevin; Youngblood, Allison; Schneider, Christian; Brown, Alexander; Hu, Renyu; Linsky, Jeffrey; Froning, Cynthia S.; Redfield, Seth; Rugheimer, Sarah; Tian, Feng

    2016-06-01

    We present a catalog of panchromatic spectral energy distributions (SEDs) for 7 M and 4 K dwarf stars that span X-ray to infrared wavelengths (5 Å -5.5 μm). These SEDs are composites of Chandra or XMM-Newton data from 5-˜50 Å, a plasma emission model from ˜50-100 Å, broadband empirical estimates from 100-1170 Å, Hubble Space Telescope data from 1170-5700 Å, including a reconstruction of stellar Lyα emission at 1215.67 Å, and a PHOENIX model spectrum from 5700-55000 Å. Using these SEDs, we computed the photodissociation rates of several molecules prevalent in planetary atmospheres when exposed to each star’s unattenuated flux (“unshielded” photodissociation rates) and found that rates differ among stars by over an order of magnitude for most molecules. In general, the same spectral regions drive unshielded photodissociations both for the minimally and maximally FUV active stars. However, for O3 visible flux drives dissociation for the M stars whereas near-UV flux drives dissociation for the K stars. We also searched for an far-UV continuum in the assembled SEDs and detected it in 5/11 stars, where it contributes around 10% of the flux in the range spanned by the continuum bands. An ultraviolet continuum shape is resolved for the star ɛ Eri that shows an edge likely attributable to Si II recombination. The 11 SEDs presented in this paper, available online through the Mikulski Archive for Space Telescopes, will be valuable for vetting stellar upper-atmosphere emission models and simulating photochemistry in exoplanet atmospheres.

  11. Degradation of sulfamethoxazole by UV, UV/H2O2 and UV/persulfate (PDS): Formation of oxidation products and effect of bicarbonate.

    PubMed

    Yang, Yi; Lu, Xinglin; Jiang, Jin; Ma, Jun; Liu, Guanqi; Cao, Ying; Liu, Weili; Li, Juan; Pang, Suyan; Kong, Xiujuan; Luo, Congwei

    2017-07-01

    The frequent detection of sulfamethoxazole (SMX) in wastewater and surface waters gives rise of concerns about their ecotoxicological effects and potential risks to induce antibacterial resistant genes. UV/hydrogen peroxide (UV/H 2 O 2 ) and UV/persulfate (UV/PDS) advanced oxidation processes have been demonstrated to be effective for the elimination of SMX, but there is still a need for a deeper understanding of product formations. In this study, we identified and compared the transformation products of SMX in UV, UV/H 2 O 2 and UV/PDS processes. Because of the electrophilic nature of SO 4 - , the second-order rate constant for the reaction of sulfate radical (SO 4 - ) with the anionic form of SMX was higher than that with the neutral form, while hydroxyl radical (OH) exhibited comparable reactivity to both forms. The direct photolysis of SMX predominately occurred through cleavage of the NS bond, rearrangement of the isoxazole ring, and hydroxylation mechanisms. Hydroxylation was the dominant pathway for the reaction of OH with SMX. SO 4 - favored attack on NH 2 group of SMX to generate a nitro derivative and dimeric products. The presence of bicarbonate in UV/H 2 O 2 inhibited the formation of hydroxylated products, but promoted the formation of the nitro derivative and the dimeric products. In UV/PDS, bicarbonate increased the formation of the nitro derivative and the dimeric products, but decreased the formation of the hydroxylated dimeric products. The different effect of bicarbonate on transformation products in UV/H 2 O 2 vs. UV/PDS suggested that carbonate radical (CO 3 - ) oxidized SMX through the electron transfer mechanism similar to SO 4 - but with less oxidation capacity. Additionally, SO 4 - and CO 3 - exhibited higher reactivity to the oxazole ring than the isoxazole ring of SMX. Ecotoxicity of transformation products was estimated by ECOSAR program based on the quantitative structure-activity relationship analysis as well as by experiments using

  12. Ultraviolet Spectra of Subluminous Objects Found in the Kiso Schmidt Survey and Systematic Reanalysis of the Archived Ultraviolet Spectra of White Dwarfs Observed with the IUE Satellite Under the Astrophysics Data Program (ADP)

    NASA Technical Reports Server (NTRS)

    Wegner, Gary A.

    1988-01-01

    Recent research under NASA grant NAG5-971 consisted of the performance of two projects in conjunction with the International Ultraviolet Explorer (IUE) satellites. These are: (1) to look at the ultraviolet spectra of subluminous stars identified from visual wavelength spectroscopy that had been originally discovered from the Kiso Schmidt survey for ultraviolet excess stars and (2) to carry out a systematic reanalysis of the archived IUE spectra of white dwarfs. This report presents information on the progress of the re-reduction of over 600 IUE white dwarf spectra and their subsequent analysis employing model atmospheres and the observation of the Kiso ultraviolet excess stars.

  13. Graphene Oxide Transparent Hybrid Film and Its Ultraviolet Shielding Property.

    PubMed

    Xie, Siyuan; Zhao, Jianfeng; Zhang, Bowu; Wang, Ziqiang; Ma, Hongjuan; Yu, Chuhong; Yu, Ming; Li, Linfan; Li, Jingye

    2015-08-19

    Herein, we first reported a facile strategy to prepare functional Poly(vinyl alcohol) (PVA) hybrid film with well ultraviolet (UV) shielding property and visible light transmittance using graphene oxide nanosheets as UV-absorber. The absorbance of ultraviolet light at 300 nm can be up to 97.5%, while the transmittance of visible light at 500 nm keeps 40% plus. This hybrid film can protect protein from UVA light induced photosensitive damage, remarkably.

  14. NASA's Ultraviolet Astrophysics Branch: Present and future detector program

    NASA Technical Reports Server (NTRS)

    Welsh, Barry Y.

    1992-01-01

    The various concepts in ultraviolet detector technology currently being funded by NASA's Astrophysics Division to carry out observations in the 100 to 3000 A region are reviewed. In order to match the science objectives of future space missions with new observational techniques, critical detector technology needs in the ultraviolet regime have been identified. The attempt by NASA's Astrophysics Division Advanced Programs Branch to formulate an integrated detector technology plan as part of the ongoing 'Astrotech 21' program in order to provide the technology base for these astrophysics missions of the 21st century is described.

  15. Far-Ultraviolet Observations of Outflows from Infrared-Luminous Galaxies

    NASA Astrophysics Data System (ADS)

    Leitherer, Claus; Chandar, Rupali; Tremonti, Christy A.; Wofford, Aida

    2013-03-01

    We have obtained ultraviolet spectra between 1150 and 1450 Å of four ultraviolet-bright, infrared-luminous starburst galaxies. Our selected sight-lines towards the starburst nuclei probe the conditions in the starburst-driven outflows. We detect outflowing gas with velocities of up to ˜900 km s-1. It is likely that the outflows are a major source of metal enrichment of the galaxies' halos. The mass outflow rates of several tens of M⊙ yr-1 are similar to the star-formation rates. The outflows may quench star formation and ultimately regulate the starburst.

  16. Ultraviolet spectrophotometry from Gemini 11 of stars in Orion

    NASA Technical Reports Server (NTRS)

    Morgan, T. H.; Spear, G. G.; Kondo, Y.; Henize, K. G.

    1975-01-01

    Ultraviolet spectrophotometry in the wavelength region 2600-3600 A is reported for the bright early-type stars beta, eta, gamma, delta, iota, epsilon, sigma, zeta, and kappa Ori. The results are in good agreement with other observations, and, with the possible exception of the supergiants, are in good agreement with recent line-blanketed model atmospheres. There is evidence that the supergiants possess a small ultraviolet deficiency shortward of 3000 A relative to main-sequence stars of similar spectral type. The most extreme example of this phenomenon is the star kappa Ori.

  17. The Extreme Ultraviolet Explorer mission - Overview and initial results

    NASA Technical Reports Server (NTRS)

    Haisch, B.; Bowyer, S.; Malina, R. F.

    1993-01-01

    The history of extreme ultraviolet (EUV) astronomy is briefly reviewed, and an overview of the Extreme Ultraviolet Explorer mission, launched into a near-earth (550 km) orbit on June 7, 1992, is presented. First, the principal objective of the mission are summarized. The instrumentation and operation of the mission are then described, with particular attention given to the sky survey instruments, the deep survey instrument, and the spectrometers. The discussion also covers the current view of the interstellar medium, early results from the mission, and future prospects for EUV astronomy.

  18. SUMER: Solar Ultraviolet Measurements of Emitted Radiation

    NASA Technical Reports Server (NTRS)

    Wilhelm, K.; Axford, W. I.; Curdt, W.; Gabriel, A. H.; Grewing, M.; Huber, M. C. E.; Jordan, S. D.; Kuehne, M.; Lemaire, P.; Marsch, E.

    1992-01-01

    The experiment Solar Ultraviolet Measurements of Emitted Radiation (SUMER) is designed for the investigations of plasma flow characteristics, turbulence and wave motions, plasma densities and temperatures, structures and events associated with solar magnetic activity in the chromosphere, the transition zone and the corona. Specifically, SUMER will measure profiles and intensities of Extreme Ultraviolet (EUV) lines emitted in the solar atmosphere ranging from the upper chromosphere to the lower corona; determine line broadenings, spectral positions and Doppler shifts with high accuracy, provide stigmatic images of selected areas of the Sun in the EUV with high spatial, temporal and spectral resolution and obtain full images of the Sun and the inner corona in selectable EUV lines, corresponding to a temperature from 10,000 to more than 1,800,000 K.

  19. Deep ultraviolet light-emitting and laser diodes

    NASA Astrophysics Data System (ADS)

    Khan, Asif; Asif, Fatima; Muhtadi, Sakib

    2016-02-01

    Nearly all the air-water purification/polymer curing systems and bio-medical instruments require 250-300 nm wavelength ultraviolet light for which mercury lamps are primarily used. As a potential replacement for these hazardous mercury lamps, several global research teams are developing AlGaN based Deep Ultraviolet (DUV) light emitting diodes (LEDs) and DUV LED Lamps and Laser Diodes over Sapphire and AlN substrates. In this paper, we review the current research focus and the latest device results. In addition to the current results we also discuss a new quasipseudomorphic device design approach. This approach which is much easier to integrate in a commercial production setting was successfully used to demonstrate UVC devices on Sapphire substrates with performance levels equal to or better than the conventional relaxed device designs.

  20. Ultraviolet spectroscopy of meteoric debris of comets

    NASA Technical Reports Server (NTRS)

    Wdowiak, T. J.; Kubinec, W. R.; Nuth, J. A.

    1986-01-01

    It is proposed to carry out slitless spectroscopy at ultraviolet wavelengths from orbit of meteoric debris associated with comets. The Eta Aquarid and Orionid/Halley and the Perseid/1962 862 Swift-Tuttle showers would be principal targets. Low light level, ultraviolet video technique will be used during night side of the orbit in a wide field, earthward viewing mode. Data will be stored in compact video cassette recorders. The experiment may be configured as a GAS package or in the HITCHHIKER mode. The latter would allow flexible pointing capability beyond that offered by shuttle orientation of the GAS package, and doubling of the data record. The 1100 to 3200 A spectral region should show emissions of atomic, ionic, and molecular species of interest on cometary and solar system studies.

  1. An ultraviolet responsive hybrid solar cell based on titania/poly(3-hexylthiophene).

    PubMed

    Wu, Jihuai; Yue, Gentian; Xiao, Yaoming; Lin, Jianming; Huang, Miaoliang; Lan, Zhang; Tang, Qunwei; Huang, Yunfang; Fan, Leqing; Yin, Shu; Sato, Tsugio

    2013-01-01

    Here we present an ultraviolet responsive inorganic-organic hybrid solar cell based on titania/poly(3-hexylthiophene) (TiO(2)/P3HT) heterojuction. In this solar cell, TiO(2) is an ultraviolet light absorber and electronic conductor, P3HT is a hole conductor, the light-to-electrical conversion is realized by the cooperation for these two components. Doping ionic salt in P3HT polymer can improve the photovoltaic performance of the solar cell. Under ultraviolet light irradiation with intensity of 100 mW·cm(-2), the hybrid solar cell doped with 1.0 wt.% lithium iodide achieves an energy conversion efficiency of 1.28%, which is increased by 33.3% compared to that of the hybrid solar cell without lithium iodide doping. Our results open a novel sunlight irradiation field for solar energy utilization, demonstrate the feasibility of ultraviolet responsive solar cells, and provide a new route for enhancing the photovoltaic performance of solar cells.

  2. An ultraviolet responsive hybrid solar cell based on titania/poly(3-hexylthiophene)

    PubMed Central

    Wu, Jihuai; Yue, Gentian; Xiao, Yaoming; Lin, Jianming; Huang, Miaoliang; Lan, Zhang; Tang, Qunwei; Huang, Yunfang; Fan, Leqing; Yin, Shu; Sato, Tsugio

    2013-01-01

    Here we present an ultraviolet responsive inorganic-organic hybrid solar cell based on titania/poly(3-hexylthiophene) (TiO2/P3HT) heterojuction. In this solar cell, TiO2 is an ultraviolet light absorber and electronic conductor, P3HT is a hole conductor, the light-to-electrical conversion is realized by the cooperation for these two components. Doping ionic salt in P3HT polymer can improve the photovoltaic performance of the solar cell. Under ultraviolet light irradiation with intensity of 100 mW·cm−2, the hybrid solar cell doped with 1.0 wt.% lithium iodide achieves an energy conversion efficiency of 1.28%, which is increased by 33.3% compared to that of the hybrid solar cell without lithium iodide doping. Our results open a novel sunlight irradiation field for solar energy utilization, demonstrate the feasibility of ultraviolet responsive solar cells, and provide a new route for enhancing the photovoltaic performance of solar cells. PMID:23412470

  3. Ultraviolet photometry from the orbiting astronomical observatory. 8: The blue Ap stars

    NASA Technical Reports Server (NTRS)

    Leckrone, D. S.

    1973-01-01

    The filter photometers in the Wisconsin Experiment Package on OAO-2 were used to obtain data for a carefully selected set of 24 blue Ap stars and 31 comparison standard B and A dwarfs and giants for a program of relative photometry. Observations were made in seven bandpasses over the effective wavelength range 1430A-4250A. The Ap stars observed include members of the Si, Hg-Mn and Sr-Cr-Eu peculiarity classes. Most of them are too blue in B-V for their published MK spectral classes. The blue Ap stars are markedly deficient in emitted ultraviolet flux and are underluminous as compared to normal stars with the same UBV colors. The Hg-Mn stars appear less flux deficient in the ultraviolet for their UBV colors than do Si or Sr-cr-Eu stars. Most of the Ap stars observed possess ultraviolet flux distributions, or ultraviolet color temperatures, consistent with their published MK spectral classes to well within the classification uncertainties.

  4. OH+ emission from cometary knots in planetary nebulae

    NASA Astrophysics Data System (ADS)

    Priestley, F. D.; Barlow, M. J.

    2018-05-01

    We model the molecular emission from cometary knots in planetary nebulae (PNe) using a combination of photoionization and photodissociation region (PDR) codes, for a range of central star properties and gas densities. Without the inclusion of ionizing extreme ultraviolet (EUV) radiation, our models require central star temperatures T* to be near the upper limit of the range investigated in order to match observed H2 and OH+ surface brightnesses consistent with observations - with the addition of EUV flux, our models reproduce observed OH+ surface brightnesses for T* ≥ 100 kK. For T* < 80 kK, the predicted OH+ surface brightness is much lower, consistent with the non-detection of this molecule in PNe with such central star temperatures. Our predicted level of H2 emission is somewhat weaker than commonly observed in PNe, which may be resolved by the inclusion of shock heating or fluorescence due to UV photons. Some of our models also predict ArH+ and HeH+ rotational line emission above detection thresholds, despite neither molecule having been detected in PNe, although the inclusion of photodissociation by EUV photons, which is neglected by our models, would be expected to reduce their detectability.

  5. Ultraviolet light absorbers having two different chromophors in the same molecule

    DOEpatents

    Vogl, O.; Li, S.

    1983-10-06

    This invention relates to novel ultraviolet light absorbers having two chromophors in the same molecule, and more particularly to benzotriazole substituted dihydroxybenzophenones and acetophenones. More particularly, this invention relates to 3,5-(di(2H-benzotriazole-2-yl))-2,4-dihydroxybenzophenone and 3,5-(di(2H-benzotriazole-2-yl))-2,4-dihydroxyacetophenone which are particularly useful as an ultraviolet light absorbers.

  6. HUBBLE IDENTIFIES SOURCE OF ULTRAVIOLET LIGHT IN AN OLD GALAXY

    NASA Technical Reports Server (NTRS)

    2002-01-01

    Hubble Space Telescope's exquisite resolution has allowed astronomers to resolve, for the first time, hot blue stars deep inside an elliptical galaxy. The swarm of nearly 8,000 blue stars resembles a blizzard of snowflakes near the core (lower right) of the neighboring galaxy M32, located 2.5 million light-years away in the constellation Andromeda. Hubble confirms that the ultraviolet light comes from a population of extremely hot helium-burning stars at a late stage in their lives. Unlike the Sun, which burns hydrogen into helium, these old stars exhausted their central hydrogen long ago, and now burn helium into heavier elements. The observations, taken in October 1998, were made with the camera mode of the Space Telescope Imaging Spectrograph (STIS) in ultraviolet light. The STIS field of view is only a small portion of the entire galaxy, which is 20 times wider on the sky. For reference, the full moon is 70 times wider than the STIS field-of-view. The bright center of the galaxy was placed on the right side of the image, allowing fainter stars to be seen on the left side of the image. These results are to be published in the March 1, 2000 issue of The Astrophysical Journal. Thirty years ago, the first ultraviolet observations of elliptical galaxies showed that they were surprisingly bright when viewed in ultraviolet light. Before those pioneering UV observations, old groups of stars were assumed to be relatively cool and thus extremely faint in the ultraviolet. Over the years since the initial discovery of this unexpected ultraviolet light, indirect evidence has accumulated that it originates in a population of old, but hot, helium-burning stars. Now Hubble provides the first direct visual evidence. Nearby elliptical galaxies are thought to be relatively simple galaxies comprised of old stars. Because they are among the brightest objects in the Universe, this simplicity makes them useful for tracing the evolution of stars and galaxies. Credits: NASA and Thomas

  7. Ultraviolet Spectra of Two Magnetic White Dwarfs and Ultraviolet Spectra of Subluminous Objects Found in the Kiso Schmidt Survey

    NASA Technical Reports Server (NTRS)

    Wegner, Gary A.

    1987-01-01

    Low resolution International Ultraviolet Explorer (IUE) spectroscopic observations of two magnetic white dwarfs BPM25114 and K813-14 were obtained using both the SWP and LWP cameras. The first object has an observed magnetic field of 4 x 10(7) Gauss and the second has one of 3 x 10(7) Gauss. Both objects have overall spectral energy distributions appropriate for cool DA white dwarfs with T(eff) near 10,000 K and accordingly show strong lambda lambda 1400 and 1600 absorption in their spectra. Compared to non-magnetic DA white dwarfs of comparable effective temperature, there are some differences in the profiles, presumably produced by the magnetic fields in these objects. In addition, the ultraviolet spectra of a number of hot subluminous stars in the Kiso Schmidt survey were observed.

  8. Engineering support for an ultraviolet imager for the ISTP mission

    NASA Technical Reports Server (NTRS)

    Torr, Douglas G.

    1991-01-01

    Design and development activities were carried out for the Ultraviolet Imager (UVI) to be flown on the Polar Spacecraft of the INternational Solar Terrestrial Physics (ISTP) Mission. The following tasks were performed: (1) design and fabrication of prototype/engineering model of the UVI imager; (2) preliminary design review; (3) vacuum ultraviolet filter design; (4) auroral energy deposition code; (5) model of LBH vehicle glow; (6) laboratory measurement program of collision cross-sections; and (7) support of ISTP meetings.

  9. Examining Dermatologist Use and Opinions of Ultraviolet Radiation for Cosmetic and Medical Purposes.

    PubMed

    Sampson, Blake P; Secrest, Aaron M; Hansen, Christopher B; Geller, Alan C

    2018-02-01

    BACKGROUND: The commercial tanning industry has opposed efforts to educate the public on the risks of tanning as well as attempts to restrict minors' access to tanning services. Despite a paucity of supporting literature, statements from the tanning industry claiming that dermatologists routinely use in-office phototherapy for cosmetic treatments and refer patients to tanning salons have successfully derailed and defeated legislation in many states. OBJECTIVE: This study aims to evaluate dermatologist referrals for ultraviolet radiation for cosmetic and medical purposes via tanning beds or phototherapy, as well as their opinions on tanning, legislation, and ultraviolet radiation counseling practices. DESIGN: The study was conducted using a 10-question anonymous survey. SETTING: The participants were surveyed during meetings of three regional dermatologic societies. PARTICIPANTS: One hundred and fifty-two dermatologists attending society meetings participated in the study. MEASURES: The authors measured physician referrals, opinions, and recommendations regarding ultraviolet exposure. RESULTS: Zero physicians (0/152) recommended tanning salons for cosmetic reasons. These 152 dermatologists referred 458 (417 adult, 41 pediatric) out of an estimated 809,369 patients (0.057%) to tanning salons for medical treatment. Of these physicians, 76 out of 152 and 15 out of 152 reported referring at least one adult or one pediatric patient, respectively, within the last year. All respondents supported ultraviolet tanning legislation and discouraged cosmetic tanning. CONCLUSION: These findings directly contradict the assertion that dermatologists use ultraviolet radiation for cosmetic purposes or routinely refer patients to tanning salons. This study underscores the complex nature of ultraviolet radiation, as dermatologists infrequently utilize ultraviolet radiation for medical purposes and unanimously support restrictive legislation. In addition, these dermatologists counsel

  10. Examining Dermatologist Use and Opinions of Ultraviolet Radiation for Cosmetic and Medical Purposes

    PubMed Central

    Secrest, Aaron M.; Hansen, Christopher B.; Geller, Alan C.

    2018-01-01

    BACKGROUND: The commercial tanning industry has opposed efforts to educate the public on the risks of tanning as well as attempts to restrict minors’ access to tanning services. Despite a paucity of supporting literature, statements from the tanning industry claiming that dermatologists routinely use in-office phototherapy for cosmetic treatments and refer patients to tanning salons have successfully derailed and defeated legislation in many states. OBJECTIVE: This study aims to evaluate dermatologist referrals for ultraviolet radiation for cosmetic and medical purposes via tanning beds or phototherapy, as well as their opinions on tanning, legislation, and ultraviolet radiation counseling practices. DESIGN: The study was conducted using a 10-question anonymous survey. SETTING: The participants were surveyed during meetings of three regional dermatologic societies. PARTICIPANTS: One hundred and fifty-two dermatologists attending society meetings participated in the study. MEASURES: The authors measured physician referrals, opinions, and recommendations regarding ultraviolet exposure. RESULTS: Zero physicians (0/152) recommended tanning salons for cosmetic reasons. These 152 dermatologists referred 458 (417 adult, 41 pediatric) out of an estimated 809,369 patients (0.057%) to tanning salons for medical treatment. Of these physicians, 76 out of 152 and 15 out of 152 reported referring at least one adult or one pediatric patient, respectively, within the last year. All respondents supported ultraviolet tanning legislation and discouraged cosmetic tanning. CONCLUSION: These findings directly contradict the assertion that dermatologists use ultraviolet radiation for cosmetic purposes or routinely refer patients to tanning salons. This study underscores the complex nature of ultraviolet radiation, as dermatologists infrequently utilize ultraviolet radiation for medical purposes and unanimously support restrictive legislation. In addition, these dermatologists counsel

  11. Note: Photodissociation of CH3COCN at 308 nm by time-resolved Fourier-transform infrared emission spectroscopy: Is CO a primary or secondary product?

    NASA Astrophysics Data System (ADS)

    Tsai, Po-Yu; Lin, King-Chuen

    2013-06-01

    This Note aims to clarify the source of CO in photodissociation of acetyl cyanide (CH3COCN) at 308 nm. From the theoretical aspects, a new pathway via isomerization transition state (TS) at 391 ± 8 kJ/mol is found leading to the CO + CH3NC products. An amount of 60% reactant molecules at 300 K is estimated to successfully surpass the average TS barrier lying above the excitation energy by 3.5 kJ/mol. Further, a prior distribution method is conducted to characterize the vibrational energy distribution of CO on a statistical basis. The pathway to CH3NC + CO yields a vibrational branching ratio (v = 0:v = 1:v = 2:v = 3˜0.63:0.25:0.093:0.032) in excellent agreement with the observation (0.62:0.25:0.09:0.05).

  12. An ultraviolet-visible spectrophotometer automation system. Part 3: Program documentation

    NASA Astrophysics Data System (ADS)

    Roth, G. S.; Teuschler, J. M.; Budde, W. L.

    1982-07-01

    The Ultraviolet-Visible Spectrophotometer (UVVIS) automation system accomplishes 'on-line' spectrophotometric quality assurance determinations, report generations, plot generations and data reduction for chlorophyll or color analysis. This system also has the capability to process manually entered data for the analysis of chlorophyll or color. For each program of the UVVIS system, this document contains a program description, flowchart, variable dictionary, code listing, and symbol cross-reference table. Also included are descriptions of file structures and of routines common to all automated analyses. The programs are written in Data General extended BASIC, Revision 4.3, under the RDOS operating systems, Revision 6.2. The BASIC code has been enhanced for real-time data acquisition, which is accomplished by CALLS to assembly language subroutines. Two other related publications are 'An Ultraviolet-Visible Spectrophotometer Automation System - Part I Functional Specifications,' and 'An Ultraviolet-Visible Spectrophotometer Automation System - Part II User's Guide.'

  13. Coherent control at its most fundamental: carrier-envelope-phase-dependent electron localization in photodissociation of a H2(+) molecular ion beam target.

    PubMed

    Rathje, T; Sayler, A M; Zeng, S; Wustelt, P; Figger, H; Esry, B D; Paulus, G G

    2013-08-30

    Measurements and calculations of the absolute carrier-envelope-phase (CEP) effects in the photodissociation of the simplest molecule, H2(+), with a 4.5-fs Ti:sapphire laser pulse at intensities up to (4±2)×10(14)  W/cm2 are presented. Localization of the electron with respect to the two nuclei (during the dissociation process) is controlled via the CEP of the ultrashort laser pulses. In contrast to previous CEP-dependent experiments with neutral molecules, the dissociation of the molecular ions is not preceded by a photoionization process, which strongly influences the CEP dependence. Kinematically complete data are obtained by time- and position-resolved coincidence detection. The phase dependence is determined by a single-shot phase measurement correlated to the detection of the dissociation fragments. The experimental results show quantitative agreement with ab initio 3D time-dependent Schrödinger equation calculations that include nuclear vibration and rotation.

  14. An Expanding H I Photodissociated Region Associated with the Compact H II Region G213.880-11.837 in the GGD 14 Complex

    NASA Astrophysics Data System (ADS)

    Gómez, Y.; Garay, G.; Rodríguez-Rico, C. A.; Neria, C.; Rodríguez, L. F.; Escalante, V.; Lizano, S.; Lebrón, M.

    2010-10-01

    We present high angular and spectral resolution H I 21 cm line observations toward the cometary-shaped compact H II region G213.880-11.837 in the GGD 14 complex. The kinematics and morphology of the photodissociated region, traced by the H I line emission, reveal that the neutral gas is part of an expanding flow. The kinematics of the H I gas along the major axis of G213.880-11.837 shows that the emission is very extended toward the SE direction, reaching local standard of rest (LSR) radial velocities in the tail of about 14 km s-1. The ambient LSR radial velocity of the molecular gas is 11.5 km s-1, which suggests a champagne flow of the H I gas. This is the second (after G111.61+0.37) cometary H II/H I region known.

  15. International Ultraviolet Explorer observations of the peculiar variable spectrum of the eclipsing binary R Arae

    NASA Technical Reports Server (NTRS)

    Mccluskey, G. E.; Kondo, Y.

    1983-01-01

    The eclipsing binary system R Arae = HD 149730 is a relatively bright southern system with an orbital period of about 4.4 days. It is a single-lined spectroscopic binary. The spectral class of the primary component is B9 Vp. The system was included in a study of mass flow and evolution in close binary systems using the International Ultraviolet Explorer satellite (IUE). Four spectra in the wavelength range from 1150 to 1900 A were obtained with the far-ultraviolet SWP camera, and six spectra in the range from 1900 to 3200 range were obtained with the mid-ultraviolet LWR camera. The close binary R Arae exhibits very unusual ultraviolet spectra. It appears that no other close binary system, observed with any of the orbiting satellites, shows outside-eclipse ultraviolet continuum flux variations of this nature.

  16. The ultraviolet interstellar extinction curve in the Pleiades

    NASA Technical Reports Server (NTRS)

    Witt, A. N.; Bohlin, R. C.; Stecher, T. P.

    1981-01-01

    The wavelength dependence of ultraviolet extinction in the Pleiades dust clouds has been determined from IUE observations of HD 23512, the brightest heavily reddened member of the Pleiades cluster. There is evidence for an anomalously weak absorption bump at 2200 A, followed by an extinction rise in the far ultraviolet with an essentially normal slope. A relatively weak absorption band at 2200 A and a weak diffuse absorption band at 4430 A seem to be common characteristics of dust present in dense clouds. Evidence is presented which suggests that the extinction characteristics found for HD 23512 are typical for a class of extinction curves observed in several cases in the Galaxy and in the LMC.

  17. Amorphous silicon carbide coatings for extreme ultraviolet optics

    NASA Technical Reports Server (NTRS)

    Kortright, J. B.; Windt, David L.

    1988-01-01

    Amorphous silicon carbide films formed by sputtering techniques are shown to have high reflectance in the extreme ultraviolet spectral region. X-ray scattering verifies that the atomic arrangements in these films are amorphous, while Auger electron spectroscopy and Rutherford backscattering spectroscopy show that the films have composition close to stoichiometric SiC, although slightly C-rich, with low impurity levels. Reflectance vs incidence angle measurements from 24 to 1216 A were used to derive optical constants of this material, which are presented here. Additionally, the measured extreme ultraviolet efficiency of a diffraction grating overcoated with sputtered amorphous silicon carbide is presented, demonstrating the feasibility of using these films as coatings for EUV optics.

  18. Method and apparatus for producing durationally short ultraviolet or x-ray laser pulses

    DOEpatents

    MacGowan, B.J.; Matthews, D.L.; Trebes, J.E.

    1987-05-05

    A method and apparatus is disclosed for producing ultraviolet or x- ray laser pulses of short duration. An ultraviolet or x-ray laser pulse of long duration is progressively refracted, across the surface of an opaque barrier, by a streaming plasma that is produced by illuminating a solid target with a pulse of conventional line focused high power laser radiation. The short pulse of ultraviolet or x-ray laser radiation, which may be amplified to high power, is separated out by passage through a slit aperture in the opaque barrier.

  19. Modification of the optoelectronic properties of two-dimensional MoS2 crystals by ultraviolet-ozone treatment

    NASA Astrophysics Data System (ADS)

    Yang, Hae In; Park, Seonyoung; Choi, Woong

    2018-06-01

    We report the modification of the optoelectronic properties of mechanically-exfoliated single layer MoS2 by ultraviolet-ozone exposure. Photoluminescence emission of pristine MoS2 monotonically decreased and eventually quenched as ultraviolet-ozone exposure time increased from 0 to 10 min. The reduction of photoluminescence emission accompanied reduction of Raman modes, suggesting structural degradation in ultraviolet-ozone exposed MoS2. Analysis with X-ray photoelectron spectroscopy revealed that the formation of Ssbnd O and Mosbnd O bonding increases with ultraviolet-ozone exposure time. Measurement of electrical transport properties of MoS2 in a bottom-gate thin-film transistor configuration suggested the presence of insulating MoO3 after ultraviolet-ozone exposure. These results demonstrate that ultraviolet-ozone exposure can significantly influence the optoelectronic properties of single layer MoS2, providing important implications on the application of MoS2 and other two-dimensional materials into optoelectronic devices.

  20. Corongraphic Observations and Analyses of The Ultraviolet Solar Corona

    NASA Technical Reports Server (NTRS)

    Kohl, John L.

    2000-01-01

    The activities supported under NASA Grant NAG5-613 included the following: 1) reduction and scientific analysis of data from three sounding rocket flights of the Rocket Ultraviolet Coronagraph Spectrometer, 2) development of ultraviolet spectroscopic diagnostic techniques to provide a detailed empirical description of the extended solar corona, 3) extensive upgrade of the rocket instrument to become the Ultraviolet Coronal Spectrometer (UVCS) for Spartan 201,4) instrument scientific calibration and characterization, 5) observation planning and mission support for a series of five Spartan 201 missions (fully successful except for STS 87 where the Spartan spacecraft was not successfully deployed and the instruments were not activated), and 6) reduction and scientific analysis of the UVCS/Spartan 201 observational data. The Ultraviolet Coronal Spectrometer for Spartan 201 was one unit of a joint payload and the other unit was a White Light Coronagraph (WLC) provided by the High Altitude Observatory and the Goddard Space Flight Center. The two instruments were used in concert to determine plasma parameters describing structures in the extended solar corona. They provided data that could be used individually or jointly in scientific analyses. The WLC provided electron column densities in high spatial resolution and high time resolution. UVCS/Spartan provided hydrogen velocity distributions, and line of sight hydrogen velocities. The hydrogen intensities from UVCS together with the electron densities from WLC were used to determine hydrogen outflow velocities. The UVCS also provided O VI intensities which were used to develop diagnostics for velocity distributions and outflow velocities of minor ions.

  1. Ultraviolet Viewing with a Television Camera.

    ERIC Educational Resources Information Center

    Eisner, Thomas; And Others

    1988-01-01

    Reports on a portable video color camera that is fully suited for seeing ultraviolet images and offers some expanded viewing possibilities. Discusses the basic technique, specialized viewing, and the instructional value of this system of viewing reflectance patterns of flowers and insects that are invisible to the unaided eye. (CW)

  2. Vacuum and ultraviolet radiation effects on binders and pigments for spacecraft thermal control coatings

    NASA Technical Reports Server (NTRS)

    Progar, D. J.; Wade, W. R.

    1971-01-01

    An evaluation of several silicone resin binders and powdered inorganic pigments for potential use in spacecraft thermal-control paint formulations is presented. The pigments were selected on the basis of a hypothesis relating the heat of formation of a compound to the compound's resistance to ultra-radiation-induced degradation. Reflectance measurements were made in situ to determine degradation rates due to ultraviolet radiation. The tested polydimethylsiloxane resins were not significantly affected by long exposures to ultraviolet radiation. All the pigments, which were dispersed in a polydimethylsiloxane resin, were degraded by ultraviolet radiation as determined by an increase of solar absorptance. For the materials evaluated in this study, no evidence was found to indicate that pigments with high heats of formation were resistant to ultraviolet degradation.

  3. Reactor for simulation and acceleration of solar ultraviolet damage

    NASA Technical Reports Server (NTRS)

    Laue, E.; Gupta, A.

    1979-01-01

    An environmental test chamber providing acceleration of UV radiation and precise temperature control (+ or -)1 C was designed, constructed and tested. This chamber allows acceleration of solar ultraviolet up to 30 suns while maintaining temperature of the absorbing surface at 30 C - 60 C. This test chamber utilizes a filtered medium pressure mercury arc as the source of radiation, and a combination of selenium radiometer and silicon radiometer to monitor solar ultraviolet (295-340 nm) and total radiant power output, respectively. Details of design and construction and operational procedures are presented along with typical test data.

  4. Observed ozone response to variations in solar ultraviolet radiation

    NASA Technical Reports Server (NTRS)

    Gille, J. C.; Smythe, C. M.; Heath, D. F.

    1984-01-01

    During the winter of 1979, the solar ultraviolet irradiance varied with a period of 13.5 days and an amplitude of 1 percent. The zonal mean ozone values in the tropics varied with the solar irradiance, with an amplitude of 0.25 to 0.60 percent. This observation agrees with earlier calculations, although the response may be overestimated. These results imply changes in ozone at an altitude of 48 kilometers of up to 12 percent over an 11-year solar cycle. Interpretation of ozone changes in the upper stratosphere will require measurements of solar ultraviolet radiation at wavelengths near 200 nanometers.

  5. Effects of near ultraviolet and green radiations on plant growth

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Klein, R.M.; Edsall, P.C.; Gentile, A.C.

    Selective removal of near ultraviolet and green wavelengths from white light permitted enhanced growth of marigold, tomato, corn, and Impatiens plants, Chlamydomonas cells and the mycelium of Sordaria. Additions of near ultraviolet and green radiations caused repressions in the growth of marigold and Sordaria. These wavelengths do not alter the oxidative mechanisms of mitochondria, intact algal cells or marigold leaf tissues. The capacity for chlorophyll and carotenoid synthesis by Euglena cells was unaffected by these wavelengths. 23 references, 2 figures, 4 tables.

  6. In situ gene expression profiling of the thermoacidophilic alga Cyanidioschyzon in relation to visible and ultraviolet irradiance.

    PubMed

    Skorupa, Dana J; Castenholz, Richard W; Mazurie, Aurélien; Carey, Charles; Rosenzweig, Frank; McDermott, Timothy R

    2014-06-01

    Ultraviolet and high-intensity visible radiation generate reactive intermediates that damage phototrophic microorganisms. In Yellowstone National Park, the thermoacidophilic alga Cyanidioschyzon exhibits an annual seasonal biomass fluctuation referred to as 'mat decline', where algal viability decreases as ultraviolet and visible irradiances increase during summer. We examined the role irradiance might play in mat decline using irradiance filters that uncouple ultraviolet and visible effects along with custom microarrays to study gene expression in situ. Of the 6507 genes, 88% showed no response to ultraviolet or visible, implying that at the biomolecular level, these algae inhabit a chemostat-like environment and is consistent with the near constant aqueous chemistry measured. The remaining genes exhibited expression changes linked to ultraviolet exposure, to increased visible radiation, or to the apparent combined effects of ultraviolet and visible. Expression of DNA repetitive elements was synchronized, being repressed by visible but also influenced by ultraviolet. At highest irradiance levels, these algae reduced transcription of genes encoding functions involved with DNA replication, photosynthesis and cell cycle progression but exhibited an uptick in activities related to repairing DNA damage. This corroborates known physiological responses to ultraviolet and visible radiation, and leads us to provisionally conclude that mat decline is linked to photoinhibition. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

  7. In situ measurements of the mesosphere and stratosphere

    NASA Technical Reports Server (NTRS)

    Crosky, C.

    1976-01-01

    The operation of a subsonic, Gerdien condenser probe for in situ measurements of the mesosphere and stratosphere is presented. The inclusion of a flashing Lyman alpha ultraviolet source provides an artifically produced ionization of particular constituents. Detailed theory of operation is presented and the data results from two flights are shown. A great deal of fine structure in mobility is observed due to the presence of various hydrated positive ions. The effect of the Lyman alpha source in the 35 km region was to dissociate a light hydrate ion rather than produce additional ionization. At the 70 km region, photodissociation of the heaviest ions (probably ice crystals) was also observed.

  8. Reduction of chlorine radical chemical etching of GaN under simultaneous plasma-emitted photon irradiation

    NASA Astrophysics Data System (ADS)

    Liu, Zecheng; Imamura, Masato; Asano, Atsuki; Ishikawa, Kenji; Takeda, Keigo; Kondo, Hiroki; Oda, Osamu; Sekine, Makoto; Hori, Masaru

    2017-08-01

    Surface chemical reactions on the GaN surface with Cl radicals are thermally enhanced in the high-temperature Cl2 plasma etching of GaN, resulting in the formation of etch pits and thereby, a roughened surface. Simultaneous irradiation of ultraviolet (UV) photons in Cl2 plasma emissions with wavelengths of 258 and 306 nm reduces the surface chemical reactions because of the photodissociation of both Ga and N chlorides, which leads to a suppression of the increase in surface roughness. Compared with Si-related materials, we point out that photon-induced reactions should be taken into account during the plasma processing of wide-bandgap semiconductors.

  9. Urban tree influences on ultraviolet irradiance

    Treesearch

    Gordon M. Heisler; Richard H. Grant; Wei Gao

    2002-01-01

    Many of the effects of ultraviolet radiation (UVR) on people and their environment - damage to various materials, survival of insects and microbial pathogens, growth of vegetation, and adverse or beneficial effects on human health - are modified by the presence of trees. Human epidemiological investigations generally consider exposure as given by indices of UVR...

  10. DELAY OF CLEAVAGE OF THE ARBACIA EGG BY ULTRAVIOLET RADIATION

    PubMed Central

    Blum, Harold F.; Price, Judith P.

    1950-01-01

    While our data do not permit us to state the exact locus or mode of action of ultraviolet radiation in the Arbacia egg, certain general conclusions may be reached. The amount of delay of cleavage of these eggs is determined by two principal factors: (1) The extent of an effect, resulting from photochemical action induced by ultraviolet radiation, which is reversible in a biological sense, the reversibility not being directly dependent upon the process of cell division. (2) The sensitivity of the cell division process to the effects of the ultraviolet-induced photochemical reaction. This factor varies with the stage of cell division, the cell being insensitive during a period corresponding to most of mitosis. It seems likely that these findings may apply to cell division in general, but, since the quantitative relationships observed must, in this case, reflect the integration of two semi-independent factors, the over-all picture may appear quite different for different kinds of cells. PMID:15410486

  11. Plasminogen activator: analysis of enzyme induction by ultraviolet irradiation mapping

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Miskin, R.; Reich, E.; Dixon, K.

    1981-10-01

    Ultraviolet irradiation mapping techniques have previously been used to study the organization of eucaryotic gene classes and transcription units. We used the same method to probe some regulatory phenomena observed in the induction of plasminogen activator (PA) biosynthesis: PA synthesis in chicken embryo fibroblasts is induced by tumor-promoting phorbol esters and by retinoic acid; furthermore, PA induction by phorbol esters is synergistic with transformation, being 10- to 20-fold greater in virus-transformed cells than in normal cells. We found that the ultraviolet irradiation inactivation cross sections for PA induction by phorbol esters and by retinoate differed significantly, suggesting that these agentsmore » induce PA biosynthesis by different mechanisms. On the other hand, the ultraviolet irradiation sensitivity of phorbol ester induction in normal chicken embryo fibroblasts was the same as in transformed cells, indicating that the synergism of transformation and phorbol esters is probably not due to different pathways of PA induction.« less

  12. Ultraviolet Radiation Induction of Mutation in Penicillium Claviforme.

    ERIC Educational Resources Information Center

    New, June; Jolley, Ray

    1986-01-01

    Cites reasons why Penicillium claviforme is an exceptionally good species for ultraviolet induced mutation experiments. Provides a set of laboratory instructions for teachers and students. Includes a discussion section. (ML)

  13. Method and apparatus for producing durationally short ultraviolet or X-ray laser pulses

    DOEpatents

    MacGowan, Brian J.; Matthews, Dennis L.; Trebes, James E.

    1988-01-01

    A method and apparatus is disclosed for producing ultraviolet or X-ray laser pulses of short duration (32). An ultraviolet or X-ray laser pulse of long duration (12) is progressively refracted, across the surface of an opaque barrier (28), by a streaming plasma (22) that is produced by illuminating a solid target (16, 18) with a pulse of conventional line focused high power laser radiation (20). The short pulse of ultraviolet or X-ray laser radiation (32), which may be amplified to high power (40, 42), is separated out by passage through a slit aperture (30) in the opaque barrier (28).

  14. EFFECT OF ULTRA-VIOLET IRRADIATION OF RIBONUCLEIC ACID ON ITS CHROMATOGRAPHIC BEHAVIOUR

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kubinski, H.

    1963-11-01

    Experiments were made to illustrate the effects of ultraviolet radiation on RNA isolated from uninfected mammalian cells as well as those from those infected with polio virus. The chromatographic recovery of irradiated RNA, as judged by ultraviolet adsorbance and radioactivity (no plaque formers were found after irradiation), was considerably lower than that of unirradiated RNA. (P.C.H.)

  15. APOLLO 16 ASTRONAUTS JOHN YOUNG AND CHARLES DUKE EXAMINE FAR ULTRAVIOLET CAMERA

    NASA Technical Reports Server (NTRS)

    1971-01-01

    Apollo 16 Lunar Module Pilot Charles M. Duke, Jr., left and Mission Commander John W. Young examine Far Ultraviolet Camera they will take to the Moon in March. They will measure the universe's ultraviolet spectrum. They will be launched to the Moon no earlier than March 17, 1972, with Command Module Pilot Thomas K. Mattingly, II.

  16. New advances in protection against solar ultraviolet radiation in textiles for summer clothing.

    PubMed

    Aguilera, José; de Gálvez, María Victoria; Sánchez-Roldán, Cristina; Herrera-Ceballos, Enrique

    2014-01-01

    Clothing is considered one of the most important tools for photoprotection against harmful solar ultraviolet radiation (UVR). The standard for sun-protective clothing is based on erythema despite other biological effects of UVR on the skin. We analyzed the potential protection against UVR in fabrics destined for summer clothing based on several action spectra. We examined 50 garments classified by type of fabric composition, structure of the fiber yarn and color. The ultraviolet protection factor was calculated based on fabric ultraviolet transmittance corrected for erythema according to the EU standard E-13758 as well as the UVA transmittance of fabrics. UVR protection was also analyzed in base of different action spectra as for previtamin D3, nonmelanoma skin cancer, photoimmunosuppression and photoaging. Most knitted fabrics used for sports T-shirts offered excellent ratings for ultraviolet protection while normal shirts showed very low ratings, particularly against photoaging. The cover is the most influential variable in fabric photoprotection, having an exponential relationship with the UPF. The relation between cover and UVA protection was linearly negative. Information about ultraviolet protection in textiles used for summer clothing should be included in labeling as some types of fabrics, especially those used for shirts, offer very low UVR protection. © 2014 The American Society of Photobiology.

  17. Auroral Observations from the POLAR Ultraviolet Imager (UVI)

    NASA Technical Reports Server (NTRS)

    Germany, G. A.; Spann, J. F.; Parks, G. K.; Brittnacher, M. J.; Elsen, R.; Chen, L.; Lummerzheim, D.; Rees, M. H.

    1998-01-01

    Because of the importance of the auroral regions as a remote diagnostic of near-Earth plasma processes and magnetospheric structure, spacebased instrumentation for imaging the auroral regions have been designed and operated for the last twenty-five years. The latest generation of imagers, including those flown on the POLAR satellite, extends this quest for multispectral resolution by providing three separate imagers for the visible, ultraviolet, and X ray images of the aurora. The ability to observe extended regions allows imaging missions to significantly extend the observations available from in situ or groundbased instrumentation. The complementary nature of imaging and other observations is illustrated below using results from tile GGS Ultraviolet Imager (UVI). Details of the requisite energy and intensity analysis are also presented.

  18. ULTRAVIOLET EXTINCTION AT HIGH GALACTIC LATITUDES

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Peek, J. E. G.; Schiminovich, David, E-mail: jegpeek@gmail.com

    In order to study the properties and effects of high Galactic latitude dust, we present an analysis of 373,303 galaxies selected from the Galaxy Evolution Explorer All-Sky Survey and Wide-field Infrared Explorer All-Sky Data Release. By examining the variation in aggregate ultraviolet colors and number density of these galaxies, we measure the extinction curve at high latitude. We additionally consider a population of spectroscopically selected galaxies from the Sloan Digital Sky Survey to measure extinction in the optical. We find that dust at high latitude is neither quantitatively nor qualitatively consistent with standard reddening laws. Extinction in the FUV andmore » NUV is {approx}10% and {approx}35% higher than expected, with significant variation across the sky. We find that no single R{sub V} parameter fits both the optical and ultraviolet extinction at high latitude, and that while both show detectable variation across the sky, these variations are not related. We propose that the overall trends we detect likely stem from an increase in very small silicate grains in the interstellar medium.« less

  19. Far-ultraviolet Bidirectional Photometry of Apollo Soil 10084: New Results from The Southwest Ultraviolet Reflectance Chamber (SwURC).

    NASA Astrophysics Data System (ADS)

    Raut, U.

    2017-12-01

    We report new measurements of the far-ultraviolet (115-180 nm) bidirectional reflectance of Apollo soil 10084 in the Southwest Ultraviolet Reflectance Chamber (SwURC). We find the bidirectional reflectance distribution function (BRDF) to be featureless in this wavelength region, though with a small blue slope. The angular distribution of the BRDF at Ly-α and 160 nm shows that this mature mare soil, containing nanophase Fe and enriched in Ti, anisotropically scatters light in the forward direction. The phase angle dependence of the BRDF is fitted with Hapke's photometric model with an additional diffuse-directional term. Future plans include measurements of mare and highland soils of differing maturity index (Is/FeO), water ice frost and lunar soil-ice aggregates. Such measurements will help constrain the abundance and distribution of the water ice on the illuminated lunar surface and dark permanently shadowed regions of the moon, as reported by LRO-LAMP.

  20. ULTRAVIOLET DISINFECTION STUDIES WITH CCL LISTED MICROORGANISMS

    EPA Science Inventory

    Resistance to ultraviolet (UV) disinfection is an essential aspect regarding all microbial groups listed on the CCL. The U.S. drinking water industry is interested in including UV light treatment as an amendment to conventional treatment for disinfecting water supplies. UV disi...