WorldWideScience

Sample records for theoretical infrared spectra

  1. Theoretical modeling of infrared spectra of the hydrogen and deuterium bond in aspirin crystal

    Science.gov (United States)

    Ghalla, Houcine; Rekik, Najeh; Michta, Anna; Oujia, Brahim; Flakus, Henryk T.

    2010-01-01

    An extended quantum theoretical approach of the ν IR lineshape of cyclic dimers of weakly H-bonded species is proposed. We have extended a previous approach [M.E.-A. Benmalti, P. Blaise, H.T. Flakus, O. Henri-Rousseau, Chem. Phys. 320 (2006) 267] by accounting for the anharmonicity of the slow mode which is described by a "Morse" potential in order to reproduce the polarized infrared spectra of the hydrogen and deuterium bond in acetylsalicylic acid (aspirin) crystals. From comparison of polarized IR spectra of isotopically neat and isotopically diluted aspirin crystals it resulted that centrosymmetric aspirin dimer was the bearer of the crystal main spectral properties. In this approach, the adiabatic approximation is performed for each separate H-bond bridge of the dimer and a strong non-adiabatic correction is introduced into the model via the resonant exchange between the fast mode excited states of the two moieties. Within the strong anharmonic coupling theory, according to which the X-H→⋯Y high-frequency mode is anharmonically coupled to the H-bond bridge, this model incorporated the Davydov coupling between the excited states of the two moieties, the quantum direct and indirect dampings and the anharmonicity for the H-bond bridge. The spectral density is obtained within the linear response theory by Fourier transform of the damped autocorrelation functions. The evaluated spectra are in fairly good agreement with the experimental ones by using a minimum number of independent parameters. The effect of deuteration has been well reproduced by reducing simply the angular frequency of the fast mode and the anharmonic coupling parameter.

  2. THEORETICAL INTERPRETATION OF INFRARED-SPECTRA OF N-CYCLOHEXYL-2-PYRROLIDONE IN MIXTURES OF HEXANE AND CDCL3

    NARCIS (Netherlands)

    LOOS, D; PERJESSY, A; ENGBERTS, JBFN

    The infrared spectra of N-cyclohexyl-2-pyrrolidone (NCP) in binary mixtures of hexane and CDCl3 were interpreted theoretically in the region of C=O stretching vibrations using the AMI semiempirical method. The results were compared with those obtained for N,N-dimethylacetamide (DMA), cyclohexanone

  3. Infrared and Raman spectra and theoretical calculations for benzocyclobutane in its electronic ground state

    Science.gov (United States)

    Ocola, Esther J.; Shin, Hee Won; Laane, Jaan

    2015-02-01

    The infrared and Raman spectra of vapor-phase and liquid-phase benzocyclobutane (BCB) have been recorded and assigned. The structure of the molecule was calculated using the MP2/cc-pVTZ basis set and the vibrational frequencies and spectral intensities were calculated using the B3LYP/cc-pVTZ level of theory. The agreement between experimental and calculated spectra is excellent. In order to allow comparisons with related molecules, ab initio and DFT calculations were also carried out for indan (IND), tetralin (TET), 1,4-benzodioxan (14BZD), 1,3-benzodioxan (13BZD) and 1,4-dihydronaphthalene (14DHN). The ring-puckering, ring-twisting, and ring-flapping vibrations were of particular interest as these reflect the rigidity of the bicyclic ring system. The infrared spectra of BCB show very nice examples of vapor-phase band types and combination bands.

  4. Infrared spectra and theoretical calculations of KH and (KH)2 in solid hydrogen.

    Science.gov (United States)

    Wang, Xuefeng; Andrews, Lester

    2007-12-13

    A matrix isolation IR study of laser-ablated potassium atom reactions with H2 has been performed in solid molecular hydrogen. The KH molecule and (KH)2 cluster were identified by infrared spectra with isotopic substitution (HD and D2) and by comparison to frequencies calculated using density functional theory. In para-hydrogen, the sharp KH absorption suggests dihydrogen complex formation with the ionic KH molecule, which is also characterized by an absorption at 4095 cm(-1). The highly ionic rhombic (KH)2 molecule is formed by dimerization and trapped in solid hydrogen. Calculations at the CCSD(T) level of theory show the increasing ionic character and decreasing stability for the (MH)2 molecule series from Li to Cs.

  5. Theoretical emission line ratios for [Fe III] and [Fe VII] applicable to the optical and infrared spectra of gaseous nebulae.

    Science.gov (United States)

    Keenan, F P; Aller, L H; Ryans, R S; Hyung, S

    2001-08-14

    Recent calculations of electron impact excitation rates and Einstein A-coefficients for transitions among the 3d(6) levels of Fe III and among the 3d(2) levels of Fe VII are used to derive theoretical emission line ratios applicable to the optical and infrared spectra of gaseous nebulae. Results for [Fe III] are generated for electron temperatures T(e) = 7,000-20,000 K and densities N(e) = 10(2)-10(8) cm(-3), whereas those for [Fe VII] are provided for T(e) = 10,000-30,000 K and N(e) = 10(2)-10(8) cm(-3). The theoretical line ratios are significantly different in some instances from earlier calculations and resolve discrepancies between theory and observation found for the planetary nebulae IC 4997 and NGC 7027.

  6. Theoretical study, and infrared and Raman spectra of copper(II) chelated complex with dibenzoylmethane

    DEFF Research Database (Denmark)

    Nekoei, A.-R.; Vakili, M.; Hakimi-Tabar, M.

    2014-01-01

    There are some discrepancies in both the vibrational assignments and in the metal-ligand (M-L) bond strengths predicted in the previous studies on the copper (II) chelated complex of dibenzoylmethane, Cu(dbm)2. Also, there is a lack of theoretical structure, Raman spectrum and full vibrational as...

  7. Infrared spectra and theoretical calculations of lithium hydride clusters in solid hydrogen, neon, and argon.

    Science.gov (United States)

    Wang, Xuefeng; Andrews, Lester

    2007-07-12

    A matrix isolation IR study of laser-ablated lithium atom reactions with H2 has been performed in solid para-hydrogen, normal hydrogen, neon, and argon. The LiH molecule and (LiH)(2,3,4) clusters were identified by IR spectra with isotopic substitution (HD, D(2), and H(2) + D(2)) and comparison to frequencies calculated by density functional theory and the MP2 method. The LiH diatomic molecule is highly polarized and associates additional H(2) to form primary (H(2))(2)LiH chemical complexes surrounded by a physical cage of solid hydrogen where the ortho and para spin states form three different primary complexes and play a role in the identification of the bis-dihydrogen complex and in characterization of the matrix cage. The highly ionic rhombic (LiH)(2) dimer, which is trapped in solid matrices, is calculated to be 22 kcal/mol more stable than the inverse hydrogen bonded linear LiH-LiH dimer, which is not observed here. The cyclic lithium hydride trimer and tetramer clusters were also observed. Although the spontaneous reaction of 2 Li and H(2) to form (LiH)(2) occurs on annealing in solid H(2), the formation of higher clusters requires visible irradiation. We observed the simplest possible chemical reduction of dihydrogen using two lithium valence electrons to form the rhombic (LiH)(2) dimer.

  8. Sodium hydride clusters in solid hydrogen and neon: infrared spectra and theoretical calculations.

    Science.gov (United States)

    Wang, Xuefeng; Andrews, Lester

    2007-08-02

    Laser-ablated sodium atom reactions with H2 have been investigated in solid molecular hydrogens and neon. The NaH molecule and (NaH)2,3,4 clusters were identified by IR spectra with isotopic substitution (HD and D2) and comparison to frequencies calculated by density functional theory and the MP2 method. The use of para-hydrogen enriched samples provides evidence for a (H2)nNaH subcomplex surrounded by the solid hydrogen matrix cage. The ionic rhombic (NaH)2 dimer is characterized by strong absorptions at 761.7, 759.1, and 757.0 cm(-1), respectively, in solid neon, para-hydrogen, and normal hydrogen matrices. The cyclic sodium hydride trimer and tetramer clusters are also observed. Although the spontaneous reaction of two Li and H2 to form (LiH)2 occurs on annealing in solid H2, the formation of (NaH)2 requires near uv photoexcitation.

  9. Reactions of Ti, Zr, and Hf atoms with hydrogen sulfide: argon matrix infrared spectra and theoretical calculations.

    Science.gov (United States)

    Wang, Qiang; Zhao, Jie; Wang, Xuefeng

    2015-03-19

    Laser-ablated Ti, Zr, and Hf atoms have been codeposited at 4 K with hydrogen sulfide in excess argon. The metal atoms insert into the S-H bond of hydrogen sulfide to form the HMSH, H2MS, and H2M(SH)2 molecules (M = Ti, Zr, Hf), which were identified on the basis of the D2S and H2(34)S isotopic substitutions. The observed vibrational frequencies of these species were reproduced by B3LYP functional calculations. The reaction mechanisms have been proposed on the potential energy surface of the studied system to account for the formation of these molecules. We have made a theoretical prediction about the H2MS complexes dehydrogenation, which can provide a novel proposal for generating hydrogen from H2S.

  10. THEORETICAL SPECTRA OF TERRESTRIAL EXOPLANET SURFACES

    Energy Technology Data Exchange (ETDEWEB)

    Hu Renyu; Seager, Sara [Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Ehlmann, Bethany L., E-mail: hury@mit.edu [Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125 (United States)

    2012-06-10

    We investigate spectra of airless rocky exoplanets with a theoretical framework that self-consistently treats reflection and thermal emission. We find that a silicate surface on an exoplanet is spectroscopically detectable via prominent Si-O features in the thermal emission bands of 7-13 {mu}m and 15-25 {mu}m. The variation of brightness temperature due to the silicate features can be up to 20 K for an airless Earth analog, and the silicate features are wide enough to be distinguished from atmospheric features with relatively high resolution spectra. The surface characterization thus provides a method to unambiguously identify a rocky exoplanet. Furthermore, identification of specific rocky surface types is possible with the planet's reflectance spectrum in near-infrared broad bands. A key parameter to observe is the difference between K-band and J-band geometric albedos (A{sub g}(K) - A{sub g}(J)): A{sub g}(K) - A{sub g}(J) > 0.2 indicates that more than half of the planet's surface has abundant mafic minerals, such as olivine and pyroxene, in other words primary crust from a magma ocean or high-temperature lavas; A{sub g}(K) - A{sub g}(J) < -0.09 indicates that more than half of the planet's surface is covered or partially covered by water ice or hydrated silicates, implying extant or past water on its surface. Also, surface water ice can be specifically distinguished by an H-band geometric albedo lower than the J-band geometric albedo. The surface features can be distinguished from possible atmospheric features with molecule identification of atmospheric species by transmission spectroscopy. We therefore propose that mid-infrared spectroscopy of exoplanets may detect rocky surfaces, and near-infrared spectrophotometry may identify ultramafic surfaces, hydrated surfaces, and water ice.

  11. Double and Triple Si-H-M Bridge Bonds: Matrix Infrared Spectra and Theoretical Calculations for Reaction Products of Silane with Ti, Zr, and Hf Atoms.

    Science.gov (United States)

    Xu, Bing; Shi, Peipei; Huang, Tengfei; Wang, Xuefeng; Andrews, Lester

    2017-05-25

    Infrared spectra of matrix isolated dibridged Si(μ-H) 2 MH 2 and tribridged Si(μ-H) 3 MH molecules (M = Zr and Hf) were observed following the laser-ablated metal atom reactions with SiH 4 during condensation in excess argon and neon, but only the latter species was observed with titanium. Assignments of the major vibrational modes, which included terminal MH, MH 2 and hydrogen bridge Si-H-M stretching modes, were confirmed by the appropriate SiD 4 isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). The Si-H-M hydrogen bridge bond is calculated as weak covalent interaction and compared with the C-H···M agostic interaction in terms of electron localization function (ELF) analysis and noncovalent interaction index (NCI) calculations. Furthermore, the different products of Ti, Zr, and Hf reactions with SiH 4 are discussed in detail.

  12. Infrared spectra of mineral species

    CERN Document Server

    Chukanov, Nikita V

    2014-01-01

    This book details more than 3,000 IR spectra of more than 2,000 mineral species collected during last 30 years. It features full descriptions and analytical data of each sample for which IR spectrum was obtained.

  13. Infrared spectra of thyroid tumor tissues

    Science.gov (United States)

    Tolstorozhev, G. B.; Skornyakov, I. V.; Butra, V. A.

    2010-07-01

    We used infrared spectroscopy methods to study thyroid tumor tissues removed during surgery. The IR spectra of the surgical material are compared with data from histological examination. We show that in malignant neoplasms, the spectra of proteins in the region of C=O vibrations are different from the spectra of these substances in benign tumors and in tissues outside the pathological focus at a distance >1 cm from the margin of the tumor. The differences in the spectra are due to changes in the supermolecular structure of the proteins, resulting from rearrangement of the system of hydrogen bonds. We identify the spectral signs of malignant pathologies.

  14. Oxidation of carbynes: signatures in infrared spectra

    NARCIS (Netherlands)

    Cinquanta, Eugenio; Manini, Nicola; Ravagnan, Luca; Caramella, Lucia; Onida, Giovanni; Milani, Paolo; Rudolf, Petra

    2014-01-01

    We report and solidly interpret the infrared spectrum of both pristine and oxidized carbynes embedded in a pure-carbon matrix. The spectra probe separately the effects of oxidation on sp- and on sp 2-hybridized carbon, and provide information on the stability of the different structures in an

  15. Intrinsic Spectra of Hyperluminous Infrared Galaxies

    Science.gov (United States)

    Rieke, George; Hines, Dean

    2004-09-01

    We will use the low and high spectral resolution capabilities of the IRS aboard SIRTF to obtain high signal-to-noise mid-infrared spectra of a small sample of the most luminous Active Galactic Nuclei, which are characterized by their "warm" far-infrared spectral energy distributions as obtained by IRAS (the so called Hyperluminous Infrared Galaxies or HIGs). The sample consists of both Type 2 and Type 1 AGNs. The Type 1 objects present a relatively unobscured view of the central engine, and also have a polarized (scattered) component that is completely unobscured. The Type 2 objects have Type 1 polarized spectra, but this scattered light is highly extinguished indicating some obscuration even along the line of sight to the scattering region. The sample will allow us to compare the properties of the Type 1s and Type 2s, thus providing a check on the orientation and providing strong constraints on the geometry and internal structure of all four objects.

  16. Gas Cell Development for Infrared Spectra Calibration

    Science.gov (United States)

    Valdivielso, Luisa; Esparza, Pedro; Martín, Eduardo L.

    NAHUAL is a high-resolution near-infrared echelle spectrograph of high stability on preliminary phase development for GTC (Gran Telescopio de Canarias). Its natural location is a Nasmyth focus. One of the principal scientific aims is to carry out high precision radial velocity measurements (from 1 to 10 m/s) in the near infrared. To achieve high stability on radial velocity measurements, NAHUAL needs a calibration unit that uses a mixture of gases whose absorption spectra must be as homogeneous as possible between 0.95 and 2.4 μm. We report on the measurements done to date with potentially active gas mixtures as acetylene, methane, nitrous oxide or hydrocarbons.

  17. Machine learning molecular dynamics for the simulation of infrared spectra.

    Science.gov (United States)

    Gastegger, Michael; Behler, Jörg; Marquetand, Philipp

    2017-10-01

    Machine learning has emerged as an invaluable tool in many research areas. In the present work, we harness this power to predict highly accurate molecular infrared spectra with unprecedented computational efficiency. To account for vibrational anharmonic and dynamical effects - typically neglected by conventional quantum chemistry approaches - we base our machine learning strategy on ab initio molecular dynamics simulations. While these simulations are usually extremely time consuming even for small molecules, we overcome these limitations by leveraging the power of a variety of machine learning techniques, not only accelerating simulations by several orders of magnitude, but also greatly extending the size of systems that can be treated. To this end, we develop a molecular dipole moment model based on environment dependent neural network charges and combine it with the neural network potential approach of Behler and Parrinello. Contrary to the prevalent big data philosophy, we are able to obtain very accurate machine learning models for the prediction of infrared spectra based on only a few hundreds of electronic structure reference points. This is made possible through the use of molecular forces during neural network potential training and the introduction of a fully automated sampling scheme. We demonstrate the power of our machine learning approach by applying it to model the infrared spectra of a methanol molecule, n -alkanes containing up to 200 atoms and the protonated alanine tripeptide, which at the same time represents the first application of machine learning techniques to simulate the dynamics of a peptide. In all of these case studies we find an excellent agreement between the infrared spectra predicted via machine learning models and the respective theoretical and experimental spectra.

  18. Infrared spectra of hydrogen-bonded salicylic acid and its derivatives : Salicylic acid and acetylsalicylic acid

    Science.gov (United States)

    Wójcik, Marek J.

    1981-11-01

    Infrared spectra of hydrogen-bonded salicylic acid, O-deutero-salicylic acid and acetylsalicylic acid crystals have been studied experimentally and theoretically. Interpretation of these spectra was based on the Witkowski-Maréchal model. Semi-quantitative agreement between experimental and theoretical spectra can be achieved with the simplest form of this model, with values of interaction parameters transferable for equivalent intermolecular hydrogen bonds.

  19. Theoretical modelling of actinide spectra in solution

    International Nuclear Information System (INIS)

    Danilo, Cecile

    2009-01-01

    The framework of this PhD is the interpretation of Nuclear Magnetic Relaxation Dispersion experiments performed on solvated U 4+ , NpO 2 + and PuO 2 2+ , which all have a f 2 configuration. Unexpectedly the two actinyl ions have a much higher relaxivity than U 4+ ,. One possible explanation is that the electronic relaxation rate is faster for Uranium(IV) than for the actinyl ions. We address this problem by exploring the electronic spectrum of the three compounds in gas phase and in solution with a two-step SOCI (Spin-Orbit Configuration-Interaction) method. The influence of electron correlation (treated in the first step) and spin-orbit relaxation effects (considered in the second step) has been discussed thoroughly. Solvent effects have been investigated as well. Another issue that has been questioned is the accuracy of Density Functional Theory for the study of actinide species. This matter has been discussed by comparing its performance to wave-function based correlated methods. The chemical problem chosen was the water exchange in [UO 2 2+ (H 2 O) 5 ]. We looked at the associative and at the dissociative mechanisms using a model with one additional water in the second hydration sphere. The last part of the thesis dealt with the spectroscopy of coordinated Uranyl(V). Absorption spectrum of Uranyl(V) with various ligands has been recorded. The first sharp absorption bands in the Near-Infrared region were assigned to the Uranium centered 5f-5f transitions, but uncertainties remained for the assignment of transitions observed in the Visible region. We computed the spectra of naked UO 2 + and [UO 2 (CO 3 ) 3 ] 5- to elucidate the spectral changes induced by the carbonate ligands. (author) [fr

  20. Synthesis and infrared spectra of alkaline earth metal carbonates ...

    Indian Academy of Sciences (India)

    The metal carbonate, MCO3 (M = Ca, Sr and Ba), was synthesized by a novel method of reacting aqueous solution of each of Ca2+, Sr2+ and Ba2+ salts with urea at high temperature, ∼ 80°C. The reaction products were characterized through elemental analysis and infrared spectra. The infrared spectra of the products are ...

  1. Synthesis and infrared spectra of alkaline earth metal carbonates ...

    Indian Academy of Sciences (India)

    Unknown

    ... Sr2+ and Ba2+ salts with urea at high temperature, ~ 80°C. The reaction products were characterized through elemental analysis and infrared spectra. The infrared spectra of the products are the same as those of the corresponding commercially obtained carbonates. A general reaction describing the formation of MCO3 ...

  2. Infrared spectra of inorganic compounds (3800-45cm- 1)

    National Research Council Canada - National Science Library

    Nyquist, Richard A; Kagel, Ronald O; Kagel, Ron

    1971-01-01

    ... availability of low- cost infrared spectrometers. For these reasons, over the last 30 years large numbers of standard spectra of organic compounds have been collected and catalogued, and are presently available for reference...

  3. Prediction of pork quality attributes from near infrared reflectance spectra

    NARCIS (Netherlands)

    Geesink, G.H.; Schreutelkamp, F.H.; Frankhuizen, R.; Vedder, H.W.; Faber, N.M.; Kranen, R.W.; Gerritzen, M.A.

    2003-01-01

    Near infrared spectroscopy (NIRS) is one of the most promising techniques for large-scale meat quality evaluation. We investigated the potential of NIRS-based models to predict drip loss and shear force of pork samples. Near infrared reflectance spectra (1000¿2500 nm), water-holding capacity, shear

  4. Fourier transform infrared emission spectra of atomic rubidium: g- and h-states

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Ferus, Martin; Kubelík, Petr; Chernov, Vladislav E.; Zanozina, Ekaterina M.

    2012-01-01

    Roč. 45, č. 17 (2012), s. 175002 ISSN 0953-4075 R&D Projects: GA AV ČR IAAX00100903 Institutional support: RVO:61388955 Keywords : Fourier transform infrared emission spectra * atomic rubidium * physical chemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.031, year: 2012

  5. Infrared spectra of lunar soils. [using a Michelson interferometer

    Science.gov (United States)

    Aronson, J. R.; Emslie, A. G.; Smith, E. M.

    1979-01-01

    Measured data obtained by Michelson interferometer spectrometer were stored in a computer file and smoothed by being passed forward and backward through a digital four-pole low pass filter. Infrared spectra of the 10 lunar samples are presented in the format of brightness temperature versus frequency. The mol % of feldspar, pyroxene, olivine, ilmenite and ferromagnetic silicate in each sample is presented in tables. The reflectance spectra of ilmenite and enstatite are shown in graphs.

  6. Connecting infrared spectra with plant traits to identify species

    Science.gov (United States)

    Buitrago, Maria F.; Skidmore, Andrew K.; Groen, Thomas A.; Hecker, Christoph A.

    2018-05-01

    Plant traits are used to define species, but also to evaluate the health status of forests, plantations and crops. Conventional methods of measuring plant traits (e.g. wet chemistry), although accurate, are inefficient and costly when applied over large areas or with intensive sampling. Spectroscopic methods, as used in the food industry and mineralogy, are nowadays applied to identify plant traits, however, most studies analysed visible to near infrared, while infrared spectra of longer wavelengths have been little used for identifying the spectral differences between plant species. This study measured the infrared spectra (1.4-16.0 μm) on individual, fresh leaves of 19 species (from herbaceous to woody species), as well as 14 leaf traits for each leaf. The results describe at which wavelengths in the infrared the leaves' spectra can differentiate most effectively between these plant species. A Quadratic Discrimination Analysis (QDA) shows that using five bands in the SWIR or the LWIR is enough to accurately differentiate these species (Kappa: 0.93, 0.94 respectively), while the MWIR has a lower classification accuracy (Kappa: 0.84). This study also shows that in the infrared spectra of fresh leaves, the identified species-specific features are correlated with leaf traits as well as changes in their values. Spectral features in the SWIR (1.66, 1.89 and 2.00 μm) are common to all species and match the main features of pure cellulose and lignin spectra. The depth of these features varies with changes of cellulose and leaf water content and can be used to differentiate species in this region. In the MWIR and LWIR, the absorption spectra of leaves are formed by key species-specific traits including lignin, cellulose, water, nitrogen and leaf thickness. The connection found in this study between leaf traits, features and spectral signatures are novel tools to assist when identifying plant species by spectroscopy and remote sensing.

  7. Retrieval of temperature profiles from Martian infrared spectra

    Science.gov (United States)

    Mcmillan, W. Wallace; Pearl, John C.; Conrath, Barney J.

    1993-01-01

    In theory, a thermal emission spectrum of Mars (220-1600 cm(exp -1)) contains a wealth of information about the composition and thermal structure of the atmosphere and surface. However, in practice, the ability to retrieve quantitative information from the spectrum is limited by a number of factors including (1) the ill-posed nature of the spectral inversion problem and the resulting nonuniqueness of all solutions; (2) assumptions built into any spectral inversion program; (3) uncertainties in surface pressure, temperature, and emissivity; and (4) uncertainties in the optical properties of atmospheric aerosols. Below, factors (1) and (2) are discussed as fundamental limitations on temperature retrievals from Mariner 9 Infrared Interferometer Spectrometer (IRIS) spectra. In preparation for the Mars Observer mission and the return of tens of thousands of infrared spectra per day from the Thermal Emission Spectrometer (TES), we have developed a fast inversion algorithm to retrieve temperature structure and aerosol opacity from the infrared spectra. The derived atmospheric models will be used to provide the atmospheric contribution to the TES spectra, so that the thermal emission spectra of the underlying surface can be determined for making mineralogical identifications. As a test of our algorithm, we are undertaking a systematic analysis of the entire Mariner 9 Infrared Interferometric Spectrometer (IRIS) dataset of 21,000 plus spectra. While portions of the IRIS dataset have been previously analyzed, the lack of a speedy and robust algorithm to invert the IRIS spectra to retrieve temperature profiles and aerosol opacities has been a major impediment to a truly comprehensive analysis.

  8. Infrared spectra of zinc doped lead borate glasses

    Indian Academy of Sciences (India)

    Unknown

    Abstract. The infrared spectra of zinc-doped lead borate glasses (10–30 mol% ZnO) were measured over a continuous spectral range (400–4000 cm–1) in an attempt to study their structure systematically. No boroxol ring formation was observed in the structure of these glasses. The formation of Zn in tetrahedral ...

  9. Magnetic measurements, Raman and infrared spectra of metal ...

    Indian Academy of Sciences (India)

    70

    Magnetic measurements, Raman and infrared spectra of metal- ligand complex derived from CoCl2·6H2Oand ... molecule derived transition metal (TM) ion based complexes have opened a wide research field in the interface of physics and ..... will give the proper value of the magnetic moment. The present value suggests.

  10. Quantitative Infrared Spectra of Vapor Phase Chemical Agents

    Energy Technology Data Exchange (ETDEWEB)

    Sharpe, Steven W.; Johnson, Timothy J.; Chu, P M.; Kleimeyer, J; Rowland, Brad; Gardner, Patrick J.

    2003-04-21

    Quantitative high resolution (0.1 cm -1) infrared spectra have been acquired for a number of pressure broadened (101.3 KPa N2), vapor phase chemicals including: Sarin (GB), Soman (GD), Tabun (GA), Cyclosarin (GF), VX, nitrogen mustard (HN3), sulfur mustard (HD) and Lewisite (L).

  11. A Simulation Program for Dynamic Infrared (IR) Spectra

    Science.gov (United States)

    Zoerb, Matthew C.; Harris, Charles B.

    2013-01-01

    A free program for the simulation of dynamic infrared (IR) spectra is presented. The program simulates the spectrum of two exchanging IR peaks based on simple input parameters. Larger systems can be simulated with minor modifications. The program is available as an executable program for PCs or can be run in MATLAB on any operating system. Source…

  12. Infrared spectra, Raman laser, XRD, DSC/TGA and SEM ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 34; Issue 4. Infrared spectra, Raman laser, XRD, DSC/TGA and SEM investigations on the preparations of selenium metal, (Sb2O3, Ga2O3, SnO and HgO) oxides and lead carbonate with pure grade using acetamide precursors. Moamen S Refat Khaled M Elsabawy.

  13. Magnetic measurements, Raman and infrared spectra of metal ...

    Indian Academy of Sciences (India)

    2018-04-06

    Apr 6, 2018 ... [24] Bandyopadhyay A, Sutradhar S, Sarkar B J, Deb A. K and Chakbarti P K 2012 Appl. Phys. Lett. 100. 252411. [25] Nakamoto K 1997 Infrared and Raman spectra of inorganic and coordination compounds (New York: John Wiley & Sons. Inc.) 5th edn. [26] Faulques E, Perry D I, Lott S, Zubkowski J D and ...

  14. Far-infrared spectra of mesoporous ZnS nanoparticles

    Science.gov (United States)

    Trajić, J.; Romčević, M.; Romčević, N.; Babić, B.; Matović, B.; Baláž, P.

    2016-07-01

    ZnS nanoparticles were synthesized mechanochemically by high-energy milling, with three different milling times (5 min, 10 min and 20 min). Nitrogen adsorption method was used for examining specific surface area and texture of obtained powders. It was found that all samples are completely mesoporous. The optical properties were studied by far-infrared spectroscopy at room temperature in spectral region of 50-600 cm-1. The analysis of the far-infrared reflectivity spectra was made by the fitting procedure. The dielectric function of ZnS nanoparticles is modeled as a mixture of homogenous spherical inclusions in air by the Maxwell-Garnet formula. In the analysis of the far-infrared reflection spectra, appearance of combined plasmon-LO phonon modes (CPPMs) with high phonon damping are observed, which causes decrease of coupled plasmon-phonon frequencies.

  15. Far-infrared spectra of lateral quantum dot molecules

    Science.gov (United States)

    Helle, M.; Harju, A.; Nieminen, R. M.

    2006-02-01

    We study effects of electron electron interactions and confinement potential on the magneto-optical absorption spectrum in the far-infrared (FIR) range of lateral quantum dot molecules (QDMs). We calculate FIR spectra for three different QDM confinement potentials. We use an accurate exact diagonalization technique for two interacting electrons and calculate dipole transitions between two-body levels with perturbation theory. We conclude that the two-electron FIR spectra directly reflect the symmetry of the confinement potential and interactions cause only small shifts in the spectra. These predictions could be tested in experiments with non-parabolic quantum dots (QDs) by changing the number of confined electrons. We also calculate FIR spectra for up to six non-interacting electrons and observe some additional features in the spectrum.

  16. Improving interpretation of infrared spectra for OM characterization by subtraction of spectra from incinerated samples

    Science.gov (United States)

    Ellerbrock, Ruth H.; Gerke, Horst H.; Leue, Martin

    2017-04-01

    Non-destructive methods such as diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) have been applied to characterize organic matter (OM) at intact structural surfaces among others. However, it is often difficult to distinguish effects of organic components on DRIFT signal intensities from those of mineral components. The objective of this study was to re-evaluate DRIFT spectra from intact earthworm burrow walls and coated cracks to improve the interpretation of C-H and C=O bands. We compared DRIFT and transmission Fourier transform infrared (FTIR) spectra of entire samples that were from the same pedogenetic soil horizon, but different in mineral composition and texture (i.e., glacial till versus loess). Spectra of incinerated samples were subtracted from the original spectra. Transmission FTIR and DRIFT spectra were almost identical for entire soil samples. However, the DRIFT spectra were affected by the bulk mode bands (i.e., wavenumbers 2000 to 1700 cm-1) that affected spectral resolution and reproducibility. The ratios between C-H and C=O band intensities as indicator for OM quality obtained with DRIFT were smaller than those obtained from transmission FTIR. A spectral subtraction procedure was found to reduce effects of mineral absorption bands on DRIFT spectra allowing an improved interpretation. DRIFT spectroscopy as a non-destructive method for analyzing OM composition at intact surfaces in structured soils could be calibrated with information obtained with the more detailed transmission FTIR and complementary methods.

  17. Infrared spectra of carbon stars with silicate-like emission

    Science.gov (United States)

    Noguchi, Kunio; Murakami, Hiroshi; Matsuo, Hiroshi; Noda, Manabu; Hamada, Hiroyuki; Watabe, Toyoki

    1990-06-01

    Near-infrared photometry was carried out for 15 carbon stars, including three peculiar carbon stars (BM Gem, V778 Cyg, and EU And) which have a 10-micron emission feature similar to the silicate emission characteristic of oxygen-rich stars. It was found that these carbon stars with silicatelike emission have excesses at both the 12- and 25-micron bands regarding IRAS photometric data which are characteristic of M-type stars with strong silicate emission features. This fact supports the suggestion that the silicatelike emission in peculiar carbon stars is the same as the silicate emission in M-type stars. The near-infrared spectra of these three peculiar carbon stars between 1.9 micron and 4.2 microns were obtained with a grating spectrometer. The spectra of these stars show a 3-micron absorption feature characteristic of carbon stars.

  18. Infrared absorption spectra of human malignant tumor tissues

    Science.gov (United States)

    Skornyakov, I. V.; Tolstorozhev, G. B.; Butra, V. A.

    2008-05-01

    We used infrared spectroscopy methods to study the molecular structure of tissues from human organs removed during surgery. The IR spectra of the surgical material from breast, thyroid, and lung are compared with data from histological examination. We show that in malignant neoplasms, a change occurs in the hydrogen bonds of protein macromolecules found in the tissue of the studied organs. We identify the spectral signs of malignant pathology.

  19. Theoretical study on absorption and emission spectra of adenine analogues.

    Science.gov (United States)

    Liu, Hongxia; Song, Qixia; Yang, Yan; Li, Yan; Wang, Haijun

    2014-04-01

    Fluorescent nucleoside analogues have attracted much attention in studying the structure and dynamics of nucleic acids in recent years. In the present work, we use theoretical calculations to investigate the structural and optical properties of four adenine analogues (termed as A1, A2, A3, and A4), and also consider the effects of aqueous solution and base pairing. The results show that the fluorescent adenine analogues can pair with thymine to form stable H-bonded WC base pairs. The excited geometries of both adenine analogues and WC base pairs are similar to the ground geometries. The absorption and emission maxima of adenine analogues are greatly red shifted compared with nature adenine, the oscillator strengths of A1 and A2 are stronger than A3 and A4 in both absorption and emission spectra. The calculated low-energy peaks in the absorption spectra are in good agreement with the experimental data. In general, the aqueous solution and base pairing can slightly red-shift both the absorption and emission maxima, and can increase the oscillator strengths of absorption spectra, but significantly decrease the oscillator strengths of A3 in emission spectra.

  20. Quantitative Infrared Spectra of Vapor Phase Chemical Agents

    Energy Technology Data Exchange (ETDEWEB)

    Sharpe, Steven W.; Johnson, Timothy J.; Chu, P. M.; Kleimeyer, J.; Rowland, Brad

    2003-08-01

    Quantitative, moderately high resolution (0.1 cm-1) infrared spectra have been acquired for a number of nitrogen broadened (1 atm N2) vapor phase chemicals including: Sarin (GB), Soman (GD), Tabun (GA), Cyclosarin (GF), VX, Nitrogen Mustard (HN3), Sulfur Mustard (HD), and Lewisite (L). The spectra are acquired using a heated, flow-through White Cell1 of 5.6 meter optical path length. Each reported spectrum represents a statistical fit to Beer’s law, which allows for a rigorous calculation of uncertainty in the absorption coefficients. As part of an ongoing collaboration with the National Institute of Standards and Technology (NIST), cross-laboratory validation is a critical aspect of this work. In order to identify possible errors in the Dugway flow-through system, quantitative spectra of isopropyl alcohol from both NIST and Pacific Northwest National Laboratory (PNNL) are compared to similar data taken at Dugway proving Grounds (DPG).

  1. Recommendations for the presentation of infrared absorption spectra in data collections condensed phases

    CERN Document Server

    Becker, E D

    2013-01-01

    Recommendations for the Presentation of Infrared Absorption Spectra in Data Collections-A. Condensed Phases presents the recommendations related to the infrared spectra of condensed phase materials that are proposed for permanent retention in data collections. These recommendations are based on two reports published by the Coblentz Society. This book emphasizes the three levels of quality evaluation for infrared spectra as designated by the Coblentz Society, including critically defined physical data, research quality analytical spectra, and approved analytical spectra. This text discusses the

  2. Infrared reflectance spectra: effects of particle size, provenance and preparation

    Science.gov (United States)

    Su, Yin-Fong; Myers, Tanya L.; Brauer, Carolyn S.; Blake, Thomas A.; Forland, Brenda M.; Szecsody, J. E.; Johnson, Timothy J.

    2014-10-01

    We have recently developed methods for making more accurate infrared total and diffuse directional - hemispherical reflectance measurements using an integrating sphere. We have found that reflectance spectra of solids, especially powders, are influenced by a number of factors including the sample preparation method, the particle size and morphology, as well as the sample origin. On a quantitative basis we have investigated some of these parameters and the effects they have on reflectance spectra, particularly in the longwave infrared. In the IR the spectral features may be observed as either maxima or minima: In general, upward-going peaks in the reflectance spectrum result from strong surface scattering, i.e. rays that are reflected from the surface without bulk penetration, whereas downward-going peaks are due to either absorption or volume scattering, i.e. rays that have penetrated or refracted into the sample interior and are not reflected. The light signals reflected from solids usually encompass all such effects, but with strong dependencies on particle size and preparation. This paper measures the reflectance spectra in the 1.3 - 16 micron range for various bulk materials that have a combination of strong and weak absorption bands in order to observe the effects on the spectral features: Bulk materials were ground with a mortar and pestle and sieved to separate the samples into various size fractions between 5 and 500 microns. The median particle size is demonstrated to have large effects on the reflectance spectra. For certain minerals we also observe significant spectral change depending on the geologic origin of the sample. All three such effects (particle size, preparation and provenance) result in substantial change in the reflectance spectra for solid materials; successful identification algorithms will require sufficient flexibility to account for these parameters.

  3. Theoretical design of near - infrared organic compounds

    Science.gov (United States)

    Brymora, Katarzyna; Ducasse, Laurent; Dautel, Olivier; Lartigau-Dagron, Christine; Castet, FréDéRic

    The world follows the path of digital development faster than ever before. In consequence, the Human Machine Interfaces (HMI) market is growing as well and it requires some innovations. The goal of our work is to achieve an organic Infra-Red (IR) photodetectors hitting the performance requirements for HMI applications. The quantum chemical calculations are used to guide the synthesis and technology development. In this work, in the framework of density functional theory (DFT) and time-dependent density functional theory (TD-DFT), we consider a large variety of materials exploring small donor-acceptor-donor molecules and copolymers alternating donor and acceptor monomers. We provide a structure-property relationship in view of designing new Near-Infrared (NIR) absorbing organic molecules and polymers.

  4. Infrared spectra in monitoring biochemical parameters of human blood

    International Nuclear Information System (INIS)

    Prabhakar, S; Singh, R A; Jain, N

    2012-01-01

    Infrared spectroscopy is gaining recognition as a promising method. The infrared spectra of selected regions (2000-400cm -1 ) of blood tissue samples are reported. Present study related to the role of spectral peak fitting in the study of human blood and quantitative interpretations of infrared spectra based on chemometrics. The spectral variations are interpreted in terms of the biochemical and pathological processes involved. The mean RNA/DNA ratio of fitted intensities and analytical area as calculated from the transmittance peaks at 1121cm -1 /1020cm -1 is found to be 0.911A.U and 2.00A.U. respectively. The ratio of 1659cm -1 /1544cm -1 (amide-I/amide-II) bands is found to shed light on the change in the DNA content. The ratio of amide-I/amide-II is almost unity (≅1.054) for blood spectra. The deviation from unity is an indication of DNA absorption from the RBC cells. The total phosphate content has found to be 25.09A.U. The level for glycogen/phosphate ratio (areas under peaks 1030cm -1 /1082cm -1 ) is found to be 0.286A.U. The ratio of unsaturated and saturated carbonyl compounds (C=O) in blood samples is in form of esters and the analytical areas under the spectral peaks at 1740cm -1 and 1731cm -1 for unsaturated esters and saturated esters respectively found to be 0.618A.U.

  5. The influence of particle size on infrared reflectance spectra

    Science.gov (United States)

    Myers, Tanya L.; Brauer, Carolyn S.; Su, Yin-Fong; Blake, Thomas A.; Johnson, Timothy J.; Richardson, Robert L.

    2014-06-01

    Reflectance spectra of solids are influenced by the absorption coefficient and index of refraction as well as particle size and morphology. In the infrared, spectral features may be observed as either maxima or minima: in general, the upwardgoing peaks in the reflectance spectrum result from surface scattering, which are rays that have reflected from the surface without penetration, whereas downward-going peaks result from either absorption or volume scattering, i.e. rays that have penetrated into the sample to be absorbed or refracted into the sample interior and are not reflected. The light signal reflected from solids usually encompasses all these effects which include dependencies on particle size, morphology and sample density. This paper measures the reflectance spectra in the 1.3 - 16 micron range for various bulk materials that have a combination of strong and weak absorption bands in order to understand the effects on the spectral features as a function of the mean grain size of the sample. The bulk materials were ground and sieved to separate the samples into various size fractions: 0-45, 45-90, 90-180, 180-250, 250-500, and >500 microns. The directional-hemispherical spectra were recorded using a Fourier transform infrared spectrometer equipped with an integrating sphere to measure the reflectance for all of the particle-size fractions. We have studied both organic and inorganic materials, but this paper focuses on inorganic salts, NaNO3, in particular. Our studies clearly show that particle size has an enormous influence on the measured reflectance spectra for bulk materials and that successful identification requires sufficient representative reflectance data so as to include the particle size(s) of interest. Origins of the effects are discussed.

  6. Infrared emission spectra of candidate interstellar aromatic molecules

    Science.gov (United States)

    Schlemmer, S.; Balucani, N.; Wagner, D. R.; Steiner, B.; Saykally, R. J.

    1996-01-01

    Interstellar dust is responsible, through surface reactions, for the creation of molecular hydrogen, the main component of the interstellar clouds in which new stars form. Intermediate between small, gas-phase molecules and dust are the polycyclic aromatic hydrocarbons (PAHs). Such molecules could account for 2-30% of the carbon in the Galaxy, and may provide nucleation sites for the formation of carbonaceous dust. Although PAHs have been proposed as the sources of the unidentified infrared emission bands that are observed in the spectra of a variety of interstellar sources, the emission characteristics of such molecules are still poorly understood. Here we report laboratory emission spectra of several representative PAHs, obtained in conditions approximating those of the interstellar medium, and measured over the entire spectral region spanned by the unidentified infrared bands. We find that neutral PAHs of small and moderate size can at best make only a minor contribution to these emission bands. Cations of these molecules, as well as much larger PAHs and their cations, remain viable candidates for the sources of these bands.

  7. Hydrogen Dimers in Giant-planet Infrared Spectra

    Science.gov (United States)

    Fletcher, Leigh N.; Gustafsson, Magnus; Orton, Glenn S.

    2018-03-01

    Despite being one of the weakest dimers in nature, low-spectral-resolution Voyager/IRIS observations revealed the presence of (H2)2 dimers on Jupiter and Saturn in the 1980s. However, the collision-induced H2–H2 opacity databases widely used in planetary science have thus far only included free-to-free transitions and have neglected the contributions of dimers. Dimer spectra have both fine-scale structure near the S(0) and S(1) quadrupole lines (354 and 587 cm‑1, respectively), and broad continuum absorption contributions up to ±50 cm‑1 from the line centers. We develop a new ab initio model for the free-to-bound, bound-to-free, and bound-to-bound transitions of the hydrogen dimer for a range of temperatures (40–400 K) and para-hydrogen fractions (0.25–1.0). The model is validated against low-temperature laboratory experiments, and used to simulate the spectra of the giant planets. The new collision-induced opacity database permits high-resolution (0.5–1.0 cm‑1) spectral modeling of dimer spectra near S(0) and S(1) in both Cassini Composite Infrared Spectrometer observations of Jupiter and Saturn, and in Spitzer Infrared Spectrometer (IRS) observations of Uranus and Neptune for the first time. Furthermore, the model reproduces the dimer signatures observed in Voyager/IRIS data near S(0) on Jupiter and Saturn, and generally lowers the amount of para-H2 (and the extent of disequilibrium) required to reproduce IRIS observations.

  8. Infrared absorption spectra of selenate compounds of indium (3)

    International Nuclear Information System (INIS)

    Kharitonov, Yu.Ya.; Kadoshnikova, N.V.; Tananaev, I.V.

    1979-01-01

    Obtained and discussed are infrared absorption spectra (400-4000 cm -1 ) of the following indium selenates: In 2 (SeO 4 ) 3 x5H 2 O, In 2 (SeO 4 ) 3 x9H 2 O, NaIn(SeO 4 ) 2 x6H 2 O, NaIn(SeO 4 ) 2 xH 2 O, MIn(SeO 4 ) 2 x4H 2 O (M=NH 4 , K, Rb), CsIn(SeO 4 ) 2 x2H 2 O, Na 3 In(SeO 4 ) 3 x7H 2 O, MIn(SeO 4 ) 2 (M=NH 4 , Na, K, Rb, Cs), M 2 InOH(SeO 4 ) 2 xyH 2 O (M=NH 4 , Na, K, Rb) and K 2 InOD(SeO 4 ) 2 xyD 2 O

  9. Simulation of two-dimensional infrared spectra by numerical integration of the schrodinger equation

    NARCIS (Netherlands)

    Jansen, Thornas la Cour; Knoester, Jasper; Simos, T; Maroulis, G

    2006-01-01

    A method is presented for simulating infrared absorption and two-dimensional infrared spectra including dynamical effects as motional narrowing, population transfer and reorientation. Interactions between the considered vibrations and the surrounding bath give rise to these effects. These

  10. Infrared absorption spectra of nanosized silica with organic additives

    Directory of Open Access Journals (Sweden)

    Мaria О. Savchenko

    2014-12-01

    Full Text Available The prospects of using of silica nanoparticles modified with urea-formaldehyde polymers which is obtained by sulfuric acid sol-gel technology are shown. The aim is a detailed research on the infrared absorption spectra of nanodispersed silica modified with urea-formaldehyde polymers with identification of the absorption bands of the spectrum. The method of infrared spectroscopy is used to research spectral characteristics of nanosized silica, urea-formaldehyde polymer and nanodispersed silica modified with urea-formaldehyde polymers in different ratio. It is found that interaction of initial ingredients occurs at the stage of phase formation in solutions in colloidal silica products containing urea-formaldehyde polymers. Organic components are localized on the surface of the globules and in the interglobular space. This result of such interaction is the physical and structural transformation of globular surfaces of silica and new chemical compounds formation. This allows to give to final product a variety of properties required for practical use in many industries.

  11. Infrared Spectra and Optical Constants of Elusive Amorphous Methane

    Science.gov (United States)

    Gerakines, Perry A.; Hudson, Reggie L.

    2015-01-01

    New and accurate laboratory results are reported for amorphous methane (CH4) ice near 10 K for the study of the interstellar medium (ISM) and the outer Solar System. Near- and mid-infrared (IR) data, including spectra, band strengths, absorption coefficients, and optical constants, are presented for the first time for this seldom-studied amorphous solid. The apparent IR band strength near 1300 cm(exp -1) (7.69 micrometer) for amorphous CH4 is found to be about 33% higher than the value long used by IR astronomers to convert spectral observations of interstellar CH4 into CH4 abundances. Although CH4 is most likely to be found in an amorphous phase in the ISM, a comparison of results from various laboratory groups shows that the earlier CH4 band strength at 1300 cm(exp -1) (7.69 micrometer) was derived from IR spectra of ices that were either partially or entirely crystalline CH4 Applications of the new amorphous-CH4 results are discussed, and all optical constants are made available in electronic form.

  12. Far-infrared spectra for copper-zinc mixed ferrites

    Energy Technology Data Exchange (ETDEWEB)

    Zaki, H.M., E-mail: dakdik2001@yahoo.co [Physics Department, Faculty of Science, King Abdul Aziz University, Jeddah (Saudi Arabia); Physics Department, Faculty of Science, Zagazig University (Egypt); Dawoud, H.A. [University of Gaza, P.O. Box 108, Gaza Strip, Palestine Physics Department (Palestinian Territory, Occupied)

    2010-11-01

    Infrared spectra of Zn{sup 2+} ions substituted Cu ferrites with the general formula Cu{sub 1-x}Zn{sub x}Fe{sub 2}O{sub 4} (where x=0.0, 0.2, 0.4, 0.6, 0.8 and 1) have been analyzed in the frequency range 200-1000 cm{sup -1}. These mixed ferrites were prepared by the standard double sintering ceramic method. Two prominent bands were observed, high-frequency band {nu}{sub 1} around 550 cm{sup -1} and low-frequency band {nu}{sub 2} around 395 cm{sup -1} and assigned to tetrahedral and octahedral sites for spinel lattice, respectively. On introducing zinc ions IR spectra indicate new shoulders or splitting on tetrahedral absorption bands around 600 and 700 cm{sup -1}. A small absorption band {nu}{sub 3} was observed around 310 cm{sup -1}. This indicates the migration of some Zn{sup 2+} ions to octahedral site. Another small weak absorption band was also observed around 265 cm{sup -1}; its intensity increased with Zn content. Force constant was calculated for both tetrahedral and octahedral sites. Threshold frequency {nu}{sub th} for the electronic transition was determined and found to increase with an increase in Zn ions. The half bandwidth for each site was calculated and the ratio seemed to increase with an increase in zinc content. The cation distribution for these ferrites was estimated in the light of IR spectra.

  13. Cis- and trans-perfluorodecalin: Infrared spectra, radiative efficiency and global warming potential

    Science.gov (United States)

    Le Bris, Karine; DeZeeuw, Jasmine; Godin, Paul J.; Strong, Kimberly

    2017-12-01

    Perfluorodecalin (PFD) is a molecule used in various medical applications for its capacity to dissolve gases. This potent greenhouse gas was detected for the first time in the atmosphere in 2005. We present infrared absorption cross-section spectra of a pure vapour of cis- and trans-perfluorodecalin at a resolution of 0.1 cm-1. Measurements were performed in the 560-3000 cm-1 spectral range using Fourier transform spectroscopy. The spectra have been compared with previous experimental data and theoretical calculations by density functional theory. The new experimental absorption cross-sections have been used to calculate a lifetime-corrected radiative efficiency at 300 K of 0.62 W m-2 ppb-1 and 0.57 W.m-2.ppb-1 for the cis and trans isomers respectively. This leads to a 100-year time horizon global warming potential of 8030 for cis-PFD and 7440 for trans-PFD.

  14. [Investigation of typical melamine urinary stones using infrared spectra].

    Science.gov (United States)

    Si, Min-Zhen; Li, Qing-Yun; Liu, Ren-Ming; Kang, Yi-Pu; Wang, Kun-Hua; Zhang, Zhi-Guo

    2010-02-01

    A typical melamine kidney stone confirmed by some medicine expert was collected from the first people's hospital of Yunnan. The kidney stone was adequately determined by PE corporation spectra 100(with resolution of 1 cm(-1)). The stone samples for FTIR analysis were prepared using the KBr pellet technique, where 2 mg of the pretreated stone powder was mixed with 200 mg of analytical grade KBr using an agate pestle and mortar. The digital spectrum was then scanned in the mid-infrared region from 4 000 to 400 cm(-1) at room temperature. The appearing bands between 4 000 and 2 000 cm(-1) were 3 487, 3 325, 3 162 and 2 788 cm(-1), those between 1 700 and 1 000 cm(-1) were 1 694, 1 555, 1 383, 1 340, 1 189 and 1 122 cm(-1), and those between 1 000 and 400 cm(-1) were 993, 782, 748, 709, 624, 585, 565 and 476 cm(-1). It was found that the main constituent of calculi showed few comparability with cat kidney stone, which was from cats that died after consuming the contaminated food, and confirmed that these deposits were primarily composed of melamine and cyanuric acid compared to the IR spectra of calculi in literature. It was also found that the main constituent of calculi showed few comparability with popular kidney stone by comparison with the IR spectra of calculi in literature. The spectrum of calculi was 50% respectively similar with melamine and uric acid as compared with the IR spectrum. It was found that the main constituent of calculi was melamine itself and uric acid as compared with the IR spectra of calculi and melamine: (1 : 1), because the spectrum of calculi was 83. 3% similar to melamine and uric acid (1 : 1). The appearing bands of melamine and uric acid (1 : 1) between 4 000 and 2 000 cm(-1) were 3 469, 3 419, 3 333, 3 132, 3 026, 2 827 cm(-1), those between 1 700 and 1 000 cm(-1) were 1 696, 1 656, 1 555, 1 489, 1 439, 1 350, 1 311, 1 198, 1 124 and 1 028 cm(-1), and those between 1 000 and 400 cm(-1) were 993, 878, 814, 784, 745, 708, 619, 577 and

  15. The experimental and theoretical investigation of vibration spectra in ferroelectric semiconductor SbSBrxI1-x crystals

    International Nuclear Information System (INIS)

    Audzijonis, A.; Zigas, L.; Kvedaravicius, A.; Zaltauskas, R.

    2009-01-01

    The vapor grown SbSBr x I 1-x (x=0.1; 0.5; 0.9) crystals with clear mirror surfaces have been used for infrared reflection measurements with Fourier spectrometer. The vibration frequencies along c(z)-axis have been derived from Kramers-Kroning and optical parameters fitting analysis of the experimental reflectivity spectra at T=300 K. The theoretical vibration spectra of SbSBr x S 1-x (x=0.1; 0.5; 0.9) crystals in paraelectric phase (T=300 K) along c(z)-axis have been determined in quasiharmonic approximation by diagonalization of dynamical matrix. The theoretical vibration spectra of these crystals in a-b(x-y) plane have been determined in harmonic approximation. In this work we discuss the nature of anharmonism in SbSBr x I 1-x crystals along the c(z)-axis.

  16. Analysis of Spitzer-IRS spectra of hyperluminous infrared galaxies

    Science.gov (United States)

    Ruiz, A.; Risaliti, G.; Nardini, E.; Panessa, F.; Carrera, F. J.

    2013-01-01

    Context. Hyperluminous infrared galaxies (HLIRG) are the most luminous persistent objects in the Universe. They exhibit extremely high star formation rates, and most of them seem to harbour an active galactic nucleus (AGN). They are unique laboratories for investigating the most extreme star formation and its connection to super-massive black hole growth. Aims: The relative AGN and starburst (SB) contributions to the total output in these objects is still debated. Our aim is to disentangle the AGN and SB emission of a sample of thirteen HLIRG. Methods: We studied the MIR low-resolution spectra of a sample of thirteen HLIRG obtained with the Infrared Spectrograph on board Spitzer. The 5-8 μm range is an optimal window for detecting AGN activity even in a heavily obscured environment. We performed an SB/AGN decomposition of the continuum using templates, which has been successfully applied for ULIRG in previous works. Results: The MIR spectra of all sources is largely dominated by AGN emission. By converting the 6 μm luminosity into IR luminosity, we found that ~80% of the sample shows an IR output dominated by the AGN emission. However, the SB activity is significant in all sources (mean SB contribution ~30%), showing star formation rates ~300-3000 M⊙ yr-1. With X-ray and MIR data we estimated the dust covering factor (CF) of these HLIRG, finding that a significant fraction presents a CF consistent with unity. Along with the high X-ray absorption shown by these sources, this suggests that large amounts of dust and gas enshroud the nucleus of these HLIRG, as also observed in ULIRG. Conclusions: Our results agree with previous studies of the IR SED of HLIRG using radiative transfer models, and we find strong evidence that all HLIRG harbour an AGN. Moreover, this work provides further support for the idea that AGN and SB are both crucial to understanding the properties of HLIRG. Our study of the CF supports the hypothesis that HLIRG can be divided into two

  17. Data fusion of near-infrared and mid-infrared spectra for identification of rhubarb

    Science.gov (United States)

    Sun, Wenjuan; Zhang, Xin; Zhang, Zhuoyong; Zhu, Ruohua

    2017-01-01

    Rhubarb has different medicinal efficacy to official rhubarb and may affect the clinical medication safety. In order to guarantee the quality of rhubarb, we established a method to distinguish unofficial rhubarbs. 52 official and unofficial rhubarb samples were analyzed using near-infrared (NIR) spectroscopy and mid-infrared (MIR) spectroscopy for classification. The feature vectors, which were selected by wavelet compression (WC) and interval partial least squares (iPLS) from NIR, MIR spectra, were fused together for identifying rhubarb samples. Partial least squares-discriminant analysis (PLS-DA), soft independent modeling of class analogies (SIMCA), support vector machine (SVM) and artificial neural network (ANN) were compared for classifying rhubarb. The use of data fusion strategies improved the classification model and allowed correct classification of all the samples.

  18. Investigation of Effect of KBr Matrix on Drift Infrared Spectra of Some ...

    African Journals Online (AJOL)

    MBI

    2014-09-28

    Sep 28, 2014 ... ABSTRACT. Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy was used in this work to investigate the effect of KBr on infrared spectra of calcite and illite/smectite. 30 mg of each of these minerals were dispersed in. 270 mg of KBr and their drifts spectra were obtained and analysed using ...

  19. A relationship between Raman and infrared spectra: the case of push pull molecules

    Science.gov (United States)

    Del Zoppo, M.; Tommasini, M.; Castiglioni, C.; Zerbi, G.

    1998-04-01

    Vibrational spectra of push-pull polyenes show a peculiar feature namely, in infrared and Raman spectra strong, coincident bands appear, arising from vibrations localised on the polyene bridge. A simple model, based on the introduction of an effective internal field due to the charge transfer between end groups allows the infrared and Raman intensities of these bands to be related.

  20. Using Molecular Modeling in Teaching Group Theory Analysis of the Infrared Spectra of Organometallic Compounds

    Science.gov (United States)

    Wang, Lihua

    2012-01-01

    A new method is introduced for teaching group theory analysis of the infrared spectra of organometallic compounds using molecular modeling. The main focus of this method is to enhance student understanding of the symmetry properties of vibrational modes and of the group theory analysis of infrared (IR) spectra by using visual aids provided by…

  1. Theoretical modeling of infrared spectra of twinned lead zirconate

    Czech Academy of Sciences Publication Activity Database

    Dočekalová, Zuzana; Pasciak, Marek; Hlinka, Jiří

    2017-01-01

    Roč. 90, č. 1 (2017), s. 17-23 ISSN 0141-1594 R&D Projects: GA ČR GA15-04121S Institutional support: RVO:68378271 Keywords : domains * IR spectroscopy * dielectric permittivity * lead zirconate * shell model * Born effective charge Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.060, year: 2016

  2. Temporally resolved infrared spectra from the detonation of advanced munitions

    Science.gov (United States)

    Gordon, Joe Motos; Gross, Kevin C.; Perram, Glen P.

    2009-05-01

    A suite of instruments including a 100 kHz 4-channel radiometer, a rapid scanning Fourier-transform infrared spectrometer, and two high-speed visible imagers was used to observe the detonation of several novel insensitive munitions being developed by the Air Force Research Laboratory. The spectral signatures exhibited from several different explosive compositions are discernable and may be exploited for event classification. The spectra are initially optically thick, resembling a Planckian distribution. In time, selective emission in the wings of atmospheric absorption bands becomes apparent, and the timescale and degree to which this occurs is correlated with aluminum content in the explosive formulation. By analyzing the high-speed imagery in conjunction with the time-resolved spectral measurements, it may be possible to interpret these results in terms of soot production and oxidation rates. These variables allow for an investigation into the chemical kinetics of explosions and perhaps reveal other phenomenology not yet readily apparent. With an increased phenomenological understanding, a model could be created to explain the kinetic behavior of the temperature and by-product concentration profiles and thus improve the ability of military sensing platforms to identify explosive types and sources.

  3. Matrix infrared spectra and electronic structure calculations of the first actinide borylene: FB=ThF(2).

    Science.gov (United States)

    Wang, Xuefeng; Roos, Björn O; Andrews, Lester

    2010-03-14

    Laser-ablated Th atoms react with BF(3) during condensation in excess argon at 6 K to form the first actinide borylene (FB=ThF(2)) and actinide-boron multiple bond. Three new product absorptions in the B-F and Th-F stretching regions of matrix infrared spectra are assigned to FB=ThF(2) from comparison to theoretically predicted vibrational frequencies.

  4. Laboratory-based grain-shape models for simulating dust infrared spectra

    NARCIS (Netherlands)

    Mutschke, H.; Min, M.; Tamanai, A.

    2009-01-01

    Context. Analysis of thermal dust emission spectra for dust mineralogy and physical grain properties depends on comparison spectra, which are either laboratory-measured infrared extinction spectra or calculated extinction cross sections based on certain grain models. Often, the agreement between

  5. IHW COMET HALLEY INFRARED SPECTRA, V2.0

    Data.gov (United States)

    National Aeronautics and Space Administration — This data set presents the infrared spectroscopy of Comet 1P/Halley archived with the Infrared Studies Network (IRSN) of the International Halley Watch (IHW). 59...

  6. Comet Mineralogy as Inferred from Infrared Spectra of Comets

    Science.gov (United States)

    Wooden, Diane H.

    2006-01-01

    For most comets, infrared (IR) spectroscopy (remote sensing) is the method through which we diagnose the mineralogy and size distribution of dust in their comae. The shape and contrast of the IR spectral features depend on the particle size: optically active minerals (absorbing of visible and near-IR solar photons) and submicron solid grains or highly porous (> 90% vacuum) grains primarily contribute to the shapes of the observed resonances. Comet mineralogies typically are determined by fitting thermal emission models of ensembles of discrete mineral grains to observed IR spectral energy distributions. The absorptivities (Q-abs) and scattering efficiencies (Q-scat) of the discrete mineral grains are computed using Mie scattering, Maxwell-Garnet mixing, Discrete Dipole Approximation, and Multi-Layered Sphere codes. These techniques when applied to crystalline minerals, specifically olivine (Mg_x, Fe_1-x)2 Si04, x>0.9, require the use of ellipsoidal shaped particles with elongated axial ratios or hollow spheres to produce the shapes of the resonances observed both from comet comae and laboratory samples. The wavelength positions of the distinct resonances from submicron-radii crystalline silicates, as well as their thermal equilibrium temperatures, constrain the crystalline olivine to have a relatively high Mg-content (x>0.9, or Fo>90). Only resonances computed for submicron Mg-rich crystalline olivine and crystalline orthopyroxene match the observed IR spectral features. However, this has led to the interpretation that micron-radii and larger crystals are absent from comet comae. Furthermore, the mass fraction of silicate crystals is dependent upon whether just the submicron portion of the size distribution is being compared or the submicron crystals compare to the aggregates of porous amorphous silicates that are computationally tractable as porous spheres. We will discuss the Deep Impact results as examples of these challenges to interpreting mid-IR spectra of

  7. Quantum Calculation for Musk Molecules Infrared Spectra towards the Understanding of Odor

    Directory of Open Access Journals (Sweden)

    Elaine Rose Maia

    2014-01-01

    Full Text Available It is not clear so far how humans can recognize odor. One of the theories regarding structure-odor relationship is vibrational theory, which claims that odors can be recognized by their modes of vibration. In this sense, this paper brings a novel comparison made between musky and nonmusky molecules, as to check the existence of correlation between their modes on the infrared spectra and odor. For this purpose, sixteen musky odorants were chosen, as well as seven other molecules that are structurally similar to them, but with no musk odor. All of them were submitted to solid theoretical methodology (using molecular mechanics/molecular dynamics and Neglect of Diatomic Differential Overlap Austin Model 1 methods to optimize geometries as to achieve density functional theory spectra information, with both Gradient Corrected Functional Perdew-Wang generalized-gradient approximation (GGA/PW91 and hybrid Becke, three-parameter, Lee-Yang-Parr (B3LYP functional. For a proper analysis over spectral data, a mathematical method was designed, generating weighted averages for theoretical frequencies and computing deviations from these averages. It was then devised that musky odorants satisfied demands of the vibrational theory, while nonmusk compounds belonging either to nitro group or to acyclic group failed to fulfill the same criteria.

  8. Thermal Infrared Spectra of a Suite of Forsterite Samples and Ab-initio Modelling of theirs Spectra

    Science.gov (United States)

    Maturilli, A.; Stangarone, C.; Helbert, J.; Tribaudino, M.; Prencipe, M.

    2017-12-01

    Forsterite is the dominating component in olivine, a major constituent in ultrafemic rocks, as well as planetary bodies. Messenger X-ray spectrometer has shown that Mg-rich silicate minerals, such as enstatite and forsterite, dominate Mercury's surface (Weider et al 2012). A careful and detailed acquaintance with the forsterite spectral features and their dependence wrt environmental conditions on Mercury is needed to interpret the remote sensing data from previous and forthcoming missions. We propose an experimental vs calculation approach to reproduce and describe the spectral features of forsterite. TIR emissivity measurements are performed by the Planetary Spectroscopy Laboratory (PSL) of DLR. PSL offers the unique capability to measure the emissivity of samples at temperature up to 1000K under vacuum conditions. TIR emissivity and reflectance measurements are performed on 11 olivine samples having a different composition within the forsterite-fayalite series. When available, the sample has been measured in 2 different grain sizes (chameleon-like effects of Mercury surface already observed (Helbert et al. 2013), this study wants to point out the main spectral features due to the composition and temperature. Our results are used to create a theoretical background to interpret the high temperature infrared emissivity spectra from MERTIS onboard the ESA BepiColombo mission to Mercury (Helbert et al. 2010).

  9. Improved assignments of the vibrational fundamental modes of ortho-, meta-, and para-xylene using gas- and liquid-phase infrared and Raman spectra combined with ab initio calculations: Quantitative gas-phase infrared spectra for detection

    Science.gov (United States)

    Lindenmaier, Rodica; Scharko, Nicole K.; Tonkyn, Russell G.; Nguyen, Kiet T.; Williams, Stephen D.; Johnson, Timothy J.

    2017-12-01

    Xylenes contain a blend of the ortho-, meta-, and para- isomers, and all are abundant contaminants in the ground, surface waters, and air. To better characterize xylene and to better enable its detection, high quality quantitative vapor-phase infrared spectra of all three isomers over the 6500 - 540 cm-1 range are reported. All fundamental vibrational modes are assigned based on these vapor-phase infrared spectra, liquid-phase infrared and Raman spectra, along with density functional theory (DFT), ab initio MP2 and high energy-accuracy compound theoretical model (W1BD) calculations. Both MP2 and DFT predict a single conformer with C2v symmetry for ortho-xylene, and two conformers each for meta- and para-xylene, depending on the preferred orientations of the methyl groups. For meta-xylene the two conformers have Cs and C2 symmetry, and for para-xylene these conformers have C2v or C2h symmetry. Since the relative population of the two conformers is approximately 50% for both isomers and predicted frequencies and intensities are very similar for each conformer, an arbitrary choice to discuss the Cs conformer for meta-xylene and the C2v conformer for para-xylene is made. Integrated band intensities for all isomers are reported. Using the quantitative infrared data, the global warming potential values of each isomer are determined. Potential bands for atmospheric monitoring are also discussed.

  10. Estimation of leaf water content from far infrared (2.5-14µm) spectra using continuous wavelet analysis

    NARCIS (Netherlands)

    Ullah, S.; Skidmore, A.K.; Naeem, M.; Schlerf, M.

    2012-01-01

    The objective of this study was to estimate leaf water content based on continuous wavelet analysis from the far infrared (2.5 - 14.0 μm) spectra. The entire dataset comprised of 394 far infrared spectra which were divided into calibration (262 spectra) and validation (132 spectra) subsets. The far

  11. Thermal Infrared Spectra of Microcrystalline Sedimentary Phases: Effects of Natural Surface Roughness on Spectral Feature Shape

    Science.gov (United States)

    Hardgrove, C.; Rogers, A. D.

    2012-03-01

    Thermal infrared spectral features of common microcrystalline phases (chert, alabaster, micrite) are presented. Spectra are sensitive to mineralogy and micron-scale (~1-25 µm) surface roughness. Roughness is on the scale of the average crystal size.

  12. Infrared spectra and ultraviolet-tunable laser induced photochemistry of matrix-isolated phenol and phenol-d5.

    Science.gov (United States)

    Giuliano, Barbara Michela; Reva, Igor; Lapinski, Leszek; Fausto, Rui

    2012-01-14

    Monomers of phenol and its ring-perdeuterated isotopologue phenol-d(5) were isolated in argon matrices at 15 K. The infrared (IR) spectra of these species were recorded and analyzed. In situ photochemical transformations of phenol and phenol-d(5) were induced by tunable UV laser light. The photoproducts have been characterized by IR spectroscopy supported by theoretical calculations of the infrared spectra. The primary product photogenerated from phenol was shown to be the phenoxyl radical. The analysis of the progress of the observed phototransformations led to identification of 2,5-cyclohexadienone as one of the secondary photoproducts. Spectral indications of other secondary products, such as the Dewar isomer and the open-ring ketene, were also detected. Identification of the photoproducts provided a guide for the interpretation of the mechanisms of the observed photoreactions.

  13. Generating the Infrared Spectra of Large Interstellar Molecules with Density Functional Theory

    Science.gov (United States)

    Bauschlicher, Charles W., Jr.; Arnold, James (Technical Monitor)

    1999-01-01

    It is now possible to compute IR (infrared) spectra of large molecules with an accuracy of 30 per cm, or better, using density function theory. This is true for cations, anions, and neutrals. Thus it possible to generate synthetic IR spectra that can help interpret experimental spectra and fill in for missing experimental data. These synthetic spectra can be used as input into interstellar models. In addition to IR spectra, it is possible to compute energetic properties to help understand which molecules can be formed in the interstellar environment.

  14. Quantitative infrared and near-infrared gas-phase spectra for pyridine: Absolute intensities and vibrational assignments

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, T. J.; Aker, P. M.; Scharko, N. K.; Williams, S. D.

    2018-02-01

    Using vetted methods for generating quantitative absorption reference data, broadband infrared and near-infrared spectra (total range 11,000 – 600 cm-1) of pyridine vapor were recorded at 0.1 cm-1 spectral resolution, with the analyte thermostatted at 298 K and pressure-broadened to 1 atmosphere using N2 ballast gas. The quantitative spectrum is reported for the first time, and we have re-assigned some of the 27 fundamental modes. Fundamental assignments were confirmed by IR vapor phase band shapes, FT-Raman measurements and comparison with previous analyses. For the 760-Torr vapor-phase IR data several bands show resolved peaks (Q-branches). We have also assigned for the first time hundreds of combination and overtone bands in the mid- and near-IR. All assignments were made via comparison to theoretically calculated frequencies and intensities: The frequencies were computed with Gaussian03 with the anharmonic option, using MP2 and the ccpvtz basis set. The intensities were taken from a VSCF calculation in GAMESS using Hartree-Fock (for overtones and combination bands) or from the harmonic MP2 for fundamentals. Overtone and combination band harmonic and anharmonic frequencies, as well as intensities were also calculated using the CFOUR program. It is seen in the NIR spectrum near 6000 cm-1 that the very strong bands arise from the C-H first overtones, whereas only much weaker bands are observed for combination bands of C-H stretching modes. Certain features are discussed for their potential utility for atmospheric monitoring.

  15. Infrared spectra of the gaseous iodides of chromium, iron and nickel

    International Nuclear Information System (INIS)

    Konings, R.J.M.; Booij, A.S.

    1991-11-01

    The infrared spectra of the vapours over chromium, iron and nickel di-iodide have been studied by high-temperature infrared spectroscopy. The gaseous molecules CrI 2 , FeI 2 and NiI 2 were all identified and the interpretation of the spectra is in agreement with a linear structure. Additional strong absorption bands in the spectra of the vapour phase above liquid CrI 2 and FeI 2 were assigned to dimeric (MI 2 ) 2 molecules. Valence force constants and thermodynamic quantities have been calculated. (author). 41 refs.; 4 figs.; 5 tabs

  16. Fourier transform infrared spectra applications to chemical systems

    CERN Document Server

    Ferraro, John R

    1978-01-01

    Fourier Transform Infrared Spectroscopy: Applications to Chemical Systems presents the chemical applications of the Fourier transform interferometry (FT-IR).The book contains discussions on the applications of FT-IR in the fields of chromatography FT-IR, polymers and biological macromolecules, emission spectroscopy, matrix isolation, high-pressure interferometry, and far infrared interferometry. The final chapter is devoted to the presentation of the use of FT-IR in solving national technical problems such as air pollution, space exploration, and energy related subjects.Researc

  17. Infrared spectra of zinc doped lead borate glasses

    Indian Academy of Sciences (India)

    Unknown

    subject of numerous infrared studies due to their structural peculiarities (Wang and Angell 1976; Kamitsos and. Karakassides 1989). Recently, the study of oxide glasses has received considerable attention due to their structural peculiarities. In borate glasses, B2O3 is a basic glass former because of its higher bond strength ...

  18. Infrared spectra of peculiar emission-line stars

    International Nuclear Information System (INIS)

    Andrillat, Yvette; Houziaux, Leo

    1975-01-01

    230A/mm spectra of HD51585, V1016Cyg, HBV475 and XXOph between 8,000 and 11,000A are described. Important spectral variations have been noted between 1974 and 1975. Satisfactory identifications cannot be proposed for lines at 9,180 and 9,204A [fr

  19. Coronene and pyrene (5, 7)-member ring defects. Infrared spectra, energetics, and alternative formation pathways

    Science.gov (United States)

    Öttl, S.; Huber, S. E.; Kimeswenger, S.; Probst, M.

    2014-08-01

    Context. Polycyclic aromatic hydrocarbons (PAHs) are known today to be one of the carriers of the ubiquitous aromatic infrared (IR) bands. The IR spectra of many astrophysical objects show IR emission features derived from PAH molecules of different size. Space-based observations have shown that these IR emission features are omnipresent and can be found in most objects. However, some of the characteristics of the emitting population remain unclear. The emission bands show details that cannot be explained so far. These unidentified IR features require more laboratory and observational investigations. Aims: We present a theoretical study of the IR spectra of PAHs containing (5, 7)-member ring defects, focusing on pyrene (C16H10) and coronene (C24H12). Methods: Using density functional theory, we investigated the effects of these defects on the IR spectra of pyrene and coronene and their cations and anions. In addition, we explored parts of the potential energy surface of the neutral species and discuss alternative formation pathways. Results: The addition of (5, 7)-membered ring defects in pyrene and coronene results in a change of the IR spectra: both molecules lose their typical spectroscopic signature. We find shifts in the positions of the band as well as different intensities and an increase in the number of features. The boundaries in terms of the size of the PAHs exhibiting a (5, 7)-membered ring defect are studied and shown. Investigating the minimum energy pathway leads to a result of 8.21 eV for pyrene and 8.41 eV for coronene as the minimum activation barriers for the transformation from ground to defected state. Whereas pyrene retains some of its symmetry because of the symmetry exhibited by the Stone-Wales defect itself, coronene loses much more of its symmetry. The formation of these (5, 7)-ring defects in PAHs may be well supported in asymptotic giant branch stars or planetary nebulae. These environments strongly enable the transition from the ground

  20. Photoluminescence and infrared absorption spectra of aminated nanocrystalline diamond surface

    Czech Academy of Sciences Publication Activity Database

    Remeš, Zdeněk; Kozak, Halyna; Babchenko, Oleg; Ukraintsev, Egor; Kromka, Alexander

    2013-01-01

    Roč. 5, č. 6 (2013), s. 515-518 ISSN 2164-6627 R&D Projects: GA ČR(CZ) GBP108/12/G108; GA ČR GPP205/12/P331; GA MŠk LH12236; GA MŠk LH12186 Institutional support: RVO:68378271 Keywords : nanocrystalline diamond * infrared spectroscopy * photoluminescence * fluorescamine Subject RIV: BM - Solid Matter Physics ; Magnetism

  1. Infrared spectra measured during polymer weathering evaluated by factor analysis

    Czech Academy of Sciences Publication Activity Database

    Šeděnková, Ivana; Trchová, Miroslava; Pilař, Jan

    2009-01-01

    Roč. 5, č. 9 (2009), s. 92 ISSN 1336-7242. [Zjazd chemikov /61./. 07.09.2009-11.09.2009, Tatranské Matliare, Vysoké Tatry] R&D Projects: GA ČR GA203/08/0686 Institutional research plan: CEZ:AV0Z40500505 Keywords : degradation * polypropylene * infrared spectroscopy * factor analysis Subject RIV: CD - Macromolecular Chemistry

  2. Infrared spectra, Raman laser, XRD, DSC/TGA and SEM ...

    Indian Academy of Sciences (India)

    Administrator

    infrared inactive, its weak appearance in the spectrum of. MCO3⋅nH2O could be related to weak solid–solid interac- tions causing the symmetry of CO. 2. 3. – .... enge free radicals in vitro in a size-dependent fashion. Accordingly the present techniques of synthesizing sele- nium metal within the range 15–35 nm is a unique ...

  3. Stratospheric HBr mixing ratio obtained from far infrared emission spectra

    Science.gov (United States)

    Park, J. H.; Carli, B.; Barbis, A.

    1989-01-01

    Emission features of HBr isotopes have been identified in high-resolution FIR emission spectra obtained with a balloon-borne Fourier-transform spectrometer in the spring of 1979 at 32 deg N latitude. When six single-scan spectra at a zenith angle of 93.2 deg were averaged, two features of HBr isotopes at 50.054 and 50.069/cm were obtained with a signal-to-noise ratio of 2.5. The volume mixing ratio retrieved from the average spectrum is 2.0 x 10 to the -11th, which is assumed to be constant above 28 km, with an uncertainty of 35 percent. This stratospheric amount of HBr is about the same as the current level of tropospheric organic bromine compounds, 25 pptv. Thus HBr could be the major stratospheric bromine species.

  4. Analysis of far-infrared emission Fourier transform spectra

    Science.gov (United States)

    Park, J. H.; Carli, B.

    1986-01-01

    An analysis method that uses the nonlinear least-squares fit technique has been developed for emission spectra obtained with a Fourier transform spectrometer. This method is used for the analysis of submillimeter-region atmospheric emission spectra obtained with a balloon-borne FT spectrometer that was carried out as a correlative measurement for the Limb IR Monitor of the Stratosphere (LIMS) satellite experiment. The retrieved mixing ratios of H2O and O3 in the stratosphere from four spectral intervals have standard deviations of about 10 percent, and the average values agree to within 10 percent of corresponding results from the LIMS satellite experiment which used a broadband emission radiometer in the IR region.

  5. Fourier transform infrared spectra applications to chemical systems

    CERN Document Server

    Ferraro, John R

    1985-01-01

    The final and largest volume to complete this four-volume treatise is published in response to the intense commercial and research interest in Fourier Transform Interferometry.Presenting current information from leading experts in the field, Volume 4 introduces new information on, for example, applications of Diffuse Reflectance Spectroscopy in the Far-Infrared Region. The editors place emphasis on surface studies and address advances in Capillary Gas Chromatography - Fourier Transform Interferometry.Volume 4 especially benefits spectroscopists and physicists, as well as researchers

  6. FT-Raman and FTIR spectra of photoactive aminobenzazole derivatives in the solid state: A combined experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Alves, Rodrigo Martins [Universidade Federal do Pampa, Campus Bagé, Grupo de Pesquisa em Espectroscopia de Materiais Fotônicos, 96400-970 Bagé, RS (Brazil); Rodembusch, Fabiano Severo [Universidade Federal do Rio Grande do Sul, Grupo de Pesquisa em Fotoquímica Orgânica Aplicada, Av. Bento Gonçalves 9500, CEP 91501-970 Porto Alegre, RS (Brazil); Habis, Charles [Northern Virginia Community College, Manassas, VA (United States); Moreira, Eduardo Ceretta, E-mail: eduardomoreira@unipampa.edu.br [Universidade Federal do Pampa, Campus Bagé, Grupo de Pesquisa em Espectroscopia de Materiais Fotônicos, 96400-970 Bagé, RS (Brazil)

    2014-12-15

    This study reports the experimental investigation of two photoactive aminobenzazole derivatives in the solid state by FT-Raman and Infrared Spectroscopies (FTIR) and its comparison with theoretical models. The optimized molecular structure, vibrational frequencies, and corresponding vibrational assignments of these compounds have been investigated experimentally and theoretically using Spanish Initiative for Electronic Simulations with Thousands of Atoms (SIESTA) and Gaussian03 Software Package. The FT-Raman and FTIR spectra were acquired with high resolution and emission frequencies identified by simulating the vibrational modes. The most intense peak observed in the FT-Raman spectra is the in-plane deformation vibrational of O–H bond that could be related to the vibrational region responsible for the stabilization of the enol conformer in the ground state which undergoes ESIPT to form a keto tautomer in the excited state. Additionally, the position of the amino group played an important role on the vibrational characteristics of the studied compounds. Also, the simulations proved to be a good approach in undertaking the FTIR and FT-Raman experiments. The use of graphic correlations helps us to determine the method and basis that best fit the experimental results. - Highlights: • Structural and vibrational properties of two aminobenzazoles were reported. • Comparison between experimental techniques and theoretical models. • The position of the amino group played an important role on the vibrational characteristics of the studied compounds.

  7. Quantitative mid-infrared spectra of allene and propyne from room to high temperatures

    KAUST Repository

    Es-sebbar, Et-touhami

    2014-11-01

    Allene (a-C3H4; CH2CCH2) and propyne (p-C3H4; CH3C2H) have attracted much interest because of their relevance to the photochemistry in astrophysical environments as well as in combustion processes. Both allene and propyne have strong absorption in the infrared region. In the present work, infrared spectra of a-C3H4 and p-C3H4 are measured in the gas phase at temperatures ranging from 296 to 510 K. The spectra are measured over the 580-3400 cm-1 spectral region at resolutions of 0.08 and 0.25 cm-1 using Fourier Transform Infrared spectroscopy. Absolute integrated intensities of the main infrared bands are determined at room temperature and compared with values derived from literature for both molecules. Integrated band intensities are also determined as a function of temperature in various spectral regions.

  8. A method for comparison of experimental and theoretical differential neutron spectra in the Zenith reactor

    International Nuclear Information System (INIS)

    Reed, D.L.; Symons, C.R.

    1965-01-01

    A method of calculation is given which assists the analyses of chopper measurements of spectra from ZENITH and enables complex multigroup theoretical calculations of the spectra to be put into a form which may be compared with experiment. In addition the theory of the cut-off function has been extended to give analytical expressions which take into account the effects of sub-collimators, off centre slits and of a rotor made of a material partially transparent to neutrons. The theoretical cut-off function suggested shows good agreement with experiment. (author)

  9. Improved assignments of the vibrational fundamental modes of ortho -, meta -, and para -xylene using gas- and liquid-phase infrared and Raman spectra combined with ab initio calculations: Quantitative gas-phase infrared spectra for detection

    Energy Technology Data Exchange (ETDEWEB)

    Lindenmaier, Rodica; Scharko, Nicole K.; Tonkyn, Russell G.; Nguyen, Kiet T.; Williams, Stephen D.; Johnson, Timothy J.

    2017-07-25

    Xylenes contain a blend of the ortho-, meta-, and para- isomers, and all are abundant contaminants in the ground, surface waters, and air. To better characterize xylene and to better enable its detection, we report high quality quantitative vapor-phase infrared spectra of all three isomers over the 540-6500 cm-1 range. All fundamental vibrational modes are assigned based on these vapor-phase infrared spectra, liquid-phase infrared and Raman spectra, along with density functional theory (DFT), ab initio MP2 and high energy-accuracy compound theoretical model (W1BD) calculations. Both MP2 and DFT predict a single conformer with C2v symmetry for ortho-xylene, and two conformers each for meta- and para-xylene, depending on the preferred orientations of the methyl groups. For meta-xylene the two conformers have Cs and C2 symmetry, and for para-xylene these conformers have C2v or C2h symmetry. Since the relative population of the two conformers is approximately 50% for both isomers and predicted frequencies and intensities are very similar for each conformer, we made an arbitrary choice to discuss the Cs conformer for meta-xylene and the C2v conformer for para-xylene. We report integrated band intensities for all isomers. Using the quantitative infrared data, we determine the global warming potential values of each isomer and discuss potential bands for atmospheric monitoring.

  10. Infrared and Raman scattering spectra of layered structured Ga3InSe4 crystals

    Science.gov (United States)

    Isik, M.; Gasanly, N. M.; Korkmaz, F.

    2013-03-01

    The infrared reflectivity and transmittance and Raman scattering in Ga3InSe4 layered crystals were investigated in the frequency ranges of 100-400, 400-4000 and 25-500 cm-1. The refractive and absorption indices, the frequencies of transverse and longitudinal optical modes, high- and low-frequency dielectric constants were obtained from the analysis of the IR reflectivity spectra. The bands observed in IR transmittance spectra were interpreted in terms of two-phonon absorption processes.

  11. Structural properties of maize hybrids established by infrared spectra

    Directory of Open Access Journals (Sweden)

    Radenović Čedomir N.

    2015-01-01

    Full Text Available This paper discusses the application of the infrared (IR spectroscopy method for determination of structural properties of maize hybrid grains. The IR spectrum of maize grain has been registered in the following hybrids: ZP 341, ZP 434 and ZP 505. The existence of spectral bands varying in both number and intensity, as well as their shape, frequency and kinetics have been determined. They have been determined by valence oscillations and deformation oscillations of the following organic compounds: alkanes, alkenes, alkynes, amides, alcohols, ethers, carboxylic acids, esters and aldehydes and ketones, characteristic for biogenic compounds such as carbohydrates, proteins and lipids. In this way, possible changes in the grain structure of observed maize hybrids could be detected.

  12. Standardization of milk mid-infrared spectra from a European dairy network.

    Science.gov (United States)

    Grelet, C; Fernández Pierna, J A; Dardenne, P; Baeten, V; Dehareng, F

    2015-04-01

    The goal of this study was to find a procedure to standardize dairy milk mid-infrared spectra from different Fourier transform mid-infrared spectrophotometers (different brands or models) inside a European dairy network to create new farm-management indicators (e.g., fertility, health, feed, environmental impact) based on milk infrared spectra. This step is necessary to create common spectral databases, allowing the building of statistical tools, to be used by all instruments of the network. The method used was piecewise direct standardization (PDS), which matches slave-instrument spectra on master-instrument spectra. To evaluate the possibility of using common equations on different instruments, the PDS method was tested on a set of milk samples measured on each machine, and an equation predicting fat content of milk is applied on all. Regressions were performed between master and slaves fat predictions, before and after PDS. Bias and root mean square error between predictions were decreased after PDS, respectively, from 0.3781 to 0.0000 and from 0.4609 to 0.0156 (g of fat/100mL of milk). The stability over time of these results was confirmed by an application of the coefficients created by PDS 1 mo later on the slave spectra. These preliminary results showed that the PDS method permits a reduction of the inherent spectral variability between instruments, allowing the merging of Fourier transform mid-infrared milk spectra from different instruments into a common database, the creation of new types of dairy farm management indicators, and the use of these common calibrations for all Fourier transform mid-infrared instruments of the European dairy network. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  13. Infrared absorption spectra of various doping states in cuprate superconductors

    International Nuclear Information System (INIS)

    Yonemitsu, K.; Bishop, A.R.; Lorenzana, J.

    1992-01-01

    Doping states in a two-dimensional three-band extended Peierls-Hubbard model was investigated within inhomogeneous Hartree-Fock and random phase approximation. They are very sensitive to small changes of interaction parameters and their distinct vibrational and optical absorption spectra can be used to identify different doping states. For electronic parameters relevant to cuprate superconductors, as intersite electron-phonon interaction strength increases, the doping state changes from a Zhang-Rice state to a covalent molecular singlet state accompanied by local quenching of the Cu magnetic moment and large local lattice distortion in an otherwise undistorted antiferromagnetic background. In a region where both intersite electron-phonon interaction and on-site electron-electron repulsion are large, we obtain new stable global phases including a bond-order-wave state and a mixed state of spin-Peierls bonds and antiferromagnetic Cu spins, as well as many metastable states. Doping in the bond-order-wave region induces separation of spin and charge. 9 refs

  14. Estimating and correcting mie scattering in synchrotron-based microscopic fourier transform infrared spectra by extended multiplicative signal correction.

    Science.gov (United States)

    Kohler, A; Sulé-Suso, J; Sockalingum, G D; Tobin, M; Bahrami, F; Yang, Y; Pijanka, J; Dumas, P; Cotte, M; van Pittius, D G; Parkes, G; Martens, H

    2008-03-01

    We present an approach for estimating and correcting Mie scattering occurring in infrared spectra of single cells, at diffraction limited probe size, as in synchrotron based microscopy. The Mie scattering is modeled by extended multiplicative signal correction (EMSC) and subtracted from the vibrational absorption. Because the Mie scattering depends non-linearly on alpha, the product of the radius and the refractive index of the medium/sphere causing it, a new method was developed for estimating the Mie scattering by EMSC for unknown radius and refractive index of the Mie scatterer. The theoretically expected Mie contributions for a range of different alpha values were computed according to the formulae developed by Van de Hulst (1957). The many simulated spectra were then summarized by a six-dimensional subspace model by principal component analysis (PCA). This subspace model was used in EMSC to estimate and correct for Mie scattering, as well as other additive and multiplicative interference effects. The approach was applied to a set of Fourier transform infrared (FT-IR) absorbance spectra measured for individual lung cancer cells in order to remove unwanted interferences and to estimate ranges of important alpha values for each spectrum. The results indicate that several cell components may contribute to the Mie scattering.

  15. Infrared spectra alteration in water proximate to the palms of therapeutic practitioners.

    Science.gov (United States)

    Schwartz, Stephan A; De Mattei, Randall J; Brame, Edward G; Spottiswoode, S James P

    2015-01-01

    Through standard techniques of infrared (IR) spectrophotometry, sterile water samples in randomly selected sealed vials evidence alteration of infrared (IR) spectra after being proximate to the palms of the hands of both Practicing and Non-practicing Therapy Practitioners, each of whom employed a personal variation of the Laying-on-of-Hands/Therapeutic Touch processes. This pilot study presents 14 cases, involving 14 Practitioners and 14 Recipients. The first hypothesis, that a variation in the spectra of all (84) Treated spectra compared with all (57) Control spectra would be observed in the 2.5-3.0µm range, was confirmed (P = .02). Overall, 10% (15) of the spectra were done using a germanium internal reflection element (IRE), and 90% of the spectra (126) were done with a zinc selenide IRE. The difference in refractive index between the two IREs skews the data. The zinc selenide IRE spectra alone yield P = .005. The authors believe the most representative evidence for the effect appeared in the sample group of Treated vs Calibration Controls using the zinc selenide IRE (P = .0004). The second hypothesis, that there existed a direct relationship between intensity of effect and time of exposure, was not confirmed. This study replicates earlier findings under conditions of blindness, randomicity, and several levels of controls. Environmental factors are considered as explanations for the observed IR spectrum alteration, including temperature, barometric pressure, and variations dependent on sampling order. They do not appear to explain the effect. Copyright © 2015. Published by Elsevier Inc.

  16. A theoretical and experimental analysis of modulated laser fields and power spectra

    DEFF Research Database (Denmark)

    Olesen, Henning; Jacobsen, G.

    1982-01-01

    A general theoretical description of modulated laser fields and power spectra for a current modulated single-mode laser is derived, taking into account both the intensity and frequency modulation (IM and FM) of the emitted light. The theory relies on an explicit knowledge of the modulus as well...

  17. Matrix isolation infrared spectra of O-H···π Hydrogen bonded ...

    Indian Academy of Sciences (India)

    Matrix isolation infrared spectra of O-H···π Hydrogen bonded complexes of Acetic acid and Trifluoroacetic acid with Benzene. PUJARINI BANERJEE, INDRANI BHATTACHARYA and TAPAS CHAKRABORTY. ∗. Department of Physical Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India.

  18. Retrieval of leaf water content spanning the visible to thermal infrared spectra

    CSIR Research Space (South Africa)

    Ullah, S

    2014-05-01

    Full Text Available The objective of this study was to investigate the entire spectra (from visible to the thermal infrared; 0.390 µm -14.0 µm) to retrieve leaf water content in a consistent manner. Narrow-band spectral indices (calculated from all possible two band...

  19. Gas-phase infrared spectra of cationized nitrogen-substituted polycyclic aromatic hydrocarbons

    NARCIS (Netherlands)

    Galué, Alvaro; Pirali, O.; Oomens, J.

    2010-01-01

    Gas-phase infrared spectra of several ionized nitrogen substituted polycyclic aromatic hydrocarbons (PANHs) have been recorded in the 600-1600 cm(-1) region via IR multiple-photon dissociation (IRMPD) spectroscopy. The UV photoionized PANH ions are trapped and isolated in a quadrupole ion trap where

  20. A New Indicator for Optimal Preprocessing and Wavelengths Selection of Near-Infrared Spectra

    NARCIS (Netherlands)

    Skibsted, E.; Boelens, H.F.M.; Westerhuis, J.A.; Witte, D.T.; Smilde, A.K.

    2004-01-01

    Preprocessing of near-infrared spectra to remove unwanted, i.e., non-related spectral variation and selection of informative wavelengths is considered to be a crucial step prior to the construction of a quantitative calibration model. The standard methodology when comparing various preprocessing

  1. New indicator for optimal preprocessing and wavelength selection of near-infrared spectra

    NARCIS (Netherlands)

    Skibsted, E. T. S.; Boelens, H. F. M.; Westerhuis, J. A.; Witte, D. T.; Smilde, A. K.

    2004-01-01

    Preprocessing of near-infrared spectra to remove unwanted, i.e., non-related spectral variation and selection of informative wavelengths is considered to be a crucial step prior to the construction of a quantitative calibration model. The standard methodology when comparing various preprocessing

  2. Motional narrowing in the time-averaging approximation for simulating two-dimensional nonlinear infrared spectra

    NARCIS (Netherlands)

    Jansen, Thomas la Cour; Ruszel, Wioletta M.

    2008-01-01

    The diagonal linewidth in two-dimensional infrared spectra is often narrower than the distribution of transition frequencies. The width along the antidiagonal is broader than predicted by the lifetime broadening. These effects arise from time-dependent fluctuations of the transition frequencies.

  3. Gas-phase infrared spectra of cationized nitrogen-substituted polycyclic aromatic hydrocarbons

    NARCIS (Netherlands)

    Galué, H.A.; Pirali, O.; Oomens, J.

    2010-01-01

    Gas-phase infrared spectra of several ionized nitrogen substituted polycyclic aromatic hydrocarbons (PANHs) have been recorded in the 600-1600 cm-1 region via IR multiple-photon dissociation (IRMPD) spectroscopy. The UV photoionized PANH ions are trapped and isolated in a quadrupole ion trap where

  4. Nonadiabatic effects in the two-dimensional infrared spectra of peptides : Application to alanine dipeptide

    NARCIS (Netherlands)

    la Cour Jansen, T.; Knoester, J.

    2006-01-01

    A method of simulating two-dimensional infrared spectra accounting for nonadiabatic effects is presented. The method is applied to the amide I modes of a dipeptide. The information necessary to construct the time-dependent Hamiltonian for the system is extracted from molecular dynamics simulations

  5. STELLAR POPULATIONS IN MEDIUM REDSHIFT CLUSTERS .2. OPTICAL-INFRARED PHOTOMETRY AND SPECTRA

    NARCIS (Netherlands)

    PICKLES, AJ; VANDERKRUIT, PC

    1991-01-01

    We present optical and infrared photometry (BV RI, J H K) and spectra of galaxies in 6 medium redshift clusters covering the redshift range 0.19 less-than-or-equal-to z less-than-or-equal-to 0.4. The array photometry is used to note the radial distribution of the cluster galaxies with optical and

  6. Prediction of beta-lactoglobulin genotypes based on milk Fourier transform infrared spectra

    NARCIS (Netherlands)

    Rutten, M.J.M.; Bovenhuis, H.; Heck, J.M.L.; Arendonk, van J.A.M.

    2011-01-01

    ß-Lactoglobulin (ß-LG) genotypes are associated with differences in bovine milk protein composition. Therefore, ß-LG genotypes are of direct relevance for the dairy industry. In this study, we predicted ß-lactoglobulin genotypes based on routinely recorded milk Fourier transform infrared spectra

  7. The NASA Ames Polycyclic Aromatic Hydrocarbon Infrared Spectroscopic Database : The Computed Spectra

    NARCIS (Netherlands)

    Bauschlicher, C. W.; Boersma, C.; Ricca, A.; Mattioda, A. L.; Cami, J.; Peeters, E.; de Armas, F. Sanchez; Saborido, G. Puerta; Hudgins, D. M.; Allamandola, L. J.

    The astronomical emission features, formerly known as the unidentified infrared bands, are now commonly ascribed to polycyclic aromatic hydrocarbons (PAHs). The laboratory experiments and computational modeling done at the NASA Ames Research Center to create a collection of PAH IR spectra relevant

  8. AN ATLAS OF BRIGHT STAR SPECTRA IN THE NEAR-INFRARED FROM CASSINI-VIMS

    International Nuclear Information System (INIS)

    Stewart, Paul N.; Tuthill, Peter G.; Nicholson, Philip D.; Sloan, G. C.; Hedman, Matthew M.

    2015-01-01

    We present the Cassini Atlas Of Stellar Spectra (CAOSS), comprised of near-infrared, low-resolution spectra of bright stars recovered from space-based observations by the Cassini spacecraft. The 65 stellar targets in the atlas are predominately M, K, and S giants. However, it also contains spectra of other bright nearby stars including carbon stars and main-sequence stars from A to F. The spectra presented are free of all spectral contamination caused by the Earth's atmosphere, including the detrimental telluric molecular bands which put parts of the near-infrared spectrum out of reach of terrestrial observations. With a single instrument, a spectro-photometric data set is recovered that spans the near-infrared from 0.8 to 5.1 μm with spectral resolution ranging from R = 53.5 to R = 325. Spectra have been calibrated into absolute flux units after careful characterization of the instrumental spectral efficiency. Spectral energy distributions for most stars match closely with literature values. All final data products have been made available online

  9. AN ATLAS OF BRIGHT STAR SPECTRA IN THE NEAR-INFRARED FROM CASSINI-VIMS

    Energy Technology Data Exchange (ETDEWEB)

    Stewart, Paul N.; Tuthill, Peter G. [Sydney Institute for Astronomy, School of Physics, The University of Sydney, NSW 2006 (Australia); Nicholson, Philip D. [Department of Astronomy, Cornell University, Ithaca, NY 14853 (United States); Sloan, G. C. [Cornell Center for Astrophyics and Planetary Science, Cornell University, Ithaca, NY 14853 (United States); Hedman, Matthew M., E-mail: p.stewart@physics.usyd.edu.au [Department of Physics, University of Idaho, Moscow, ID 83844 (United States)

    2015-12-15

    We present the Cassini Atlas Of Stellar Spectra (CAOSS), comprised of near-infrared, low-resolution spectra of bright stars recovered from space-based observations by the Cassini spacecraft. The 65 stellar targets in the atlas are predominately M, K, and S giants. However, it also contains spectra of other bright nearby stars including carbon stars and main-sequence stars from A to F. The spectra presented are free of all spectral contamination caused by the Earth's atmosphere, including the detrimental telluric molecular bands which put parts of the near-infrared spectrum out of reach of terrestrial observations. With a single instrument, a spectro-photometric data set is recovered that spans the near-infrared from 0.8 to 5.1 μm with spectral resolution ranging from R = 53.5 to R = 325. Spectra have been calibrated into absolute flux units after careful characterization of the instrumental spectral efficiency. Spectral energy distributions for most stars match closely with literature values. All final data products have been made available online.

  10. Visible and infrared absorption spectra of covering materials for solar collectors

    International Nuclear Information System (INIS)

    Pelece, I.

    2008-01-01

    Use of solar energy increases every year. In Latvia, solar energy is used mainly by solar collectors. The main part of the solar collector is the absorber, but not less important is the covering material which protects the absorber from the cooling impact of the wind. This cover must be transparent for solar radiation, but opaque for thermal radiation of the absorber, which is at greater wavelengths. Therefore it is important to measure absorption spectra of possible covering materials at visible and infrared wavelength ranges. Absorption spectra have been measured for several materials: glass, polythene, Plexiglas, and cells Plexiglas. Absorption spectra for all these materials are measured in three ranges: ultraviolet-visible (UV-VIS): 250-1000 nm; near infrared (NIR): 700-110 nm; infrared (IR): 1200-8000 nm. UV-VIS spectra with the 'Ocean Optics' device HR-4000 have been measured, but NIR and IR - with 'Bruker' Furje spectrometer EQUINOX 55. Evaluation of absorption spectra showed that the most suitable material (from the considered) for covering of solar collectors is Plexiglas

  11. Infrared spectra of protonated coronene and its neutral counterpart in solid parahydrogen: implications for unidentified interstellar infrared emission bands.

    Science.gov (United States)

    Bahou, Mohammed; Wu, Yu-Jong; Lee, Yuan-Pern

    2014-01-20

    Large protonated polycyclic aromatic hydrocarbons (H(+) PAHs) are possible carriers of unidentified infrared (UIR) emission bands from interstellar objects, but the characterization of infrared (IR) spectra of large H(+) PAHs in the laboratory is challenging. IR absorption spectra of protonated coronene (1-C24 H13 (+) ) and mono-hydrogenated coronene (1-C24 H13 (.) ), which were produced upon electron bombardment of parahydrogen containing a small proportion of coronene (C24 H12 ) during matrix deposition, were recorded. The spectra are of a much higher resolution than those obtained by IR multiphoton dissociation by Dopfer and co-workers. The IR spectra of protonated pyrene and coronene collectively appear to have the required chromophores for features of the UIR bands, and the spectral shifts on an increase in the number of benzenoid rings point in the correct direction towards the positions of the UIR bands. Larger protonated peri-condensed PAHs might thus be key species among the carriers of UIR bands. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. INFRARED PHOTOLUMINESCENCE SPECTRA OF PBS NANOPARTICLES PREPARED BY LANGMUIR–BLODGETT AND LASER ABLATION METHODS

    Directory of Open Access Journals (Sweden)

    Zdeněk Remes

    2014-12-01

    Full Text Available We optimized the optical setup originally designed for the photoluminescence measurements in the spectral range 400‒1100 nm. New design extends the spectral range into the near infrared region 900‒1700 nm and allows the colloidal solutions measurements in cuvettes as well as the measurements of nanoparticles deposited in the form of thin films on glass substrates. The infrared photoluminescence spectra of the PbS nanoparticles prepared by the Langmuir–Blodgett technique show the higher photoluminescence intensity and the shift to the shorter wavelengths compared to the infrared photoluminescence spectra of the PbS nanoparticles prepared by the laser ablation from PbS target. We aslo proved the high stability of PbS nanoparticles prepared in the form of thin layers.

  13. Diffuse reflectance infrared Fourier-Transform spectra of selected organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Harmon, S.H.; Caton, J.E.

    1982-05-01

    Diffuse reflectance infrared spectra of a variety of different organic compounds have been determined. Profiles of the spectra along with the location and relative intensity of the principal bands have been included for each compound studied. In addition both diffuse reflectance and transmittance infrared spectra were obtained for the same samples, and the spectral results were compared. Although some minor variations are observed between a diffuse reflectance spectrum and the corresponding transmittance spectrum, the diffuse reflectance is quite useful and may be a superior technique for the study of many samples because it possesses an inherently higher signal-to-noise response, requires less sample preparation and allows a very wide range of samples (solids, liquids of low volatility, neat sample, or sample diluted in a reflecting medium) to be studied under very similar conditions.

  14. Synthesis, crystal structure, vibrational spectra and theoretical calculations of quantum chemistry of a potential antimicrobial Meldrum's acid derivative

    Science.gov (United States)

    Campelo, M. J. M.; Freire, P. T. C.; Mendes Filho, J.; de Toledo, T. A.; Teixeira, A. M. R.; da Silva, L. E.; Bento, R. R. F.; Faria, J. L. B.; Pizani, P. S.; Gusmão, G. O. M.; Coutinho, H. D. M.; Oliveira, M. T. A.

    2017-10-01

    A new derivative of Meldrum's acid 5-((5-chloropyridin-2-ylamino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (CYMM) of molecular formula C12H11ClN2O4 was synthesized and structurally characterized using single crystal X-ray diffraction technique. The vibrational properties of the crystal were studied by Fourier Transform infrared (FT-IR), Fourier Transform Raman (FT-Raman) techniques and theoretical calculations of quantum chemistry using Density functional theory (DFT) and Density functional perturbation theory (DFPT). A comparison with experimental spectra allowed the assignment of all the normal modes. The descriptions of the normal modes were carried by means of potential energy distribution (PED). Additionally, analysis of the antimicrobial activity and antibiotic resistance modulatory activity was carried out to evaluate the antibacterial potential of the CYMM.

  15. Spatial decomposition and assignment of infrared spectra of simple ions in water from mid-infrared to THz frequencies: Li+(aq) and F-(aq)

    Science.gov (United States)

    Śmiechowski, Maciej; Forbert, Harald; Marx, Dominik

    2013-07-01

    Ionic hydration is of fundamental relevance from chemical reactivity in aqueous solution to biomolecular function at physiological conditions. Vibrational spectroscopy belongs to the most widely used experimental methods in studies of solvation phenomena. There is, however, still limited molecular understanding as to how the vibrational response of solutions is modulated by the presence of solvation shells around solutes, i.e., by interfacial water. Liquid-state THz spectroscopy has been demonstrated to be able to detect even small solute-induced changes of the hydrogen bond dynamics at the solute-water interface. In many cases it reveals rather long-ranged dynamical correlations around solutes, involving many solvent molecules, that can be tackled theoretically by analyzing vibrational spectra in a distance-resolved manner. Here, several spatial decomposition schemes for infrared spectra are used to reveal the distinct distance- and frequency-dependent contributions of the solvation shells to the spectral response in aqueous solutions of Li+ and F-. The importance of an explicit representation of the solute's electronic structure for the proper description of solute-solvent polarization effects is demonstrated. The solvent's response to the presence of the solute is systematically disentangled and reveals important differences between the spectral responses due to intra- and intermolecular motion as probed in the mid- and far-infrared spectral windows, respectively.

  16. Overview of the use of theory to understand infrared and Raman spectra and images of biomolecules: colorectal cancer as an example

    DEFF Research Database (Denmark)

    Piva, J. A. A. C.; Silva, J. L. R.; Raniero, L.

    2011-01-01

    In this work, we present the state of the art in the use of theory (first principles, molecular dynamics, and statistical methods) for interpreting and understanding the infrared (vibrational) absorption and Raman scattering spectra. It is discussed how they can be used in combination with purely...... and that the models used must take this into account. Hence, the use of statistical methods to interpret and understand the infrared and Raman spectra and images from biological tissues, cells, parts of cells, fluids, and even whole organism should change accordingly. As the species, conformers and structures...... of biomolecules are very sensitive to their environment and aggregation state, the combined use of infrared and Raman spectroscopy and imaging and theoretical simulations are clearly fields, which can benefit from their joint and mutual development....

  17. Resonant Mie scattering (RMieS) correction of infrared spectra from highly scattering biological samples.

    Science.gov (United States)

    Bassan, Paul; Kohler, Achim; Martens, Harald; Lee, Joe; Byrne, Hugh J; Dumas, Paul; Gazi, Ehsan; Brown, Michael; Clarke, Noel; Gardner, Peter

    2010-02-01

    Infrared spectra of single biological cells often exhibit the 'dispersion artefact' observed as a sharp decrease in intensity on the high wavenumber side of absorption bands, in particular the Amide I band at approximately 1655 cm(-1), causing a downward shift of the true peak position. The presence of this effect makes any biochemical interpretation of the spectra unreliable. Recent theory has shed light on the origins of the 'dispersion artefact' which has been attributed to resonant Mie scattering (RMieS). In this paper a preliminary algorithm for correcting RMieS is presented and evaluated using simulated data. Results show that the 'dispersion artefact' appears to be removed; however, the correction is not perfect. An iterative approach was subsequently implemented whereby the reference spectrum is improved after each iteration, resulting in a more accurate correction. Consequently the corrected spectra become increasingly more representative of the pure absorbance spectra. Using this correction method reliable peak positions can be obtained.

  18. Improved experimental energy levels of carbon I from solar infrared spectra

    International Nuclear Information System (INIS)

    Chang, E.S.; Geller, M.

    1998-01-01

    We have improved the energy levels in neutral carbon using high resolution infrared solar spectra. The main source is the space-based ATMOS spectrum measured by the Fourier transform spectroscopy technique from 600 to 4800 cm -1 . From these infrared data, we have determined 19 new energy levels in the 5f, 5g, 6g and 6h configurations. To extend measurements to higher frequencies, we also use other FTS solar spectra: the MARK IV balloon data, covering from 4700 to 5700 cm -1 , and the ground-based NOAO spectra, up to 9000 cm -1 of Livingston and Wallace and 8900 to 13 600 cm -1 of Wallace et al. For completeness' sake, we include the 63 new levels found by Feldman et al. plus 8 new levels derived from the VUV data. Utilizing all existing carbon spectra from the far infrared to the vacuum ultraviolet, we have revised Johansson's energy levels and the ionization potential, resulting in improving the accuracy by about an order of magnitude to about 3 mK. (orig.)

  19. [The evaluation of hydrocarbon potential generation for source rocks by near-infrared diffuse reflection spectra].

    Science.gov (United States)

    Zhang, Yu-Jia; Xu, Xiao-Xuan; Song, Ning; Wu, Zhong-Chen; Zhou, Xiang; Chen, Jin; Cao, Xue-Wei; Wang, Bin

    2011-04-01

    Near-infrared (NIR) and mid-infrared (MIR) diffuse reflection spectra were compared and evaluated for hydrocarbon potential generation of source rocks. Near-infrared diffuse reflectance often exhibits significant differences in the spectra due to the non-homogeneous distribution of the particles, so the signal-to-noise ratio of NIR is much lower than MIR It is too difficult to get accurate results by NIR without using a strong spectral preprocessing method to remove systematic noise such as base-line variation and multiplicative scatter effects. In the present paper, orthogonal signal correction (OSC) and an improved algorithm of it, i.e. direct orthogonal signal correction (DOSC), are used as different methods to preprocess both the NIR and MIR spectra of the hydrocarbon source rocks. Another algorithm, wavelet multi-scale direct orthogonal signal correction (WMDOSC), which is a combination of discrete wavelet transform (DWT) and DOSC, is also used as a preprocessing method. Then, the calibration model of hydrocarbon source rocks before and after pretreatment was established by interval partial least square (iPLS). The experimental results show that WMDOSC is more successfully applied to preprocess the NIR spectra data of the hydrocarbon source rocks than other two algorithms, and NIR performed as good as MIR in the analysis of hydrocarbon potential generation of source rocks with WMDOSC-iPLS pretreatment calibration model.

  20. Spectra Transfer Between a Fourier Transform Near-Infrared Laboratory and a Miniaturized Handheld Near-Infrared Spectrometer.

    Science.gov (United States)

    Hoffmann, Uwe; Pfeifer, Frank; Hsuing, Chang; Siesler, Heinz W

    2016-05-01

    The aim of this contribution is to demonstrate the transfer of spectra that have been measured on two different laboratory Fourier transform near-infrared (FT-NIR) spectrometers to the format of a handheld instrument by measuring only a few samples with both spectrometer types. Thus, despite the extreme differences in spectral range and resolution, spectral data sets that have been collected and quantitative as well as qualitative calibrations that have been developed thereof, respectively, over a long period on a laboratory instrument can be conveniently transferred to the handheld system. Thus, the necessity to prepare completely new calibration samples and the effort required to develop calibration models when changing hardware platforms is minimized. The enabling procedure is based on piecewise direct standardization (PDS) and will be described for the data sets of a quantitative and a qualitative application case study. For this purpose the spectra measured on the FT-NIR laboratory spectrometers were used as "master" data and transferred to the "target" format of the handheld instrument. The quantitative test study refers to transmission spectra of three-component liquid solvent mixtures whereas the qualitative application example encompasses diffuse reflection spectra of six different current polymers. To prove the performance of the transfer procedure for quantitative applications, partial least squares (PLS-1) calibrations were developed for the individual components of the solvent mixtures with spectra transferred from the master to the target instrument and the cross-validation parameters were compared with the corresponding parameters obtained for spectra measured on the master and target instruments, respectively. To test the retention of the discrimination ability of the transferred polymer spectra sets principal component analyses (PCAs) were applied exemplarily for three of the six investigated polymers and their identification was demonstrated by

  1. Pinus taeda L. wood property calibrations based on variable numbers of near infrared spectra per core and cores per plantation

    Science.gov (United States)

    Laurence R. Schimleck; Justin A. Tyson; David Jones; Gary F. Peter; Richard F. Daniels; Alexander III Clark

    2007-01-01

    Near infrared (NIR) spectroscopy provides a rapid, non-destructive method for the estimation of several wood properties of increment cores. MR spectra are collected from adjacent sections of the same core; however, not all spectra are required for calibration purposes as spectra from the same core are autocorrelated. Previously, we showed that wood property...

  2. Variations in the Infrared Spectra of Wüstite with Defects and Disorder

    Science.gov (United States)

    Koike, C.; Matsuno, J.; Chihara, H.

    2017-08-01

    The presence of FeO particles in circumstellar space has been suggested based on the observation of a mysterious 21 μm emission band. However, the complete infrared spectra of FeO have not been obtained so far; hence, data of the infrared (IR) spectra of FeO need to be investigated. We prepared synthetic and commercial samples of FeO, which were obtained by crushing bulk samples, annealing iron oxalate dihydrate ({{FeC}}2{{{O}}}4\\cdot 2{{{H}}}2{{O}}), and mechanical milling of a powder mixture comprising (Fe and {{Fe}}2{{{O}}}3) particles with different milling times. We present a new study on the IR spectra of these samples, and show that these spectra changed according to defects and disorders. Furthermore, FeO particles are very sensitive to oxygen fugacity and temperature. The spectra of FeO particles were compared with the unidentified observed feature. It may be difficult for FeO particles to exist alone in the ISM and circumstellar space. This may be connected to the problem of missing iron in the ISM.

  3. Simulation of attenuated total reflection infrared absorbance spectra: applications to automotive clear coat forensic analysis.

    Science.gov (United States)

    Lavine, Barry K; Fasasi, Ayuba; Mirjankar, Nikhil; Nishikida, Koichi; Campbell, Jay

    2014-01-01

    Attenuated total reflection (ATR) is a widely used sampling technique in infrared (IR) spectroscopy because minimal sample preparation is required. Since the penetration depth of the ATR analysis beam is quite shallow, the outer layers of a laminate or multilayered paint sample can be preferentially analyzed with the entire sample intact. For this reason, forensic laboratories are taking advantage of ATR to collect IR spectra of automotive paint systems that may consist of three or more layers. However, the IR spectrum of a paint sample obtained by ATR will exhibit distortions, e.g., band broadening and lower relative intensities at higher wavenumbers, compared with its transmission counterpart. This hinders library searching because most library spectra are measured in transmission mode. Furthermore, the angle of incidence for the internal reflection element, the refractive index of the clear coat, and surface contamination due to inorganic contaminants can profoundly influence the quality of the ATR spectrum obtained for automotive paints. A correction algorithm to allow ATR spectra to be searched using IR transmission spectra of the paint data query (PDQ) automotive database is presented. The proposed correction algorithm to convert transmission spectra from the PDQ library to ATR spectra is able to address distortion issues such as the relative intensities and broadening of the bands, and the introduction of wavelength shifts at lower frequencies, which prevent library searching of ATR spectra using archived IR transmission data.

  4. Infrared and Raman scattering spectra of layered structured Ga3InSe4 crystals

    International Nuclear Information System (INIS)

    Isik, M.; Gasanly, N.M.; Korkmaz, F.

    2013-01-01

    The infrared reflectivity and transmittance and Raman scattering in Ga 3 InSe 4 layered crystals were investigated in the frequency ranges of 100–400, 400–4000 and 25–500 cm −1 . The refractive and absorption indices, the frequencies of transverse and longitudinal optical modes, high- and low-frequency dielectric constants were obtained from the analysis of the IR reflectivity spectra. The bands observed in IR transmittance spectra were interpreted in terms of two-phonon absorption processes

  5. 8200 to 11200 A spectra of peculiar emission-line objects with infrared excess

    International Nuclear Information System (INIS)

    Andrillat, Y.; Swings, J.P.

    1976-01-01

    Spectra of 25 peculiar emission-line stars with infrared excesses were obtained in the 8200--11200 A region, using a grating spectrograph equipped with an S-1 photocathode image-tube at the Cassegrain focus of the 1.93 m (77 inch) telescope at the Haute Provence Observatory. The strongest emission features shown on the figure are due essentially to lines of the Paschen series, of the Ca II triplet, and of He I lambda 10830, O I lambda 8446, [S III] lambda lambda 9069 and 9532, and [Fe III] lambda 10504; a strong emission present at 9999 A on most of the spectra remains unidentified

  6. X-ray spectra of PG quasars. I. The continuum from X-rays to infrared

    International Nuclear Information System (INIS)

    Elvis, M.; Green, R.F.; Bechtold, J.; Schmidt, M.; Neugebauer, G.; Kitt Peak National Observatory, Tucson, AZ; Steward Observatory, Tucson, AZ; Palomar Observatory, Pasadena, CA)

    1986-01-01

    Einstein IPC X-ray spectra for a sample of eight optically selected quasars from the Palomar Bright Quasar survey are presented. The quasars have a mean power law energy slope which in five individual cases is inconsistent with the value found in hard X-ray selection criterion rather than luminosity, redshift, or U-B color. New IUE and optical continuum spectra and infrared photometry are presented for these quasars. The data are combined into log vf(v) and log v distributions which support the decomposition of the overall quasar spectrum into a power law plus a superposed optical-UV big bump which may be due to an accretion disk. At least six of the quasars have vf(v)s which are roughly constant between their infrared and X-ray power laws, suggesting a strong link between the two regions. 104 references

  7. Fast forward modeling of Titan's infrared spectra to invert VIMS/Cassini hyperspectral images

    Science.gov (United States)

    Rodriguez, S.; Le Mouélic, Stéphane; Rannou, P.; Combe, J.-P.; Corre, L.L.; Tobie, G.; Barnes, J.W.; Sotin, Christophe; Brown, R.H.; Baines, K.H.; Buratti, B.J.; Clark, R.N.; Nicholson, P.D.

    2009-01-01

    The surface of Titan, the largest icy moon of Saturn, is veiled by a very thick and hazy atmosphere. The Visual and Infrared Mapping Spectrometer onboard the Cassini spacecraft, in orbit around Saturn since July 2004, conduct an intensive survey of Titan with the objective to understand the complex nature of the atmosphere and surface of the mysterious moon and the way they interact. Accurate radiative transfer modeling is necessary to analyze Titan's infrared spectra, but are often very computer resources demanding. As Cassini has gathered hitherto millions of spectra of Titan and will still observe it until at least 2010, we report here on the development of a new rapid, simple and versatile radiative transfer model specially designed to invert VIMS datacubes. ?? 2009 IEEE.

  8. The infrared spectra and structure of acetylsalicylic acid (aspirin) and its oxyanion: an ab initio force field treatment

    Science.gov (United States)

    Binev, I. G.; Stamboliyska, B. A.; Binev, Y. I.

    1996-05-01

    The structures of acetylsalicylic acid (aspirin) (I) and its oxyanion (II) have been studied by means of infrared spectra and ab initio 3-21 G force field calculations. The 3100-1100 cm -1 region bands of both the aspirin molecule and its oxyanion have been assigned. The theoretical infrared data for the free aspirin anion are in good agreement with the experimental data for aspirin alkali-metal salts in dimethyl sulfoxide- d6. The theoretical geometrical parameters for the isolated aspirin molecule are close to the literature X-ray diffraction data for its dimer in the solid state, except for those of the carboxy group, which participates directly in hydrogen bond formation. The changes in both the spectral and geometrical parameters, caused by the conversion of the aspirin molecule into the anion, are essential, but they are localized mainly within the carboxy group and the adjacent C-Ph bond. This is also true for the changes in the corresponding bond indices and electronic charges.

  9. Baseline Correction of Diffuse Reflection Near-Infrared Spectra Using Searching Region Standard Normal Variate (SRSNV).

    Science.gov (United States)

    Genkawa, Takuma; Shinzawa, Hideyuki; Kato, Hideaki; Ishikawa, Daitaro; Murayama, Kodai; Komiyama, Makoto; Ozaki, Yukihiro

    2015-12-01

    An alternative baseline correction method for diffuse reflection near-infrared (NIR) spectra, searching region standard normal variate (SRSNV), was proposed. Standard normal variate (SNV) is an effective pretreatment method for baseline correction of diffuse reflection NIR spectra of powder and granular samples; however, its baseline correction performance depends on the NIR region used for SNV calculation. To search for an optimal NIR region for baseline correction using SNV, SRSNV employs moving window partial least squares regression (MWPLSR), and an optimal NIR region is identified based on the root mean square error (RMSE) of cross-validation of the partial least squares regression (PLSR) models with the first latent variable (LV). The performance of SRSNV was evaluated using diffuse reflection NIR spectra of mixture samples consisting of wheat flour and granular glucose (0-100% glucose at 5% intervals). From the obtained NIR spectra of the mixture in the 10 000-4000 cm(-1) region at 4 cm intervals (1501 spectral channels), a series of spectral windows consisting of 80 spectral channels was constructed, and then SNV spectra were calculated for each spectral window. Using these SNV spectra, a series of PLSR models with the first LV for glucose concentration was built. A plot of RMSE versus the spectral window position obtained using the PLSR models revealed that the 8680–8364 cm(-1) region was optimal for baseline correction using SNV. In the SNV spectra calculated using the 8680–8364 cm(-1) region (SRSNV spectra), a remarkable relative intensity change between a band due to wheat flour at 8500 cm(-1) and that due to glucose at 8364 cm(-1) was observed owing to successful baseline correction using SNV. A PLSR model with the first LV based on the SRSNV spectra yielded a determination coefficient (R2) of 0.999 and an RMSE of 0.70%, while a PLSR model with three LVs based on SNV spectra calculated in the full spectral region gave an R2 of 0.995 and an RMSE of

  10. Source brightness fluctuation correction of solar absorption fourier transform mid infrared spectra

    Directory of Open Access Journals (Sweden)

    T. Ridder

    2011-06-01

    Full Text Available The precision and accuracy of trace gas observations using solar absorption Fourier Transform infrared spectrometry depend on the stability of the light source. Fluctuations in the source brightness, however, cannot always be avoided. Current correction schemes, which calculate a corrected interferogram as the ratio of the raw DC interferogram and a smoothed DC interferogram, are applicable only to near infrared measurements. Spectra in the mid infrared spectral region below 2000 cm−1 are generally considered uncorrectable, if they are measured with a MCT detector. Such measurements introduce an unknown offset to MCT interferograms, which prevents the established source brightness fluctuation correction. This problem can be overcome by a determination of the offset using the modulation efficiency of the instrument. With known modulation efficiency the offset can be calculated, and the source brightness correction can be performed on the basis of offset-corrected interferograms. We present a source brightness fluctuation correction method which performs the smoothing of the raw DC interferogram in the interferogram domain by an application of a running mean instead of high-pass filtering the corresponding spectrum after Fourier transformation of the raw DC interferogram. This smoothing can be performed with the onboard software of commercial instruments. The improvement of MCT spectra and subsequent ozone profile and total column retrievals is demonstrated. Application to InSb interferograms in the near infrared spectral region proves the equivalence with the established correction scheme.

  11. Emission Lines in the Near-infrared Spectra of the Infrared Quintuplet Stars in the Galactic Center

    Energy Technology Data Exchange (ETDEWEB)

    Najarro, F. [Departamento de Astrofísica, Centro de Astrobiología (CSIC-INTA), Ctra. Torrejón a Ajalvir km 4, E-28850 Torrejón de Ardoz (Spain); Geballe, T. R. [Gemini Observatory, 670 North A’ohoku Place, Hilo, HI 96720 (United States); Figer, D. F. [Center for Detectors, Rochester Institute of Technology, 74 Lomb Memorial Drive, Rochester, NY 14623 (United States); Fuente, D. de la [Instituto de Astronomía, Unidad Académica en Ensenada, Universidad Nacional Autónoma de México, Ensenada 22860, México (Mexico)

    2017-08-20

    We report the detection of a number of emission lines in the 1.0–2.4 μ m spectra of four of the five bright-infrared dust-embedded stars at the center of the Galactic center’s (GC) Quintuplet Cluster. Spectroscopy of the central stars of these objects is hampered not only by the large interstellar extinction that obscures all of the objects in the GC, but also by the large amounts of warm circumstellar dust surrounding each of the five stars. The pinwheel morphologies of the dust observed previously around two of them are indicative of Wolf–Rayet colliding wind binaries; however, infrared spectra of each of the five have until now revealed only dust continua steeply rising to long wavelengths and absorption lines and bands from interstellar gas and dust. The emission lines detected, from ionized carbon and from helium, are broad and confirm that the objects are dusty late-type carbon Wolf–Rayet stars.

  12. A theoretical study on the pH dependence of X-ray emission spectra for aqueous acetic acid

    Science.gov (United States)

    Nishida, Naohiro; Tokushima, Takashi; Takahashi, Osamu

    2016-04-01

    We performed theoretical calculations to reproduce the site-selective XES spectra for aqueous acetic acid at the oxygen K-edge. The shape of the experimental XES spectra obtained from aqueous acetic acid drastically changed when the pH value was high. Structure sampling of an aqueous acetic acid cluster model was performed by the ab initio molecular dynamics trajectory. Relative XES peak intensities for the core⿿hole excited state dynamics simulations were calculated using density functional theory. We found that the theoretical XES spectra reproduced well the experimental spectra and that these calculations gave us electronic and molecular structure information about aqueous acetic acid.

  13. Protonation effects on the UV/Vis absorption spectra of imatinib: A theoretical and experimental study

    Science.gov (United States)

    Grante, Ilze; Actins, Andris; Orola, Liana

    2014-08-01

    An experimental and theoretical investigation of protonation effects on the UV/Vis absorption spectra of imatinib showed systematic changes of absorption depending on the pH, and a new absorption band appeared below pH 2. These changes in the UV/Vis absorption spectra were interpreted using quantum chemical calculations. The geometry of various imatinib cations in the gas phase and in ethanol solution was optimized with the DFT/B3LYP method. The resultant geometries were compared to the experimentally determined crystal structures of imatinib salts. The semi-empirical ZINDO-CI method was employed to calculate the absorption lines and electronic transitions. Our study suggests that the formation of the extra near-UV absorption band resulted from an increase of imatinib trication concentration in the solution, while the rapid increase of the first absorption maximum could be attributed to both the formation of imatinib trication and tetracation.

  14. Theoretical study of the infrared frequencies of crystalline methyl acetate under interstellar medium conditions.

    Science.gov (United States)

    Narayanan, Radhika; Inomata, Kensuke; Gopakumar, Geetha; Sivaraman, Bhalamurugan; Zempo, Yasunari; Hada, Masahiko

    2016-01-15

    Identification of methyl acetate in the interstellar medium (ISM) and its spectroscopic studies have prompted us to investigate the structure of crystalline methyl acetate using numerical calculations. Here, we present a theoretical study of the structure of crystalline methyl acetate and its isotopologues and compare the calculated infrared (IR) spectra with the available experimental data. The optimized structure and vibrational properties were calculated using SIESTA software at 0 K. In the optimization process, the Perdew-Burke-Ernzerhof functional and conjugate gradient methods were used with double zeta polarization basis functions. After optimization of the periodic structure, the vibrational frequencies and normal modes were calculated within the harmonic approximation. Using the calculated results, we refine the mode assignments of experimental work on crystalline methyl acetate and determine the low frequency modes (below 650 cm(-1)). To investigate the accuracy of the pseudopotential and confirm the IR frequencies, we performed molecular calculations using a periodic model of methyl acetate and its isotopologues using SIESTA and compared them with results obtained from Gaussian 09 (all electron method) calculations. Finally, we assigned the vibrational modes of crystalline CD3-COO-CH3 and CH3-COO-CD3, for which experimental data are not available in the crystalline phase under ISM conditions. For all of the calculation methods, the IR vibrational modes of molecular and crystalline methyl acetate and its isotopologues were in good agreement with the available experimental data and predict the unavailable values. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. [Maize Hybrid Seed Purity Identification Based on Near Infrared Reflectance (NIR) and Transmittance (NIT) Spectra].

    Science.gov (United States)

    Li, Tian-xin; Jia, Shi-qiang; Liu, Xu; Zhao, Sheng-yi; Ran, Hang; Yan, Yan-lu; An, Dong

    2015-12-01

    This article explore the feasibility of using Near Infrared Reflectance (NIR) and Transmittance (NIT) Spectroscopy (908.1-1677.2 nm wavelength range) to identify maize hybrid purity, and compare the performance of NIR and NIT spectroscopy. Principle Component Analysis (PCA) and Orthogonal Linear Discriminant Analysis (OLDA) were used to reduce the dimension of spectra which have been pretreated by first derivative and vector normalization. The hybrid purity identification model of Nonghua101 and Jingyu16 were built by SVM. Models based on NIR spectra obtained correct identification rate as 100% and 90% for Nonghua101 and Jingyu16 respectively. But NIR spectra were greatly influenced by the placement of seeds, and there existed significant difference between NIR spectra of embryo and non-embryo side. Models based on NIT spectroscopy yielded correct identification rate as 98% both for Nonghua101 and Jingyu16. NIT spectra of embryo and non-embryo side were highly similar. The results indicate that it is feasible to identify maize hybrid purity based on NIR and NIT spectroscopy, and NIT spectroscopy is more suitable to analyze single seed kernel than NIR spectroscopy.

  16. A consensus successive projections algorithm--multiple linear regression method for analyzing near infrared spectra.

    Science.gov (United States)

    Liu, Ke; Chen, Xiaojing; Li, Limin; Chen, Huiling; Ruan, Xiukai; Liu, Wenbin

    2015-02-09

    The successive projections algorithm (SPA) is widely used to select variables for multiple linear regression (MLR) modeling. However, SPA used only once may not obtain all the useful information of the full spectra, because the number of selected variables cannot exceed the number of calibration samples in the SPA algorithm. Therefore, the SPA-MLR method risks the loss of useful information. To make a full use of the useful information in the spectra, a new method named "consensus SPA-MLR" (C-SPA-MLR) is proposed herein. This method is the combination of consensus strategy and SPA-MLR method. In the C-SPA-MLR method, SPA-MLR is used to construct member models with different subsets of variables, which are selected from the remaining variables iteratively. A consensus prediction is obtained by combining the predictions of the member models. The proposed method is evaluated by analyzing the near infrared (NIR) spectra of corn and diesel. The results of C-SPA-MLR method showed a better prediction performance compared with the SPA-MLR and full-spectra PLS methods. Moreover, these results could serve as a reference for combination the consensus strategy and other variable selection methods when analyzing NIR spectra and other spectroscopic techniques. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. An improved algorithm for fast resonant Mie scatter correction of infrared spectra of cells and tissues.

    Science.gov (United States)

    Konevskikh, Tatiana; Lukacs, Rozalia; Kohler, Achim

    2018-01-01

    Mie scattering effects create serious problems for the interpretation of Fourier-transform infrared spectroscopy spectra of single cells and tissues. During recent years, different techniques were proposed to retrieve pure absorbance spectra from spectra with Mie distortions. Recently, we published an iterative algorithm for correcting Mie scattering in spectra of single cells and tissues, which we called "the fast resonant Mie scatter correction algorithm." The algorithm is based on extended multiplicative signal correction (EMSC) and employs a meta-model for a parameter range of refractive index and size parameters. In the present study, we suggest several improvements of the algorithm. We demonstrate that the improved algorithm reestablishes chemical features of the measured spectra, and show that it tends away from the reference spectrum employed in the EMSC. We suggest strategies for choosing parameter ranges and other model parameters such as the number of principal components of the meta-model and the number of iterations. We demonstrate that the suggested algorithm optimizes an error function of the refractive index in a forward Mie model. We suggest a stop criterion for the iterative algorithm based on the error function of the forward model. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Spectral-statistics properties of the experimental and theoretical light meson spectra

    Energy Technology Data Exchange (ETDEWEB)

    Munoz, L., E-mail: laura@nuc5.fis.ucm.es [European Centre for Theoretical Studies in Nuclear Physics and Related Areas (ECT), Villa Tambosi, Strada delle Tabarelle 286, Villazzano, I-38123 (Italy); Fernandez-Ramirez, C., E-mail: cesar@nuc2.fis.ucm.es [European Centre for Theoretical Studies in Nuclear Physics and Related Areas (ECT), Villa Tambosi, Strada delle Tabarelle 286, Villazzano, I-38123 (Italy); Grupo de Fisica Nuclear, Departamento de Fisica Atomica, Molecular y Nuclear, Facultad de Ciencias Fisicas, Universidad Complutense de Madrid, Avda. Complutense s/n, E-28040 Madrid (Spain); Relano, A., E-mail: armando.relano@gmail.com [Instituto de Estructura de la Materia, IEM-CSIC, Serrano 123, E-28006 Madrid (Spain); Departamento de Fisica Aplicada I, Facultad de Ciencias Fisicas, Universidad Complutense de Madrid, Avda. Complutense s/n, E-28040 Madrid (Spain); Retamosa, J. [Grupo de Fisica Nuclear, Departamento de Fisica Atomica, Molecular y Nuclear, Facultad de Ciencias Fisicas, Universidad Complutense de Madrid, Avda. Complutense s/n, E-28040 Madrid (Spain)

    2012-03-29

    We present a robust analysis of the spectral fluctuations exhibited by the light meson spectrum. This analysis provides information about the degree of chaos in light mesons and may be useful to get some insight on the underlying interactions. Our analysis unveils that the statistical properties of the light meson spectrum are close, but not exactly equal, to those of chaotic systems. In addition, we have analyzed several theoretical spectra including the latest lattice QCD calculation. With a single exception, their statistical properties are close to those of a generic integrable system, and thus incompatible with the experimental spectrum.

  19. Strong scintillations during atmospheric occultations Theoretical intensity spectra. [radio scattering during spacecraft occultations by planetary atmospheres

    Science.gov (United States)

    Hinson, D. P.

    1986-01-01

    Each of the two Voyager spacecraft launched in 1977 has completed a reconnaissance of the Jovian and Saturnian systems. In connection with occultation experiments, strong scintillations were observed. Further theoretical work is required before these scintillations can be interpreted. The present study is, therefore, concerned with the derivation of a theory for strong scattering during atmospheric occultation experiments, taking into account as fundamental quantity of interest the spatial spectrum (or spectral density) of intensity fluctuations. Attention is given to a theory for intensity spectra, and numerical calculations. The new formula derived for Phi-i accounts for strong scattering of electromagnetic waves during atmospheric occultations.

  20. Theoretical Atomic Physics code development IV: LINES, A code for computing atomic line spectra

    International Nuclear Information System (INIS)

    Abdallah, J. Jr.; Clark, R.E.H.

    1988-12-01

    A new computer program, LINES, has been developed for simulating atomic line emission and absorption spectra using the accurate fine structure energy levels and transition strengths calculated by the (CATS) Cowan Atomic Structure code. Population distributions for the ion stages are obtained in LINES by using the Local Thermodynamic Equilibrium (LTE) model. LINES is also useful for displaying the pertinent atomic data generated by CATS. This report describes the use of LINES. Both CATS and LINES are part of the Theoretical Atomic PhysicS (TAPS) code development effort at Los Alamos. 11 refs., 9 figs., 1 tab

  1. Does Nonlinear Modeling Play a Role in Plasmid Bioprocess Monitoring Using Fourier Transform Infrared Spectra?

    Science.gov (United States)

    Lopes, Marta B; Calado, Cecília R C; Figueiredo, Mário A T; Bioucas-Dias, José M

    2017-06-01

    The monitoring of biopharmaceutical products using Fourier transform infrared (FT-IR) spectroscopy relies on calibration techniques involving the acquisition of spectra of bioprocess samples along the process. The most commonly used method for that purpose is partial least squares (PLS) regression, under the assumption that a linear model is valid. Despite being successful in the presence of small nonlinearities, linear methods may fail in the presence of strong nonlinearities. This paper studies the potential usefulness of nonlinear regression methods for predicting, from in situ near-infrared (NIR) and mid-infrared (MIR) spectra acquired in high-throughput mode, biomass and plasmid concentrations in Escherichia coli DH5-α cultures producing the plasmid model pVAX-LacZ. The linear methods PLS and ridge regression (RR) are compared with their kernel (nonlinear) versions, kPLS and kRR, as well as with the (also nonlinear) relevance vector machine (RVM) and Gaussian process regression (GPR). For the systems studied, RR provided better predictive performances compared to the remaining methods. Moreover, the results point to further investigation based on larger data sets whenever differences in predictive accuracy between a linear method and its kernelized version could not be found. The use of nonlinear methods, however, shall be judged regarding the additional computational cost required to tune their additional parameters, especially when the less computationally demanding linear methods herein studied are able to successfully monitor the variables under study.

  2. An original data treatment for infrared spectra of organic matter, application to extracted soil organic matter

    Science.gov (United States)

    Gomes Rossin, Bruna; Redon, Roland; Raynaud, Michel; Nascimento, Nadia Regina; Mounier, Stéphane

    2017-04-01

    Infrared spectra of extracted organic matter are easy and rapid to do, but generally hard to interpreted over the presence or not of certain organic functions. Indeed, the organic matter is a complex mixture of molecules often having absorption overlapping and it is also difficult to have a well calibrated or normalised spectra due to the difficulty to have a well known solid content or homogeneity for a sample (Monakhova et al. 2015, Tadini et al. 2015, Bardy et al. 2008). In this work, the IRTF (InfraRed Fourier Transform) spectra were treated by an original algorithm developed to obtain the principal components of the IRTF spectra and their contributions for each sample. This bilinear decomposition used a PCA initialisation and the principal components were estimated from vectors calculated by PCA and linearly combined to provide non-negative signals minimizing a criterion based on cross-correlation. Hence, using this decomposition, it is possible to define IRTF signal of organic matter fractions like humic acid or fulvic acid depending on their origin like surface of depth of soil profiles. The method was used on a set of sample from Upper Negro River Basin (Amazon, Brazil) (Bueno,2009), where three soils sequences from surface to two meter depth containing 10 slices each. The sequences were sampled on a podzol well drain, a hydromorphic podzol and a cryptopodzol. From the IRTF data five representative component spectra were defined for all the extracted organic matter , and using other chemical composition information, a mechanism of organic matter fate is proposed to explain the observed results. Bardy, M., E. Fritsch, S. Derenne, T. Allard, N. R. do Nascimento, and G. T. Bueno. 2008. "Micromorphology and Spectroscopic Characteristics of Organic Matter in Waterlogged Podzols of the Upper Amazon Basin." Geoderma 145 (3-4): 222-30. Bueno, G.T. Appauvrissement et podzolisation des latérites du baissin du Rio Negro et gênese dês Podzols dans le haut bassin

  3. Field Red Horizontal Branch Star Chemical Compositions from High Resolution Infrared Spectra

    Science.gov (United States)

    Sneden, Chris; Afsar, Melike; Bozkurt, Zeynep; Bocek-Topcu, Gamze; Mace, Gregory N.; Kim, Hwihyun; Kaplan, Kyle; Kidder, Benjamin; McLane, Jacob

    2017-06-01

    We have observed three field red horizontal branch stars with the Immersion Grating Infrared Spectrograph (IGRINS). The high resolution (R~45000) high signal-to-noise (S/N > 200) spectra obtained with IGRINS cover the complete H-band (1.50-1.80 micron) and K-band (1.90-2.45 micron). We analyzed hundreds of lines of the ubiquitous OH, CN, and CO molecular bands, and found more than 80 lines of atomic species that were useful for abundance work. A combination of good laboratory transition probabilities (when available) and ones derived from reverse solar analyses were employed. Our transition data were checked through studies of the Arcturus Atlas spectrum. We derived abundances from synthetic spectra instead of from equivalent widths. With IGRINS data we were able to extract metallicities and abundance ratios for more than 20 elements, including several not detectable or poorly represented in optical wavelength regions. Our abundances from IGRINS spectra are in excellent accord with those derived from optical spectrum studies. These results are directly applicable to calibrations of results from lower-resolution and/or S/N infrared spectral surveys. IGRINS observations will give high reolution spectroscopic access to heavily obscured normal red giants and other cool stars with unusual element mixes.This work used the Immersion Grating Infrared Spectrograph (IGRINS) that was developed under a collaboration between the University of Texas at Austin and the Korea Astronomy and Space Science Institute (KASI) with the financial support of the US National Science Foundation (NSF; grant AST-1229522), of the University of Texas at Austin, and of the Korean GMT Project of KASI. Our project also has been supported by NSF grants AST~1211585 and AST~1616040, by the University of Texas Rex G. Baker, Jr. Centennial Research Endowment, and by The Scientific and Technological Research Council of Turkey (TUBITAK, project No. 112T929).

  4. Infrared Spectra and Band Strengths of CH3SH, an Interstellar Molecule

    Science.gov (United States)

    Hudson, R. L.

    2016-01-01

    Three solid phases of CH3SH (methanethiol or methyl mercaptan) have been prepared and their mid-infrared spectra recorded at 10-110 degrees Kelvin, with an emphasis on the 17-100 degrees Kelvin region. Refractive indices have been measured at two temperatures and used to estimate ice densities and infrared band strengths. Vapor pressures for the two crystalline phases of CH3SH at 110 degrees Kelvin are estimated. The behavior of amorphous CH3SH on warming is presented and discussed in terms of Ostwald's step rule. Comparisons to CH3OH under similar conditions are made, and some inconsistencies and ambiguities in the CH3SH literature are examined and corrected.

  5. Infrared dispersion analysis and Raman scattering spectra of taurine single crystals

    Science.gov (United States)

    Moreira, Roberto L.; Lobo, Ricardo P. S. M.; Dias, Anderson

    2018-01-01

    A comprehensive set of optical vibrational modes of monoclinic taurine crystals was determined by Raman scattering, and infrared reflectivity and transmission spectroscopies. By using appropriate scattering/reflection geometries, the vibrational modes were resolved by polarization and the most relevant modes of the crystal could be assigned. In particular, we were able to review the symmetry of the gerade modes and to resolve ambiguities in the literature. Owing to the non-orthogonal character of Bu modes in monoclinic crystals (lying on the optic axial plane), we carried out a generalized Lorentz dispersion analysis consisting of simultaneous adjust of infrared-reflectivity spectra at various light polarization angles. The Au modes (parallel to the C2-axis) were treated within the classical Lorentz model. The behavior of off-diagonal and diagonal terms of the complex dielectric tensors and the presence of anomalous dispersion were discussed as consequences of the low symmetry of the crystal.

  6. Infrared Spectra and Optical Constants of Astronomical Ices: II. Ethane and Ethylene

    Science.gov (United States)

    Hudson, Reggie L.; Gerakines, Perry A.; Moore, M. H.

    2014-01-01

    Infrared spectroscopic observations have established the presence of hydrocarbon ices on Pluto and other TNOs, but the abundances of such molecules cannot be deduced without accurate optical constants (n, k) and reference spectra. In this paper we present our recent measurements of near- and mid-infrared optical constants for ethane (C2H6) and ethylene (C2H4) in multiple ice phases and at multiple temperatures. As in our recent work on acetylene (C2H2), we also report new measurements of the index of refraction of each ice at 670 nm. Comparisons are made to earlier work where possible, and electronic versions of our new results are made available.

  7. Correcting attenuated total reflection-fourier transform infrared spectra for water vapor and carbon dioxide

    DEFF Research Database (Denmark)

    Bruun, Susanne Wrang; Kohler, Achim; Adt, Isabelle

    2006-01-01

    Fourier transform infrared (FT-IR) spectroscopy is a valuable technique for characterization of biological samples, providing a detailed fingerprint of the major chemical constituents. However, water vapor and CO(2) in the beam path often cause interferences in the spectra, which can hamper...... the data analysis and interpretation of results. In this paper we present a new method for removal of the spectral contributions due to atmospheric water and CO(2) from attenuated total reflection (ATR)-FT-IR spectra. In the IR spectrum, four separate wavenumber regions were defined, each containing...... of the growing yeast biofilm, the gas correction revealed otherwise hidden variations of relevance for modeling the growth dynamics. As the presented method improved the interpretation of the principle component analysis (PCA) models, it has proven to be a valuable tool for filtering atmospheric variation in ATR...

  8. Path integral Liouville dynamics: Applications to infrared spectra of OH, water, ammonia, and methane

    International Nuclear Information System (INIS)

    Liu, Jian; Zhang, Zhijun

    2016-01-01

    Path integral Liouville dynamics (PILD) is applied to vibrational dynamics of several simple but representative realistic molecular systems (OH, water, ammonia, and methane). The dipole-derivative autocorrelation function is employed to obtain the infrared spectrum as a function of temperature and isotopic substitution. Comparison to the exact vibrational frequency shows that PILD produces a reasonably accurate peak position with a relatively small full width at half maximum. PILD offers a potentially useful trajectory-based quantum dynamics approach to compute vibrational spectra of molecular systems

  9. Compositional Analyses and Implications of Visible/Near-Infrared Spectra of Outer Irregular Jovian Satellites

    Science.gov (United States)

    Vilas, Faith; Hendrix, Amanda

    2017-10-01

    The existence of a visible-near infrared absorption feature attributed to aqueous alteration products has been suggested in both grey and reddened broadband photometry of some outer irregular jovian satellites. Moderate resolution VNIR narrowband spectroscopy was obtained of the jovian irregular satellites JVI Himalia, JVII Elara, JVIII Pasiphae, JIX Sinope, JX Lysithea, JXI Carme, JXII Ananke and JXVII Callirrhoe in 2006, 2008, 2009, and 2010 using the MMT Observatory facility Red Channel spectrograph to confirm the presence of this feature. The spectra are centered near 0.64 μm in order to cover the 0.7-μm feature entirely (generally ranging from 0.57 to 0.83 μm). The spectra generally have a dispersion/element of ~0.6 nm (6Å) some spectra are smoothed. These spectra sample three prograde (i = 28o), four retrograde (i = 149o, 165o) and one independent satellite.We observe these findings among the spectra:- An absorption feature centered near 0.7 µm exists in the spectra of the three prograde (i = 28o) satellites. This feature is spectrally broader than the 0.7-µm feature observed in C-complex asteroids. None appears spectrally reddened. This suggests that these prograde satellites have a common parent body.- A different absorption feature appears in the spectra of the three retrograde (i = 149o) satellites, also suggesting a common parent body. Varying reddening is observed. This feature is similar in spectral location and width to the 0.7-µm feature.- Reddening is observed in the individual observation of JXI Carme (i = 165o), and independent satellite JIX Sinope, similar to the D-class asteroid spectra dominating the Trojan population. A suggested absorption feature is being investigated.Mixing modeling of combinations of both expected and proposed compositions including carbonaceous materials, phyllosilicates, mafic silicates, and other opaque materials, is currently underway. Results will be reported and discussed at the meeting.Acknowledgments: The

  10. X-ray absorption and infrared spectra of water and ice: A first-principles electronic structure study

    Science.gov (United States)

    Chen, Wei

    Water is of essential importance for chemistry and biology, yet the physics concerning many of its distinctive properties is not well known. In this thesis we present a theoretical study of the x-ray absorption (XA) and infrared (IR) spectra of water in liquid and solid phase. Our theoretical tools are the density functional theory (DFT), Car-Parrinello (CP) molecular dynamics (MD), and the so-called GW method. Since a systematic review of these ab initio methods is not the task of this thesis, we only briefly recall the main concepts of these methods as needed in the course of our exposition. The focus is, instead, an investigation of what is the important physics necessary for a better description of these excitation processes, in particular, core electron excitations (in XA) that reveal the local electronic structure, and vibrational excitations (in IR) associated to the molecular dynamics. The most interesting question we are trying to answer is: as we include better approximations and more complete physical descriptions of these processes, how do the aforementioned spectra reflect the underlying hydrogen-bonding network of water? The first part of this thesis consists of the first four chapters, which focus on the study of core level excitation of water and ice. The x-ray absorption spectra of water and ice are calculated with a many-body approach for electron-hole excitations. The experimental features, even the small effects of a temperature change in the liquid, are reproduced with quantitative detail using molecular configurations generated by ab initio molecular dynamics. We find that the spectral shape is controlled by two major modifications of the short range order that mark the transition from ice to water. One is associated to dynamic breaking of the hydrogen bonds which leads to a strong enhancement of the pre-edge intensity in the liquid. The other is due to densification, which follows the partial collapse of the hydrogen bond network and is

  11. Preparation and infrared spectra of differently deuterated tetramethyl-derivatives of the IV. main group

    International Nuclear Information System (INIS)

    Biedermann, S.

    1972-01-01

    19 different deuterated tetramethyl derivates of the type (CH 3 )sub(4-n)M(CH 3 )sub(n) of C, Si, Ge, Sn and Pb were prepared. Gas cuvettes with polyethylene, NaCl and KBr windows were used to absorb the infra-red spectra, the IR equipment Beckman IR 11 and IR 12 were used. The infra-red spectra of the above mentioned compounds were indicated from 33 to 4,000 cm -1 , the ground, upper and combination vibrations assigned, the PR separations of the partly well resolved rotation-vibration outlines determined and were compared with the calculated PR separations. The revision of the correlations performed by Graham for γsub(s)CH 3 and γsub(as)CH 3 in the race of vibration F 2 with Sn(CH 3 ) 4 and Pb(CH 3 ) 4 and the proposed one with C(CH 3 ) 4 , Si(CH 3 ) 4 and Ge(CH 3 ) 4 could be disproved by the new experimental results. (FW) [de

  12. Modelling telluric line spectra in the optical and infrared with an application to VLT/X-Shooter spectra

    Science.gov (United States)

    Rudolf, N.; Günther, H. M.; Schneider, P. C.; Schmitt, J. H. M. M.

    2016-01-01

    Context. Earth's atmosphere imprints a large number of telluric absorption and emission lines on astronomical spectra, especially in the near infrared, that need to be removed before analysing the affected wavelength regions. Aims: These lines are typically removed by comparison to A- or B-type stars used as telluric standards that themselves have strong hydrogen lines, which complicates the removal of telluric lines. We have developed a method to circumvent that problem. Methods: For our IDL software package tellrem we used a recent approach to model telluric absorption features with the line-by-line radiative transfer model (LBLRTM). The broad wavelength coverage of the X-Shooter at VLT allows us to expand their technique by determining the abundances of the most important telluric molecules H2O, O2, CO2, and CH4 from sufficiently isolated line groups. For individual observations we construct a telluric absorption model for most of the spectral range that is used to remove the telluric absorption from the object spectrum. Results: We remove telluric absorption from both continuum regions and emission lines without systematic residuals for most of the processable spectral range; however, our method increases the statistical errors. The errors of the corrected spectrum typically increase by 10% for S/N ~ 10 and by a factor of two for high-quality data (S/N ~ 100), I.e. the method is accurate on the percent level. Conclusions: Modelling telluric absorption can be an alternative to the observation of standard stars for removing telluric contamination. Based on observations collected at the European Southern Observatory, Paranal, Chile, 085.C-0764(A) and 60.A-9022(C).The tellrem package is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/585/A113

  13. Vibrational infrared and Raman spectra of polypeptides: Fragments-in-fragments within molecular tailoring approach

    Energy Technology Data Exchange (ETDEWEB)

    Sahu, Nityananda; Gadre, Shridhar R., E-mail: gadre@iitk.ac.in [Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208 016 (India)

    2016-03-21

    The present work reports the calculation of vibrational infrared (IR) and Raman spectra of large molecular systems employing molecular tailoring approach (MTA). Further, it extends the grafting procedure for the accurate evaluation of IR and Raman spectra of large molecular systems, employing a new methodology termed as Fragments-in-Fragments (FIF), within MTA. Unlike the previous MTA-based studies, the accurate estimation of the requisite molecular properties is achieved without performing any full calculations (FC). The basic idea of the grafting procedure is implemented by invoking the nearly basis-set-independent nature of the MTA-based error vis-à-vis the respective FCs. FIF has been tested out for the estimation of the above molecular properties for three isomers, viz., β-strand, 3{sub 10}- and α-helix of acetyl(alanine){sub n}NH{sub 2} (n = 10, 15) polypeptides, three conformers of doubly protonated gramicidin S decapeptide and trpzip2 protein (PDB id: 1LE1), respectively, employing BP86/TZVP, M06/6-311G**, and M05-2X/6-31G** levels of theory. For most of the cases, a maximum difference of 3 cm{sup −1} is achieved between the grafted-MTA frequencies and the corresponding FC values. Further, a comparison of the BP86/TZVP level IR and Raman spectra of α-helical (alanine){sub 20} and its N-deuterated derivative shows an excellent agreement with the existing experimental spectra. In view of the requirement of only MTA-based calculations and the ability of FIF to work at any level of theory, the current methodology provides a cost-effective solution for obtaining accurate spectra of large molecular systems.

  14. Vibrational infrared and Raman spectra of polypeptides: Fragments-in-fragments within molecular tailoring approach

    Science.gov (United States)

    Sahu, Nityananda; Gadre, Shridhar R.

    2016-03-01

    The present work reports the calculation of vibrational infrared (IR) and Raman spectra of large molecular systems employing molecular tailoring approach (MTA). Further, it extends the grafting procedure for the accurate evaluation of IR and Raman spectra of large molecular systems, employing a new methodology termed as Fragments-in-Fragments (FIF), within MTA. Unlike the previous MTA-based studies, the accurate estimation of the requisite molecular properties is achieved without performing any full calculations (FC). The basic idea of the grafting procedure is implemented by invoking the nearly basis-set-independent nature of the MTA-based error vis-à-vis the respective FCs. FIF has been tested out for the estimation of the above molecular properties for three isomers, viz., β-strand, 310- and α-helix of acetyl(alanine)nNH2 (n = 10, 15) polypeptides, three conformers of doubly protonated gramicidin S decapeptide and trpzip2 protein (PDB id: 1LE1), respectively, employing BP86/TZVP, M06/6-311G**, and M05-2X/6-31G** levels of theory. For most of the cases, a maximum difference of 3 cm-1 is achieved between the grafted-MTA frequencies and the corresponding FC values. Further, a comparison of the BP86/TZVP level IR and Raman spectra of α-helical (alanine)20 and its N-deuterated derivative shows an excellent agreement with the existing experimental spectra. In view of the requirement of only MTA-based calculations and the ability of FIF to work at any level of theory, the current methodology provides a cost-effective solution for obtaining accurate spectra of large molecular systems.

  15. A synthetic data set of high-spectral-resolution infrared spectra for the Arctic atmosphere

    Science.gov (United States)

    Cox, Christopher J.; Rowe, Penny M.; Neshyba, Steven P.; Walden, Von P.

    2016-05-01

    Cloud microphysical and macrophysical properties are critical for understanding the role of clouds in climate. These properties are commonly retrieved from ground-based and satellite-based infrared remote sensing instruments. However, retrieval uncertainties are difficult to quantify without a standard for comparison. This is particularly true over the polar regions, where surface-based data for a cloud climatology are sparse, yet clouds represent a major source of uncertainty in weather and climate models. We describe a synthetic high-spectral-resolution infrared data set that is designed to facilitate validation and development of cloud retrieval algorithms for surface- and satellite-based remote sensing instruments. Since the data set is calculated using pre-defined cloudy atmospheres, the properties of the cloud and atmospheric state are known a priori. The atmospheric state used for the simulations is drawn from radiosonde measurements made at the North Slope of Alaska (NSA) Atmospheric Radiation Measurement (ARM) site at Barrow, Alaska (71.325° N, 156.615° W), a location that is generally representative of the western Arctic. The cloud properties for each simulation are selected from statistical distributions derived from past field measurements. Upwelling (at 60 km) and downwelling (at the surface) infrared spectra are simulated for 260 cloudy cases from 50 to 3000 cm-1 (3.3 to 200 µm) at monochromatic (line-by-line) resolution at a spacing of ˜ 0.01 cm-1 using the Line-by-line Radiative Transfer Model (LBLRTM) and the discrete-ordinate-method radiative transfer code (DISORT). These spectra are freely available for interested researchers from the NSF Arctic Data Center data repository (doi:10.5065/D61J97TT).

  16. MID-INFRARED SPECTRA OF TRANSITIONAL DISKS IN THE CHAMAELEON I CLOUD

    International Nuclear Information System (INIS)

    Kim, K. H.; Watson, Dan M.; Manoj, P.; Forrest, W. J.; Sargent, B.; McClure, M. K.; Green, J. D.; Harrold, Samuel T.; Furlan, E.; Najita, J.; Espaillat, C.; Calvet, N.; Luhman, K. L.

    2009-01-01

    We present 5-40 μm Spitzer Infrared Spectrograph spectra of a collection of transitional disks, objects for which the spectral energy distribution (SED) indicates central clearings (holes) or gaps in the dust distribution, in the Chamaeleon I star-forming region. Like their counterparts in the Taurus-Auriga star-forming region that we have previously observed, the spectra of these young objects (1-3 Myr old) reveal that the central clearings or gaps are very sharp-edged, and are surrounded by optically thick dusty disks similar to those around other classical T Tauri stars in the Chamaeleon I association. Also like the Taurus transitional disks, the Chamaeleon I transitional disks have extremely large depletion factors for small dust grains in their gaps, compared to the full accretion disks whose SEDs are represented by the median SED of Class II objects in the region. We find that the fraction of transitional disks in the Chamaeleon I cloud is somewhat higher than that in the Taurus-Auriga cloud, possibly indicating that the frequency of transitional disks, on average, increases with cluster age. We also find a significant correlation between the stellar mass and the radius of the outer edge of the gap. We discuss the disk structures implied by the spectra and the constraints they place on gap-formation mechanisms in protoplanetary disks.

  17. Rapid assessment of soluble solids content in navel orange by near-infrared diffuse reflectance spectra

    Science.gov (United States)

    Liu, Yande; Luo, Ji; Chen, Xingmiao; Ying, Yibin

    2006-10-01

    The potential of using Near Infrared diffuse reflectance spectroscopy to assess soluble solids content (SSC) of intact navel orange was examined. A total 40 samples were used to develop the calibration and prediction models. NIR spectral data were collected in the spectral region between 350 nm and 2500 nm and its second derivative spectra was used for this study. Different scattering correction algorithms (no preprocessing and multiplicative scattering correction (MSC) were compared. Calibration models based on different spectral ranges, different derivatives and different kinds of statistical models including partial least square (PLS) and principle component regression (PCR) were also compared in this research. The best results of PLS models with the second derivative spectra are r=0.929, RMSEC=0.517 and RMSEP=0.592, in the wavelength range of 361-2488 nm. The segment length used to derivate the spectra influences the calibration model and the results are better when the segment lengths and gap sizes are lower in Norris derivate filter. The results show that this method is feasible for rapid assessing SSC of the navel orange.

  18. Modeling of aircraft exhaust emissions and infrared spectra for remote measurement of nitrogen oxides

    Directory of Open Access Journals (Sweden)

    K. Beier

    Full Text Available Infrared (IR molecular spectroscopy is proposed to perform remote measurements of NOx concentrations in the exhaust plume and wake of aircraft. The computer model NIRATAM is applied to simulate the physical and chemical properties of the exhaust plume and to generate low resolution IR spectra and synthetical thermal images of the aircraft in its natural surroundings. High-resolution IR spectra of the plume, including atmospheric absorption and emission, are simulated using the molecular line-by-line radiation model FASCODE2. Simulated IR spectra of a Boeing 747-400 at cruising altitude for different axial and radial positions in the jet region of the exhaust plume are presented. A number of spectral lines of NO can be identified that can be discriminated from lines of other exhaust gases and the natural atmospheric background in the region around 5.2 µm. These lines can be used to determine NO concentration profiles in the plume. The possibility of measuring nitrogen dioxide NO2 is also discussed briefly, although measurements turn out to be substantially less likely than those of NO. This feasibility study compiles fundamental data for the optical and radiometric design of an airborne Fourier transform spectrometer and the preparation of in-flight measurements for monitoring of aircraft pollutants.

  19. Modeling of aircraft exhaust emissions and infrared spectra for remote measurement of nitrogen oxides

    Directory of Open Access Journals (Sweden)

    K. Beier

    1994-08-01

    Full Text Available Infrared (IR molecular spectroscopy is proposed to perform remote measurements of NOx concentrations in the exhaust plume and wake of aircraft. The computer model NIRATAM is applied to simulate the physical and chemical properties of the exhaust plume and to generate low resolution IR spectra and synthetical thermal images of the aircraft in its natural surroundings. High-resolution IR spectra of the plume, including atmospheric absorption and emission, are simulated using the molecular line-by-line radiation model FASCODE2. Simulated IR spectra of a Boeing 747-400 at cruising altitude for different axial and radial positions in the jet region of the exhaust plume are presented. A number of spectral lines of NO can be identified that can be discriminated from lines of other exhaust gases and the natural atmospheric background in the region around 5.2 µm. These lines can be used to determine NO concentration profiles in the plume. The possibility of measuring nitrogen dioxide NO2 is also discussed briefly, although measurements turn out to be substantially less likely than those of NO. This feasibility study compiles fundamental data for the optical and radiometric design of an airborne Fourier transform spectrometer and the preparation of in-flight measurements for monitoring of aircraft pollutants.

  20. Investigating the fermentation of cocoa by correlating denaturing gradient gel electrophoresis profiles and near infrared spectra.

    Science.gov (United States)

    Nielsen, Dennis S; Snitkjaer, Pia; van den Berg, Frans

    2008-07-15

    Raw cocoa has an astringent, unpleasant taste and flavour, and has to be fermented, dried and roasted in order to obtain the characteristic cocoa flavour and taste. During the fermentation microbial activity outside the cocoa beans induces biochemical and physical changes inside the beans. The process is complex involving activity of several different groups of microorganisms which bring about numerous biochemical and physical changes inside the beans. Due to the complexity of these processes no thorough investigations of the interactions between the microbial activities on the outside of the beans and the chemical processes inside the beans have been carried out previously. Recently it has been shown that Denaturing Gradient Gel Electrophoresis (DGGE) offers an efficient tool for monitoring the microbiological changes taking place during the fermentation of cocoa. Near Infrared (NIR) spectroscopy has previously been used to determine various components in cocoa beans, offering a rapid alternative compared to traditional analytical methods for obtaining knowledge about changes in the chemical composition of the cocoa beans during fermentation. During a number of cocoa fermentations bean samples were taken with 24 h intervals to be dried and analysed by NIR. Cocoa pulp samples taken simultaneously during the same fermentations have previously been characterised using DGGE [Nielsen, D.S., Teniola, O.D., Ban-Koffi, L., Owusu, M., Andersson, T., Holzapfel, W.H. (2007). The microbiology of Ghanaian cocoa fermentations analysed using culture dependent and culture-independent methods. International Journal of Food Microbiology 114, 168-186.]. Here we report the first study where microbiological changes during the fermentation determined using DGGE are correlated to changes inside the beans determined by NIR using multivariate data analysis. Following data pre-processing (baseline correction followed by Co-shift correction or Correlation Optimised Warping) the DGGE spectra

  1. Quantitative Infrared Absorption Spectra and Vibrational Assignments of Crotonaldehyde and Methyl Vinyl Ketone Using Gas-Phase Mid-Infrared, Far-Infrared, and Liquid Raman Spectra: s-cis vs s-trans Composition Confirmed via Temperature Studies and ab Initio Methods

    Energy Technology Data Exchange (ETDEWEB)

    Lindenmaier, Rodica; Williams, Stephen D.; Sams, Robert L.; Johnson, Timothy J.

    2016-12-16

    Methyl vinyl ketone (MVK) and crotonaldehyde are chemical isomers; both are also important species in tropospheric chemistry. We report quantitative vapor-phase infrared spectra of crotonaldehyde and MVK vapors over the 540-6500 cm-1 range. Vibrational assignments of all fundamental modes are made for both molecules based on far- and mid-infrared vapor-phase spectra, liquid Raman spectra, along with density functional theory and ab initio MP2 and high energy-accuracy compound theoretical models (W1BD). Theoretical results indicate that at room temperature the crotonaldehyde equilibrium mixture is approximately 97% s-trans and only 3% s-cis conformer. Nearly all observed bands are thus associated with the s-trans conformer, but a few appear to be uniquely associated the s-cis conformer, notably ν16c at 730.90 cm-1, which displays a substantial intensity increase with temperature (62% upon going from 5 to 50 oC). The intensity of the corresponding mode of the s-trans conformer decreases with temperature. Under the same conditions, the MVK equilibrium mixture is approximately 69% s-trans conformer and 31% s-cis. W1BD calculations indicate that for MVK this is one of those (rare) cases where there are comparable populations of both conformers, ~doubling the number of observed bands and exacerbating the vibrational assignments. We uniquely assign the bands associated with both the MVK s-cis conformer as well as those of the s-trans, thus completing the vibrational analyses of both conformers from the same set of experimental spectra. Integrated band intensities are reported for both molecules along with global warming potential values. Using the quantitative IR data, potential bands for atmospheric monitoring are also discussed.

  2. Spectra identification and interpretation comparing the spectral informations - the example of infrared, C13 magnetic resonance and mass spectroscopy

    International Nuclear Information System (INIS)

    Kwiatkowski, J.

    1981-01-01

    A computer assisted spectra interpretation based on special comparison was developed. The search program implements three different searching strategies to be used according to the specific analytical problem: Search for a spectrum of the same substance, partial structure search and spectra identification for mixed substances. It turned out, that the success of a search program depends significantly on the used spectra collection; optimization procedures involve the information content classification for each spectral information. A combined search program is demonstrated for infrared, 13C-NMR and mass spectra. (TW)

  3. Effect of Shear Applied During a Pharmaceutical Process on Near Infrared Spectra.

    Science.gov (United States)

    Hernández, Eduardo; Pawar, Pallavi; Rodriguez, Sandra; Lysenko, Sergiy; Muzzio, Fernando J; Romañach, Rodolfo J

    2016-03-01

    This study describes changes observed in the near-infrared (NIR) diffuse reflectance (DR) spectra of pharmaceutical tablets after these tablets were subjected to different levels of strain (exposure to shear) during the mixing process. Powder shearing is important in the mixing of powders that are cohesive. Shear stress is created in a system by moving one surface over another causing displacements in the direction of the moving surface and is part of the mixing dynamics of particulates in many industries including the pharmaceutical industry. In continuous mixing, shear strain is developed within the process when powder particles are in constant movement and can affect the quality attributes of the final product such as dissolution. These changes in the NIR spectra could affect results obtained from NIR calibration models. The aim of the study was to understand changes in the NIR diffuse reflectance spectra that can be associated with different levels of strain developed during blend shearing of laboratory samples. Shear was applied using a Couette cell and tablets were produced using a tablet press emulator. Tablets with different shear levels were measured using NIR spectroscopy in the diffuse reflectance mode. The NIR spectra were baseline corrected to maintain the scattering effect associated with the physical properties of the tablet surface. Principal component analysis was used to establish the principal sources of variation within the samples. The angular dependence of elastic light scattering shows that the shear treatment reduces the size of particles and produces their uniform and highly isotropic distribution. Tablet compaction further reduces the diffuse component of scattering due to realignment of particles. © The Author(s) 2016.

  4. Post-maximum Near-infrared Spectra of SN 2014J: A Search for Interaction Signatures

    Science.gov (United States)

    Sand, D. J.; Hsiao, E. Y.; Banerjee, D. P. K.; Marion, G. H.; Diamond, T. R.; Joshi, V.; Parrent, J. T.; Phillips, M. M.; Stritzinger, M. D.; Venkataraman, V.

    2016-05-01

    We present near-infrared (NIR) spectroscopic and photometric observations of the nearby Type Ia SN 2014J. The 17 NIR spectra span epochs from +15.3 to +92.5 days after B-band maximum light, while the {{JHK}}s photometry include epochs from -10 to +71 days. These data are used to constrain the progenitor system of SN 2014J utilizing the Paβ line, following recent suggestions that this phase period and the NIR in particular are excellent for constraining the amount of swept-up hydrogen-rich material associated with a non-degenerate companion star. We find no evidence for Paβ emission lines in our post-maximum spectra, with a rough hydrogen mass limit of ≲ 0.1 M ⊙, which is consistent with previous limits in SN 2014J from late-time optical spectra of the Hα line. Nonetheless, the growing data set of high-quality NIR spectra holds the promise of very useful hydrogen constraints. Based on observations obtained at the Gemini Observatory under program GN-2014A-Q-8 (PI: Sand). Gemini is operated by the Association of Universities for Research in Astronomy, Inc., under a cooperative agreement with the NSF on behalf of the Gemini partnership: the National Science Foundation (United States), the National Research Council (Canada), CONICYT (Chile), Ministerio de Ciencia, Tecnología e Innovación Productiva (Argentina), and Ministério da Ciência, Tecnologia e Inovação (Brazil).

  5. Predicting ambient aerosol thermal-optical reflectance measurements from infrared spectra: elemental carbon

    Science.gov (United States)

    Dillner, A. M.; Takahama, S.

    2015-10-01

    Elemental carbon (EC) is an important constituent of atmospheric particulate matter because it absorbs solar radiation influencing climate and visibility and it adversely affects human health. The EC measured by thermal methods such as thermal-optical reflectance (TOR) is operationally defined as the carbon that volatilizes from quartz filter samples at elevated temperatures in the presence of oxygen. Here, methods are presented to accurately predict TOR EC using Fourier transform infrared (FT-IR) absorbance spectra from atmospheric particulate matter collected on polytetrafluoroethylene (PTFE or Teflon) filters. This method is similar to the procedure developed for OC in prior work (Dillner and Takahama, 2015). Transmittance FT-IR analysis is rapid, inexpensive and nondestructive to the PTFE filter samples which are routinely collected for mass and elemental analysis in monitoring networks. FT-IR absorbance spectra are obtained from 794 filter samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites collected during 2011. Partial least squares regression is used to calibrate sample FT-IR absorbance spectra to collocated TOR EC measurements. The FT-IR spectra are divided into calibration and test sets. Two calibrations are developed: one developed from uniform distribution of samples across the EC mass range (Uniform EC) and one developed from a uniform distribution of Low EC mass samples (EC normalized error (21 %). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision and accuracy to collocated TOR measurements. Only the normalized error is higher for the FT-IR EC measurements than for collocated TOR. FT-IR spectra are also divided into calibration and test sets by the ratios OC/EC and ammonium/EC to determine the impact of OC and ammonium on EC prediction. We conclude that FT-IR analysis with

  6. Cluster analysis of near-infrared reflectance spectra of asteroid Itokawa

    Science.gov (United States)

    Inasawa, Tomoki; Kitazato, Kohei; Hirata, Naru; Demura, Hirohide

    2017-10-01

    The data from the analysis of samples returned by Hayabusa spacecraft have provided conclusive evidence regarding mineral composition and space weathering of near-Earth S-type asteroid Itokawa. To apply these information to the Hayabusa remote sensing data towards revealing the formation history of Itokawa, we made a more precise near-infrared spectral map of Itokawa than the previous ones from the Hayabusa NIRS data and performed its cluster analysis. The NIRS instrument had acquired more than 80,000 spatially resolved 0.75 to 2.20 microns reflectance spectra from the surface of Itokawa. We used PCA and k-means clustering for cluster analysis and found that at least three different types of surface areas would exist on Itokawa.

  7. Hemoglobin concentration determination based on near infrared spatially resolved transmission spectra

    Science.gov (United States)

    Zhang, Linna; Li, Gang; Lin, Ling

    2016-10-01

    Spatially resolved diffuse reflectance spectroscopy method has been proved to be more effective than single point spectroscopy method in the experiment to predict the concentration of the Intralipid diluted solutions. However, Intralipid diluted solution is simple, cannot be the representative of turbid liquids. Blood is a natural and meaningful turbid liquid, more complicate. Hemoglobin is the major constituent of the whole blood. And hemoglobin concentration is commonly used in clinical medicine to diagnose many diseases. In this paper, near infrared spatially resolved transmission spectra (NIRSRTS) and Partial Least Square Regression (PLSR) were used to predict the hemoglobin concentration of human blood. The results showed the prediction ability for hemoglobin concentration of the proposed method is better than single point transmission spectroscopy method. This paper demonstrated the feasibility of the spatially resolved diffuse reflectance spectroscopy method for practical liquid composition analysis. This research provided a new thinking of practical turbid liquid composition analysis.

  8. Mid-infrared emission and Raman spectra analysis of Er(3+)-doped oxyfluorotellurite glasses.

    Science.gov (United States)

    Chen, Fangze; Xu, Shaoqiong; Wei, Tao; Wang, Fengchao; Cai, Muzhi; Tian, Ying; Xu, Shiqing

    2015-04-10

    This paper reports on the spectroscopic and structural properties in Er(3+)-doped oxyfluorotellurite glasses. The compositional variation accounts for the evolutions of Raman spectra, Judd-Ofelt parameters, radiative properties, and fluorescent emission. It is found that, when maximum phonon energy changes slightly, phonon density plays a crucial role in quenching the 2.7 μm emission generated by the Er(3+):(4)I11/2→(4)I13/2 transition. The comparative low phonon density contributes strong 2.7 μm emission intensity. The high branching ratio (18.63%) and large emission cross section (0.95×10(-20)  cm(2)) demonstrate that oxyfluorotellurite glass contained with 50 mol.% TeO2 has potential application in the mid-infrared region laser.

  9. Matrix radiolysis and photoionization of CFCl3. Infrared spectra of CFCl+2 and the parent cation

    International Nuclear Information System (INIS)

    Prochaska, F.T.; Andrews, L.

    1978-01-01

    The ''Freon'' compound CFCl 3 has been subjected to radiolysis and photoionization during condensation with excess argon at 15 K. Infrared spectra of the matrix samples identified stable and free radical products and new absorptions which are attributed to charged species. The molecular ion bands exhibited three different behavior patterns on filtered mercury arc photolysis: The most photosensitive bands, destroyed by 420--1000 nm light, are assigned to the parent cation; several absorptions which photodissociated with 290--1000 nm radiation are due to a molecular anionic species; and new bands reduced by 220--1000 nm light are assigned to the daughter cation CFCl + 2 . The vibrational assignments were confirmed by carbon-13 substitution

  10. Extraction of Curcumin Pigment from Indonesian Local Turmeric with Its Infrared Spectra and Thermal Decomposition Properties

    Science.gov (United States)

    Nandiyanto, A. B. D.; Wiryani, A. S.; Rusli, A.; Purnamasari, A.; Abdullah, A. G.; Ana; Widiaty, I.; Hurriyati, R.

    2017-03-01

    Curcumin is one of the pigments which is used as a spice in Asian cuisine, traditional cosmetic, and medicine. Therefore, process for getting curcumin has been widely studied. Here, the purpose of this study was to demonstrate the simple method for extracting curcumin from Indonesian local turmeric and investigate the infrared spectra and thermal decomposition properties. In the experimental procedure, the washed turmeric was dissolved into an ethanol solution, and then put into a rotary evaporator to enrich curcumin concentration. The result showed that the present method is effective to isolate curcumin compound from Indonesian local turmeric. Since the process is very simple, this method can be used for home industrial application. Further, understanding the thermal decomposition properties of curcumin give information, specifically relating to the selection of treatment when curcumin must face the thermal-related process.

  11. Communications: On artificial frequency shifts in infrared spectra obtained from centroid molecular dynamics: Quantum liquid water

    Science.gov (United States)

    Ivanov, Sergei D.; Witt, Alexander; Shiga, Motoyuki; Marx, Dominik

    2010-01-01

    Centroid molecular dynamics (CMD) is a popular method to extract approximate quantum dynamics from path integral simulations. Very recently we have shown that CMD gas phase infrared spectra exhibit significant artificial redshifts of stretching peaks, due to the so-called "curvature problem" imprinted by the effective centroid potential. Here we provide evidence that for condensed phases, and in particular for liquid water, CMD produces pronounced artificial redshifts for high-frequency vibrations such as the OH stretching band. This peculiar behavior intrinsic to the CMD method explains part of the unexpectedly large quantum redshifts of the stretching band of liquid water compared to classical frequencies, which is improved after applying a simple and rough "harmonic curvature correction."

  12. Infrared spectroscopy of copper-resveratrol complexes: A joint experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Chiavarino, B.; Crestoni, M. E.; Fornarini, S. [Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza - Universita di Roma, Piazzale A. Moro 5, 00185 Rome (Italy); Taioli, S. [Interdisciplinary Laboratory for Computational Science, FBK-CMM and University of Trento, Via Sommarive 18, 38123 Trento (Italy); Department of Physics, University of Trento, Via Sommarive 14, 38123 Trento (Italy); Istituto Nazionale di Fisica Nucleare, Sezione di Perugia (Italy); Department of Chemistry, University of Bologna, Via F. Selmi 2, I-40126 Bologna (Italy); Mancini, I.; Tosi, P. [Department of Physics, University of Trento, Via Sommarive 14, 38123 Trento (Italy)

    2012-07-14

    Infrared multiple-photon dissociation spectroscopy has been used to record vibrational spectra of charged copper-resveratrol complexes in the 3500-3700 cm{sup -1} and 1100-1900 cm{sup -1} regions. Minimum energy structures have been determined by density functional theory calculations using plane waves and pseudopotentials. In particular, the copper(I)-resveratrol complex presents a tetra-coordinated metal bound with two carbon atoms of the alkenyl moiety and two closest carbons of the adjoining resorcinol ring. For these geometries vibrational spectra have been calculated by using linear response theory. The good agreement between experimental and calculated IR spectra for the selected species confirms the overall reliability of the proposed geometries.

  13. Correlation of vapor phase infrared spectra and regioisomeric structure in synthetic cannabinoids

    Science.gov (United States)

    Smith, Lewis W.; Thaxton-Weissenfluh, Amber; Abiedalla, Younis; DeRuiter, Jack; Smith, Forrest; Clark, C. Randall

    2018-05-01

    The twelve 1-n-pentyl-2-, 3-, 4-, 5-, 6- and 7-(1- and 2-naphthoyl)-indoles each have the same substituents attached to the indole ring, identical elemental composition (C24H23NO) yielding identical nominal and accurate masses. These twelve isomers cover all possible positions of carbonyl bridge substitution for both indole (positons 2-7) and naphthalene rings (positions 1 and 2). Regioisomeric compounds can represent significant challenges for mass based analytical methods however, infrared spectroscopy is a powerful tool for the identification of positional isomers in organic compounds. The vapor phase infrared spectra of these twelve uniquely similar compounds were evaluated in GC-IR experiments. These spectra show the bridge position on the indole ring is a dominating influence over the carbonyl absorption frequency observed for these compounds. Substitution on the pyrrole moiety of the indole ring yields the lowest Cdbnd O frequency values for position 2 and 3 giving a narrow range from 1656 to 1654 cm-1. Carbonyl absorption frequencies are higher when the naphthoyl group is attached to the benzene portion of the indole ring yielding absorption values from 1674 to 1671 cm-1. The aliphatic stretching bands in the 2900 cm-1 region yield a consistent triplet pattern because the N-alkyl substituent tail group remains unchanged for all twelve regioisomers. The asymmetric CH2 stretch is the most intense of these three bands. Changes in positional bonding for both the indole and naphthalene ring systems results in unique patterns within the 700 wavenumber out-of-plane region and these absorption bands are different for all 12 regioisomers.

  14. Correlation of vapor phase infrared spectra and regioisomeric structure in synthetic cannabinoids.

    Science.gov (United States)

    Smith, Lewis W; Thaxton-Weissenfluh, Amber; Abiedalla, Younis; DeRuiter, Jack; Smith, Forrest; Clark, C Randall

    2018-05-05

    The twelve 1-n-pentyl-2-, 3-, 4-, 5-, 6- and 7-(1- and 2-naphthoyl)-indoles each have the same substituents attached to the indole ring, identical elemental composition (C 24 H 23 NO) yielding identical nominal and accurate masses. These twelve isomers cover all possible positions of carbonyl bridge substitution for both indole (positons 2-7) and naphthalene rings (positions 1 and 2). Regioisomeric compounds can represent significant challenges for mass based analytical methods however, infrared spectroscopy is a powerful tool for the identification of positional isomers in organic compounds. The vapor phase infrared spectra of these twelve uniquely similar compounds were evaluated in GC-IR experiments. These spectra show the bridge position on the indole ring is a dominating influence over the carbonyl absorption frequency observed for these compounds. Substitution on the pyrrole moiety of the indole ring yields the lowest CO frequency values for position 2 and 3 giving a narrow range from 1656 to 1654cm -1 . Carbonyl absorption frequencies are higher when the naphthoyl group is attached to the benzene portion of the indole ring yielding absorption values from 1674 to 1671cm -1 . The aliphatic stretching bands in the 2900cm -1 region yield a consistent triplet pattern because the N-alkyl substituent tail group remains unchanged for all twelve regioisomers. The asymmetric CH 2 stretch is the most intense of these three bands. Changes in positional bonding for both the indole and naphthalene ring systems results in unique patterns within the 700 wavenumber out-of-plane region and these absorption bands are different for all 12 regioisomers. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Fast forward modeling of Titan’s infrared spectra to invert VIMS/CASSINI hyperspectral images

    Science.gov (United States)

    Rodriguez, S.; Le Mouélic, S.; Rannou, P.; Combe, J.; Le Corre, L.; Griffith, C. A.; Tobie, G.; Barnes, J. W.; Sotin, C.; Brown, R. H.; Baines, K. H.; Buratti, B. J.; Clark, R. N.

    2009-12-01

    The surface of Titan, the largest icy moon of Saturn, is veiled by a very thick and hazy atmosphere. The Visual and Infrared Mapping Spectrometer onboard the Cassini spacecraft, in orbit around Saturn since July 2004, has been conducting an intensive survey of Titan with the objective of understanding the complex nature and interaction of the atmosphere and surface of this mysterious moon. Retrieving and separating contributions from the surface and the atmosphere in Titan’s infrared spectra requires accurate radiative transfer modeling, which is often very demanding of computer resources. As Cassini has gathered hitherto millions of spectra of Titan and will continue to observe it until at least 2010, we report here on the development of a new rapid, simple and versatile radiative transfer model specially designed to process VIMS datacubes. Currently, our model accounts for gas absorption, haze scattering and surface reflectance and can be implemented in an inversion scheme. First results of forward modeling provide spectral shapes that are consistent with VIMS measurements, as well as surface and aerosol properties in the range of validity for Titan. Further inversion tests will be carried on VIMS hyperspectral images for the estimate of spatial coherence of the results, accuracy of the surface reflectance within the atmospheric windows, and potential needs for improved input data and modeling. This work was partly performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to the National Aeronautics and Space Administration. Calibrated VIMS data appear courtesy of the VIMS team. We thank the CNES French agency for its financial support.

  16. Infrared spectra of extremophile bacteria under Europan conditions and their astrobiological significance

    Science.gov (United States)

    Dalton, J. B.

    2001-11-01

    Infrared spectral measurements on the sulfur-metabolizing bacteria Sulfolobus shibatae, the radiation-resistant Deinococcus radiodurans and common Escherichia coli have been performed under pressure and temperature conditions appropriate to Europa. Initial results indicate distinct correlations with infrared spectra of Europa measured by telescopic and spacecraft instruments. Several explanations have been proposed for the distorted water absorption features in the Europan spectrum, including the presence of water in a bound state (e.g. hydrates) which prevents certain allowed vibrational transitions. Living cells contain water in many bound forms, including hydrates. Additionally, the red to brown coloration of the bacteria studied appear consistent with the colors observed by Galileo SSI. Room temperature measurements of primitive biological samples reveal spectral structure strikingly similar to that of Europa, though the band positions are not correct because the cellular water is liquid. For this experiment, samples were measured under nitrogen at room temperature and every ten degrees down to 100 K. At cryogenic temperatures the chamber was evacuated to 0.01 mbar. The primary water absorption bands at 1.0, 1.25, 1.5, and 2.0 microns in the samples shifted to the positions observed in the Europa spectra. The distorted and asymmetric features of the 1.5 and 2.0 micron bands were reproduced in detail. Two extraneous bands due to amide bonds in the cells' protein coatings were observed at 2.05 and 2.17 microns. The protein amide bonds are the weakest bonds in the cellular structure and would be among the first to disintegrate upon exposure to particle bombardment at the Europan surface. Experiments involving radiation processing of frozen materials must be conducted before it will be possible to determine whether the results of this study could indeed be evidence for life on Europa.

  17. THE REINCARNATION OF INTERSTELLAR DUST: THE IMPORTANCE OF ORGANIC REFRACTORY MATERIAL IN INFRARED SPECTRA OF COMETARY COMAE AND CIRCUMSTELLAR DISKS

    Energy Technology Data Exchange (ETDEWEB)

    Kimura, Hiroshi, E-mail: hiroshi_kimura@cps-jp.org [Graduate School of Science, Kobe University, c/o CPS (Center for Planetary Science), Chuo-ku Minatojima Minamimachi 7-1-48, Kobe 650-0047 (Japan)

    2013-09-20

    We consider the reincarnation of interstellar dust to be reborn in protoplanetary disks as aggregates consisting of submicron-sized grains with a crystalline or amorphous silicate core and an organic-rich carbonaceous mantle. We find that infrared spectra of reincarnated interstellar dust reproduce emission peaks at correct wavelengths where the peaks were observed in cometary comae, debris disks, and protoplanetary disks if the volume fraction of organic refractory meets the constraints on elemental abundances. We discuss what we can learn from the infrared spectra of reincarnated interstellar dust in cometary comae and circumstellar disks.

  18. The Reincarnation of Interstellar Dust: The Importance of Organic Refractory Material in Infrared Spectra of Cometary Comae and Circumstellar Disks

    Science.gov (United States)

    Kimura, Hiroshi

    2013-09-01

    We consider the reincarnation of interstellar dust to be reborn in protoplanetary disks as aggregates consisting of submicron-sized grains with a crystalline or amorphous silicate core and an organic-rich carbonaceous mantle. We find that infrared spectra of reincarnated interstellar dust reproduce emission peaks at correct wavelengths where the peaks were observed in cometary comae, debris disks, and protoplanetary disks if the volume fraction of organic refractory meets the constraints on elemental abundances. We discuss what we can learn from the infrared spectra of reincarnated interstellar dust in cometary comae and circumstellar disks.

  19. THE REINCARNATION OF INTERSTELLAR DUST: THE IMPORTANCE OF ORGANIC REFRACTORY MATERIAL IN INFRARED SPECTRA OF COMETARY COMAE AND CIRCUMSTELLAR DISKS

    International Nuclear Information System (INIS)

    Kimura, Hiroshi

    2013-01-01

    We consider the reincarnation of interstellar dust to be reborn in protoplanetary disks as aggregates consisting of submicron-sized grains with a crystalline or amorphous silicate core and an organic-rich carbonaceous mantle. We find that infrared spectra of reincarnated interstellar dust reproduce emission peaks at correct wavelengths where the peaks were observed in cometary comae, debris disks, and protoplanetary disks if the volume fraction of organic refractory meets the constraints on elemental abundances. We discuss what we can learn from the infrared spectra of reincarnated interstellar dust in cometary comae and circumstellar disks

  20. Infrared Spectra of Protonated Pyrene and Its Neutral Counterpart in Solid para-Hydrogen.

    Science.gov (United States)

    Bahou, Mohammed; Wu, Yu-Jong; Lee, Yuan-Pern

    2013-06-20

    Protonated polycyclic aromatic hydrocarbons (H(+)PAHs) have been reported to have infrared (IR) bands at wavenumbers near those of unidentified infrared (UIR) emission bands from interstellar objects. We produced 1-C16H11(+) and 1-C16H11 upon electron bombardment during matrix deposition of p-H2 containing pyrene (C16H10) in a small proportion. Intensities of absorption features of 1-C16H11(+) decreased after the matrix was maintained in darkness or irradiated with light at 365 nm, whereas those of 1-C16H11 increased. The observed line wavenumbers and relative intensities of 1-C16H11(+) and 1-C16H11 agree satisfactorily with the scaled vibrational wavenumbers and IR intensities predicted with the B3PW91/6-311++G(2d,2p) method. Our method, being relatively clean with negligible fragmentation, is applicable to larger H(+)PAH; it has the advantages of producing excellent IR spectra covering a broad spectral range with narrow lines and accurate intensities, so that structural identification among various isomers is feasible.

  1. Water Vapor in Titan's Stratosphere from Cassini CIRS Far-Infrared Spectra

    Science.gov (United States)

    Cottini, V.; Nixon, C. A.; Jennings, D. E.; Anderson, C. M.; Gorius, N.; Bjoraker, G. L.; Coustenis, A.; Teanby, N. A.; Achterberg, R. K.; Bezard, B.; hide

    2012-01-01

    Here we report the measurement of water vapor in Titan's stratosphere using the Cassini Composite Infrared Spectrometer (CIRS). CIRS senses water emissions in the far infrared spectral region near 50 micron, which we have modeled using two independent radiative transfer codes. From the analysis of nadir spectra we have derived a mixing ratio of 0.14 +/- 0.05 ppb at an altitude of 97 km, which corresponds to an integrated (from 0 to 600 km) surface normalized column abundance of 3.7 +/- 1.3 1014 molecules/cm2. In the latitude range 80S to 30N we see no evidence for latitudinal variations in these abundances within the error bars. Using limb observations, we obtained mixing ratios of 0.13 +/- 0.04 ppb at an altitude of 115 km and 0.45 +/- 0.15 ppb at an altitude of 230 km, confirming that the water abundance has a positive vertical gradient as predicted by photochemical models. We have also fitted our data using scaling factors of 0.1-0.6 to these photochemical model profiles, indicating that the models over-predict the water abundance in Titan's lower stratosphere.

  2. Near-infrared Reflectance Spectra Of 135 Hertha, 224 Oceana, 516 Amherstia, And 872 Holda

    Science.gov (United States)

    Hardersen, Paul S.; Gaffey, M. J.; Abell, P. A.

    2006-09-01

    Near-infrared reflectance spectra of M-asteroids 135 Hertha, 224 Oceana, 516 Amherstia, and 872 Holda display spectral and mineralogical diversity that is becoming the norm for the M-asteroid taxonomic group. 224 Oceana exhibits a traditionally featureless M-asteroid spectrum, moderately reddish slope, and an IRAS albedo of 17%. Canonical interpretations include a NiFe metal-rich surface or a surface similar to that of the enstatite chondrites. 516 Amherstia, with an IRAS albedo of 16%, displays absorption features centered at 0.93- and 1.92-microns superimposed on an overall reddish slope. This suggests a surface with a single mafic silicate (i.e., pyroxene, Wo10±4Fs31±5) and NiFe metal. The Band I and II absorptions are 5% and 2% deep, respectively. Amherstia's features are similar to, but somewhat more intense and Fe-rich than, other M-asteroid spectra as discussed in Hardersen et al. (2005). 872 Holda displays a generally featureless NIR reflectance spectrum with the exception of a very broad and weak ( 2% depth) absorption that ranges from 0.5 to 1.2-microns. 872 Holda's overall spectrum is similar to that of synthetic troilite, but differs from spectra of meteoritic troilite as discussed in Cloutis and Burbine (1999). If troilite is present on Holda's surface, then a potential interpretation is a mixture of NiFe metal and troilite as seen in iron meteorites. The NIR reflectance spectrum for 135 Hertha will also be discussed and compared to this asteroid's 52-color survey spectrum, which indicates the presence of a weak 0.9-micron absorption feature. Of the 20 M-asteroid spectra that have been examined by this team thus far, 10 M-asteroids display the presence of low-Fe pyroxene absorption features at 0.9 microns, 3 suggest the presence of spinel, 2 indicate the presence of olivine, one suggests the possible presence of troilite, and 4 display featureless spectra that suggest a variety of potential interpretations.

  3. Infrared spectra of phosphate sorbed on iron hydroxide gel and the sorption products

    International Nuclear Information System (INIS)

    Nanzyo, M.

    1986-01-01

    Infrared absorption spectra of phosphate sorbed on iron hydroxide gel were obtained by applying the differential diffuse reflectance method. Absorption bands due to P-O stretching vibration were observed at 1,110 and 1,010 cm -1 at pH 12.3. With decreasing pH, these absorption bands gradually shifted to 1,100 and 1,020 cm -1 at pH 4.9. At pH 2.3, they became a broad single absorption band at 1,060 cm -1 . At pH 11 or above, the difference in the Na + adsorption between phosphated iron hydroxide gel and iron hydroxide gel was almost equal to the amount of phosphate sorption. This finding shows that phosphate was retained on the iron hydroxide gel surface as a bidentate ligand at a high pH. It was concluded that at a high pH phosphate was sorbed on iron hydroxide gel as a binuclear surface complex similar to that on goethite; the change in spectra for P-O stretching vibration with decreasing pH value was mainly caused by an increase in the fraction of amorphous iron phosphate; at pH 2.3, the phosphate sorption product consisted of amorphous iron phosphate. (author)

  4. Combining near infrared spectra of feces and geostatistics to generate forage nutritional quality maps across landscapes

    Science.gov (United States)

    Jean, Pierre-Olivier; Bradley, Robert; Tremblay, Jean-Pierre

    2015-04-01

    An important asset for the management of wild ungulates is the ability to recognize the spatial distribution of forage quality across heterogeneous landscapes. To do so typically requires knowledge of which plant species are eaten, in what abundance they are eaten, and what their nutritional quality might be. Acquiring such data may be, however, difficult and time consuming. Here, we are proposing a rapid and cost-effective forage quality monitoring tool that combines near infrared (NIR) spectra of fecal samples and easily obtained data on plant community composition. Our approach rests on the premise that NIR spectra of fecal samples collected within low population density exclosures reflect the optimal forage quality of a given landscape. Forage quality can thus be based on the Mahalanobis distance of fecal spectral scans across the landscape relative to fecal spectral scans inside exclosures (referred to as DISTEX). The Gi* spatial autocorrelation statistic can then be applied among neighbouring DISTEX values to detect and map 'hot-spots' and 'cold-spots' of nutritional quality over the landscape. We tested our approach in a heterogeneous boreal landscape on Anticosti Island (Qu

  5. Ensemble preprocessing of near-infrared (NIR) spectra for multivariate calibration

    International Nuclear Information System (INIS)

    Xu Lu; Zhou Yanping; Tang Lijuan; Wu Hailong; Jiang Jianhui; Shen Guoli; Yu Ruqin

    2008-01-01

    Preprocessing of raw near-infrared (NIR) spectral data is indispensable in multivariate calibration when the measured spectra are subject to significant noises, baselines and other undesirable factors. However, due to the lack of sufficient prior information and an incomplete knowledge of the raw data, NIR spectra preprocessing in multivariate calibration is still trial and error. How to select a proper method depends largely on both the nature of the data and the expertise and experience of the practitioners. This might limit the applications of multivariate calibration in many fields, where researchers are not very familiar with the characteristics of many preprocessing methods unique in chemometrics and have difficulties to select the most suitable methods. Another problem is many preprocessing methods, when used alone, might degrade the data in certain aspects or lose some useful information while improving certain qualities of the data. In order to tackle these problems, this paper proposes a new concept of data preprocessing, ensemble preprocessing method, where partial least squares (PLSs) models built on differently preprocessed data are combined by Monte Carlo cross validation (MCCV) stacked regression. Little or no prior information of the data and expertise are required. Moreover, fusion of complementary information obtained by different preprocessing methods often leads to a more stable and accurate calibration model. The investigation of two real data sets has demonstrated the advantages of the proposed method

  6. Oxygen infrared spectra of oxyhemoglobins and oxymyoglobins. Evidence of two major liganded O2 structures

    International Nuclear Information System (INIS)

    Potter, W.T.; Tucker, M.P.; Houtchens, R.A.; Caughey, W.S.

    1987-01-01

    The dioxygen stretch bands in infrared spectra for solutions of oxy species of human hemoglobin A and its separated subunits, human mutant hemoglobin Zurich (β63His to Arg), rabbit hemoglobin, lamprey, hemoglobin, sperm whale myoglobin, bovine myoglobin, and a sea worm chlorocruorin are examined. Each protein exhibits multiple isotope-sensitive bands between 1160 and 1060 cm -1 for the liganded 16 O 2 , 17 O 2 , and 18 O 2 . The O-O stretch bands for each of the mammalian myoglobins and hemoglobins are similar, with frequencies that differ between proteins by only 3-5 cm -1 . The spectra for the lamprey and sea worm hemoglobins exhibit greater diversity. For all proteins an O-O stretch band expected to occur near 1125 cm -1 for 16 O 2 and 17 O 2 , but not 18 O 2 , appears split by ∼25 cm -1 due to an unidentified perturbation. The spectrum for each dioxygen isotope, if unperturbed, would contain two strong bands for the mammalian myoglobins (1150 and 1120 cm -1 ) and hemoglobins (1155 and 1125 cm -1 ). Two strong bands separated by ∼30 cm -1 for each oxy heme protein subunit indicate that two major protein conformations (structure) that differ substantially in O 2 bonding are present. The two dioxygen structures can result from a combination of dynamic distal and proximal effects upon the O 2 ligand bound in a bent-end-on stereochemistry

  7. Water Vapor in Titan's Stratosphere from Cassini/CIRS Far-infrared Spectra

    Science.gov (United States)

    Cottini, V.; Nixon, C. A.; Jennings, D. E.; Anderson, C. M.; Gorius, N.; Bjoraker, G. L.; Coustenis, A.; Teanby, N. A.; Achterberg, R. K.; Bezard, B.; hide

    2012-01-01

    Since the first detection of water vapor in Titan's stratosphere by disk-average observations from the Infrared Space Observatory (Coustenis et al. 1998) we report here the successful detection of stratospheric water vapor using the Cassini Composite Infrared Spectrometer (CIRS, Flasar et al. 2004). CIRS senses water emissions in the far infrared spectral region near 50 microns, which we have modeled using two independent radiative transfer codes (NEMESIS, Irwin et al 2008 and ART, Coustenis et al. 2007, 2010). From the analysis of nadir spectra we have derived a mixing ratio of (0.14 0.05) ppb at an altitude of 97 kilometers, which corresponds to an integrated (from 0 to 600 kilometers) surface normalized column abundance of (3.7 plus or minus 1.3) x 10(exp 14) molecules per square centimeter. In the latitude range 80 S to 30 N we see no evidence for latitudinal variations in these abundances within the error bars. Using limb observations, we obtained mixing ratios of (0.13 plus or minus 0.04) ppb at an altitude of 115 kilometers and (0.45 plus or minus 0.15) ppb at an altitude of 230 kilometers, confirming that the water abundance has a positive vertical gradient as predicted by photochemical models (e.g. Lara et al. 1996, Wilson and Atreya 2004, Horst et al. 2008); retrieved scaling factors (from approximately 0.1 to approximately 0.6) to the water profile suggested by these models show that water vapor is present in Titan stratosphere with less abundance than predicted.

  8. CHARACTERIZING THE INFRARED SPECTRA OF SMALL, NEUTRAL, FULLY DEHYDROGENATED POLYCYCLIC AROMATIC HYDROCARBONS

    Energy Technology Data Exchange (ETDEWEB)

    Mackie, C. J.; Peeters, E.; Cami, J. [Department of Physics and Astronomy, University of Western Ontario, London, ON N6A 3K7 (Canada); Bauschlicher, C. W. Jr., E-mail: mackie@strw.leidenuniv.nl [NASA Ames Research Center, MS 245-6, Moffett Field, CA 94035 (United States)

    2015-02-01

    We present the results of a computational study to investigate the infrared spectroscopic properties of a large number of polycyclic aromatic hydrocarbon (PAH) molecules and their fully dehydrogenated counterparts. We constructed a database of fully optimized geometries for PAHs that is complete for eight or fewer fused benzene rings, thus containing 1550 PAHs and 805 fully dehydrogenated aromatics. A large fraction of the species in our database have clearly non-planar or curved geometries. For each species, we determined the frequencies and intensities of their normal modes using density functional theory calculations. Whereas most PAH spectra are fairly similar, the spectra of fully dehydrogenated aromatics are much more diverse. Nevertheless, these fully dehydrogenated species show characteristic emission features at 5.2 μm, 5.5 μm, and 10.6 μm; at longer wavelengths, there is a forest of emission features in the 16-30 μm range that appears as a structured continuum, but with a clear peak centered around 19 μm. We searched for these features in Spitzer-IRS spectra of various positions in the reflection nebula NGC 7023. We find a weak emission feature at 10.68 μm in all positions except that closest to the central star. We also find evidence for a weak 19 μm feature at all positions that is not likely due to C{sub 60}. We interpret these features as tentative evidence for the presence of a small population of fully dehydrogenated PAHs, and discuss our results in the framework of PAH photolysis and the formation of fullerenes.

  9. Infrared matrix isolation and theoretical studies of reactions of ozone with bicyclic alkenes: α-pinene, norbornene, and norbornadiene.

    Science.gov (United States)

    Kugel, Roger W; Ault, Bruce S

    2015-01-15

    The reactions of ozone with three bicyclic alkenes, α-pinene, norbornene, and norbornadiene, were studied by low-temperature (14 K), argon matrix isolation infrared spectroscopy including (18)O isotope-labeling studies. Theoretical calculations of some of the proposed reaction intermediates and products were carried out using the Gaussian 09 suite of programs, applying density functional theory (DFT), the B3LYP functional, and the 6-311G++(d,2p) basis set. In the α-pinene/ozone system, the thermal reaction between α-pinene and ozone was too slow to observe under the twin-jet or merged-jet deposition conditions of these experiments. However, red light (λ ≥ 600 nm) irradiation of the argon matrixes containing α-pinene and ozone caused new infrared peaks to appear that could be readily assigned to reaction products of α-pinene with O((3)P) resulting from ozone photolysis: α-pinene oxide (with an epoxide ring) and two isomeric ketones. Norbornene and norbornadiene were both found to react with ozone in the gas phase during twin-jet or merged-jet deposition of these mixtures with argon. New peaks observed in the infrared spectra were assigned to the primary ozonides, Criegee intermediates, and secondary ozonides of norbornene and norbornadiene, indicating that the bulk of these reactions proceeded via the "classic" Criegee mechanism for ozonolysis of alkenes. Calculated infrared frequencies and molecular energies support these conclusions. Ultraviolet irradiation of these mixtures resulted in complete decomposition of the early intermediates and the formation of acids, aldehydes, alcohols, carbon dioxide, and carbon monoxide. In any case, no evidence for "unusual" chemistry, prompted by the bicyclic nature of the reactants, was observed.

  10. A CATALOG OF NEAR-INFRARED SPECTRA FROM TYPE Ia SUPERNOVAE

    International Nuclear Information System (INIS)

    Marion, G. H.; Wheeler, J. C.; Robinson, E. L.; Hoeflich, P.; Gerardy, C. L.; Vacca, W. D.

    2009-01-01

    We present 41 near-infrared (NIR, 0.7-2.5 μm) spectra from normal Type Ia supernovae (SNe Ia) obtained at epochs ranging from 14 days before to 75 days with respect to the maximum light date in the V band. All data were obtained at the Infrared Telescope Facility using the SpeX instrument. We identify many spectral features, measure the Doppler velocities, and discuss the chemical distribution of explosion products in SNe Ia. We describe procedures for smoothing data, fitting continua, and measuring absorption features to ensure consistency for measurement and analysis. This sample provides the first opportunity to examine and compare a large number of SNe Ia in this wavelength region. NIR data are a rich source of information about explosion products whose signatures are blended or obscured in other spectral regions and NIR observations probe a greater radial depth than optical wavelengths. We analyze similarities and differences in the spectra and we show that the progressive development of spectral features for normal SNe Ia in the NIR is consistent with time. We confirm the presence of O I, Mg II, Ca II, Si II, Fe II, and Co II in these SNe. Possible identifications are made for S I, Si III, Mn II, and Fe III. There is no evidence in these data for H I, He I, C I, or C II. As the explosion products expand and cool, progressively deeper layers are revealed. Thus, a time sequence of spectra examines the chemical structure and provides direct evidence of the physical properties of SNe Ia from the outer layers to deep inside the SN. Measured Doppler velocities indicate that burning products in SNe Ia are distributed in distinct layers with no large-scale mixing. Carbon is not detected in these data, in agreement with previous results with NIR data establishing very low limits on carbon abundance in SNe Ia. Carbon burning products, O and Mg, are plentiful in the outer layers suggesting that the entire progenitor is burned in the explosion. The data provide a

  11. Optical and Near-infrared Spectra of σ Orionis Isolated Planetary-mass Objects

    Energy Technology Data Exchange (ETDEWEB)

    Zapatero Osorio, M. R. [Centro de Astrobiología (CSIC-INTA), Crta. Ajalvir km 4, E-28850 Torrejón de Ardoz, Madrid (Spain); Béjar, V. J. S. [Instituto de Astrofísica de Canarias, C/. Vía Láctea s/n, E-38205 La Laguna, Tenerife (Spain); Ramírez, K. Peña, E-mail: mosorio@cab.inta-csic.es, E-mail: vbejar@iac.es, E-mail: karla.pena@uantof.cl [Unidad de Astronomía de la Universidad de Antofagasta, Av. U. de Antofagasta. 02800 Antofagasta (Chile)

    2017-06-10

    We have obtained low-resolution optical (0.7–0.98 μ m) and near-infrared (1.11–1.34 μ m and 0.8–2.5 μ m) spectra of 12 isolated planetary-mass candidates ( J = 18.2–19.9 mag) of the 3 Myr σ Orionis star cluster with the aim of determining the spectroscopic properties of very young, substellar dwarfs and assembling a complete cluster mass function. We have classified our targets by visual comparison with high- and low-gravity standards and by measuring newly defined spectroscopic indices. We derived L0–L4.5 and M9–L2.5 using high- and low-gravity standards, respectively. Our targets reveal clear signposts of youth, thus corroborating their cluster membership and planetary masses (6–13 M {sub Jup}). These observations complete the σ Orionis mass function by spectroscopically confirming the planetary-mass domain to a confidence level of ∼75%. The comparison of our spectra with BT-Settl solar metallicity model atmospheres yields a temperature scale of 2350–1800 K and a low surface gravity of log g ≈ 4.0 [cm s{sup −2}], as would be expected for young planetary-mass objects. We discuss the properties of the cluster’s least-massive population as a function of spectral type. We have also obtained the first optical spectrum of S Ori 70, a T dwarf in the direction of σ Orionis. Our data provide reference optical and near-infrared spectra of very young L dwarfs and a mass function that may be used as templates for future studies of low-mass substellar objects and exoplanets. The extrapolation of the σ Orionis mass function to the solar neighborhood may indicate that isolated planetary-mass objects with temperatures of ∼200–300 K and masses in the interval 6–13 M {sub Jup} may be as numerous as very low-mass stars.

  12. INFRARED AND ULTRAVIOLET SPECTRA OF METHANE DILUTED IN SOLID NITROGEN AND IRRADIATED WITH ELECTRONS DURING DEPOSITION AT VARIOUS TEMPERATURES

    Energy Technology Data Exchange (ETDEWEB)

    Chin, Chih-Hao; Chen, Sian-Cong; Liu, Meng-Chen; Huang, Tzu-Ping; Wu, Yu-Jong, E-mail: yjwu@nsrrc.org.tw [National Synchrotron Radiation Research Center, No. 101, Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China)

    2016-06-01

    We recorded the infrared and ultraviolet absorption spectra of CH{sub 4}:N{sub 2} matrix samples that underwent electron bombardment during deposition in the temperature range of 10–44 K. In contrast to a previous experiment on the IR spectroscopy of electron-bombarded icy samples, methyl and azide radicals became the main products upon electron bombardment during deposition; furthermore, reduced production of nitrile species was observed for deposition at 10 and 20 K. On the other hand, for deposition above 33 K, the observed bands of the radical species (such as methyl and azide) decreased, and bands of large nitriles appeared. This observation may suggest that radical species easily diffuse and recombine to form more complex molecules in solid nitrogen at higher temperatures. Further measurements of similar samples at 10–33 K in the UV region revealed the intense band of azide radicals at 272.5 nm and weak, broad, overlapping features of methyl and azide radicals in the 225–197 nm region. For deposition at 44 K, only a broad feature centered at 219.4 nm was observed, and the possible carriers of nitrile species were proposed based on the corresponding IR spectrum and theoretical predictions of excitation energy. This band is similar to the observed absorption feature of Pluto’s surface recorded by the Hubble telescope in terms of both band position and bandwidth. Our findings therefore further support the suggestion that complex nitrile species may exist on the surface of Pluto.

  13. Experimental and theoretical studies on IR, Raman, and UV-Vis spectra of quinoline-7-carboxaldehyde.

    Science.gov (United States)

    Kumru, M; Küçük, V; Kocademir, M; Alfanda, H M; Altun, A; Sarı, L

    2015-01-05

    Spectroscopic properties of quinoline-7-carboxaldehyde (Q7C) have been studied in detail both experimentally and theoretically. The FT-IR (4000-50 cm(-1)), FT-Raman (4000-50 cm(-1)), dispersive-Raman (3500-50 cm(-1)), and UV-Vis (200-400 nm) spectra of Q7C were recorded at room temperature (25 °C). Geometry parameters, potential energy surface about CCH(O) bond, harmonic vibrational frequencies, IR and Raman intensities, UV-Vis spectrum, and thermodynamic characteristics (at 298.15K) of Q7C were computed at Hartree-Fock (HF) and density functional B3LYP levels employing the 6-311++G(d,p) basis set. Frontier molecular orbitals, molecular electrostatic potential, and Mulliken charge analyses of Q7C have also been performed. Q7C has two stable conformers that are energetically very close to each other with slight preference to the conformer that has oxygen atom of the aldehyde away from the nitrogen atom of the quinoline. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Proton hydration in aqueous solution: Fourier transform infrared studies of HDO spectra.

    Science.gov (United States)

    Smiechowski, Maciej; Stangret, Janusz

    2006-11-28

    This paper attempts to elucidate the number and nature of the hydration spheres around the proton in an aqueous solution. This phenomenon was studied in aqueous solutions of selected acids by means of Fourier transform infrared spectroscopy of semiheavy water (HDO), isotopically diluted in H(2)O. The quantitative version of difference spectrum procedure was applied for the first time to investigate such systems. It allowed removal of bulk water contribution and separation of the spectra of solute-affected HDO. The obtained spectral data were confronted with ab initio calculated structures of small gas-phase and polarizable continuum model (PCM) solvated aqueous clusters, H+(H2O)n, n=2-8, in order to help in establishing the structural and energetic states of the consecutive hydration spheres of the hydrated proton. This was achieved by comparison of the calculated optimal geometries with the interatomic distances derived from HDO band positions. The structure of proton hydration shells outside the first hydration sphere essentially follows the model structure of other hydrated cations, previously revealed by affected HDO spectra. The first hydration sphere complex in diluted aqueous solutions was identified as an asymmetric variant of the regular Zundel cation [The Hydrogen Bond: Recent Developments in Theory and Experiments, edited by P. Schuster, G. Zundel, and C. Sandorfy (North-Holland, Amsterdam, 1976), Vol. II, p. 683], intermediate between the ideal Zundel and Eigen structures [E. Wicke et al., Z. Phys. Chem. Neue Folge 1, 340 (1954)]. Evidence was found for the existence of strong and short hydrogen bonds, with oxygen-oxygen distance derived from the experimental affected spectra equal 2.435 A on average and in the PCM calculations about 2.41-2.44 A. It was also evidenced for the first time that the proton possesses four well-defined hydration spheres, which were characterized in terms of hydrogen bonds' lengths and arrangements. Additionally, an outer

  15. Signal-to-Noise Contribution of Principal Component Loads in Reconstructed Near-Infrared Raman Tissue Spectra

    NARCIS (Netherlands)

    Grimbergen, M. C. M.; van Swol, C. F. P.; Kendall, C.; Verdaasdonk, R. M.; Stone, N.; Bosch, J. L. H. R.

    The overall quality of Raman spectra in the near-infrared region, where biological samples are often studied, has benefited from various improvements to optical instrumentation over the past decade. However, obtaining ample spectral quality for analysis is still challenging due to device

  16. An accurate retrieval of leaf water content from mid to thermal infrared spectra using continuous wavelet analysis

    NARCIS (Netherlands)

    Ullah, S.; Skidmore, A.K.; Naeem, M.; Schlerf, M.

    2012-01-01

    Leaf water content determines plant health, vitality, photosynthetic efficiency and is an important indicator of drought assessment. The retrieval of leaf water content from the visible to shortwave infrared spectra is well known. Here for the first time, we estimated leaf water content from the mid

  17. Theoretical investigations of the structures and electronic spectra of 8-hydroxylquinoline derivatives

    Science.gov (United States)

    Ning, Pan; Ren, Tiegang; Zhang, Yanxin; Zhang, Jinglai

    2013-11-01

    The spectroscopic properties of 8-hydroxyquinoline derivatives are theoretically investigated by means of density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. The target molecules are divided into two groups: group (I): (E)-2-(2-(3,5-dimethyl-1-phenyl-1H-pyrazol-4-yl)vinyl)quinolin-8-ol (A), together with corresponding potential reaction products of A with acetic acid, i.e., (E)-2-(2-(3,5-dimethyl-1-phenyl-1H-pyrazol-4-yl)vinyl)quinolin-8-yl acetate (AR1), and (E)-2-(2-(3,5-dimethyl-1-phenyl-1H-pyrazol-4-yl)vinyl)-8-hydroxyquinolinium (AR2); group (II): (E)-2-(2-(1-(4-chlorophenyl)-3,5-dimethyl-1H-pyrazol-4-yl)vinyl)quinolin-8-ol (B), as well as potential reaction products of B with acetic acid, i.e., (E)-2-(2-(1-(4-chlorophenyl)-3,5-dimethyl-1H-pyrazol-4-yl)vinyl)quinolin-8-yl acetate (BR1), and (E)-2-(2-(1-(4-chlorophenyl)-3,5-dimethyl-1H-pyrazol-4-yl)vinyl)-8-hydroxyquinolinium (BR2). The geometries are optimized by B3LYP and M06 methods. The results indicate that product molecules tend to be effectively planar compared with reactants. Subsequently, UV absorption spectra are simulated through TD-DFT method with PCM model to further confirm the reasonable products of two reactions. AR2 and BR2 are identified as the target molecules through the experimental spectra for the real products. It is worth noting that the maximum absorption wavelengths of compounds AR2 and BR2 present prominent red shift compared the initial reactants A and B, respectively, which should be ascribed to the enhancive planarity of products that mentioned above and the decreased HOMO-LUMO energy gap. Geometric structures and optical properties for corresponding compounds are discussed in detail.

  18. Predicting ambient aerosol thermal-optical reflectance (TOR) measurements from infrared spectra: organic carbon

    Science.gov (United States)

    Dillner, A. M.; Takahama, S.

    2015-03-01

    Organic carbon (OC) can constitute 50% or more of the mass of atmospheric particulate matter. Typically, organic carbon is measured from a quartz fiber filter that has been exposed to a volume of ambient air and analyzed using thermal methods such as thermal-optical reflectance (TOR). Here, methods are presented that show the feasibility of using Fourier transform infrared (FT-IR) absorbance spectra from polytetrafluoroethylene (PTFE or Teflon) filters to accurately predict TOR OC. This work marks an initial step in proposing a method that can reduce the operating costs of large air quality monitoring networks with an inexpensive, non-destructive analysis technique using routinely collected PTFE filter samples which, in addition to OC concentrations, can concurrently provide information regarding the composition of organic aerosol. This feasibility study suggests that the minimum detection limit and errors (or uncertainty) of FT-IR predictions are on par with TOR OC such that evaluation of long-term trends and epidemiological studies would not be significantly impacted. To develop and test the method, FT-IR absorbance spectra are obtained from 794 samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites collected during 2011. Partial least-squares regression is used to calibrate sample FT-IR absorbance spectra to TOR OC. The FTIR spectra are divided into calibration and test sets by sampling site and date. The calibration produces precise and accurate TOR OC predictions of the test set samples by FT-IR as indicated by high coefficient of variation (R2; 0.96), low bias (0.02 μg m-3, the nominal IMPROVE sample volume is 32.8 m3), low error (0.08 μg m-3) and low normalized error (11%). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision to collocated TOR measurements. FT-IR spectra are also

  19. Predicting ambient aerosol Thermal Optical Reflectance (TOR) measurements from infrared spectra: elemental carbon

    Science.gov (United States)

    Dillner, A. M.; Takahama, S.

    2015-06-01

    Elemental carbon (EC) is an important constituent of atmospheric particulate matter because it absorbs solar radiation influencing climate and visibility and it adversely affects human health. The EC measured by thermal methods such as Thermal-Optical Reflectance (TOR) is operationally defined as the carbon that volatilizes from quartz filter samples at elevated temperatures in the presence of oxygen. Here, methods are presented to accurately predict TOR EC using Fourier Transform Infrared (FT-IR) absorbance spectra from atmospheric particulate matter collected on polytetrafluoroethylene (PTFE or Teflon) filters. This method is similar to the procedure tested and developed for OC in prior work (Dillner and Takahama, 2015). Transmittance FT-IR analysis is rapid, inexpensive, and non-destructive to the PTFE filter samples which are routinely collected for mass and elemental analysis in monitoring networks. FT-IR absorbance spectra are obtained from 794 filter samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites collected during 2011. Partial least squares regression is used to calibrate sample FT-IR absorbance spectra to collocated TOR EC measurements. The FTIR spectra are divided into calibration and test sets. Two calibrations are developed, one which is developed from uniform distribution of samples across the EC mass range (Uniform EC) and one developed from a~uniform distribution of low EC mass samples (EC TOR EC samples in the same mass range and an estimate of the minimum detection limit (MDL) that is on par with TOR EC MDL. For all samples, this hybrid approach leads to precise and accurate TOR EC predictions by FT-IR as indicated by high coefficient of variation (R2; 0.96), no bias (0.00 μg m-3, concentration value based on the nominal IMPROVE sample volume of 32.8 m-3), low error (0.03 μg m-3) and reasonable normalized error (21 %). These performance metrics can be achieved with various degrees of spectral pretreatment

  20. A combined experimental and theoretical studies on FT-IR, FT-Raman and UV-vis spectra of 2-chloro-3-quinolinecarboxaldehyde.

    Science.gov (United States)

    Prasad, M V S; Udaya Sri, N; Veeraiah, V

    2015-09-05

    In the present study, the FT-IR and FT-Raman spectra of 2-chloro-3-quinolinecarboxaldehyde (2Cl3QC) have been recorded in the region 4000-400 and 3500-50 cm(-1), respectively. The fundamental modes of vibrational frequencies of 2Cl3QC are assigned. Theoretical information on the optimized geometry, harmonic vibrational frequencies, infrared and Raman intensities were obtained by means of density functional theory (DFT) gradient calculations with complete relaxation in the potential energy surface using 6-31G(d,p) basis set. The vibrational frequencies which were determined experimentally from the spectral data are compared with those obtained theoretically from DFT calculations. A close agreement was achieved between the observed and calculated frequencies by refinement of the scale factors. The infrared and Raman spectra were also predicted from the calculated intensities. Thermodynamic properties like entropy, heat capacity, zero point energy, have been calculated for the molecule. The predicted first hyperpolarizability also shows that the molecule might have a reasonably good non-linear optical (NLO) behavior. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. Stability of the molecule arising from hyper conjugative interactions, charge delocalization have been analyzed using natural bond orbitals (NBO) analysis. The results show that charge in electron density (ED) in the π(∗) antibonding orbitals and E((2)) energies confirms the occurrence of ICT (intra-molecular charge transfer) within the molecule. UV-visible spectrum of the title molecule has also been calculated using TD-DFT/CAM-B3LYP/6-31G(d,p) method. The calculated energy and oscillator strength almost exactly reproduces reported experimental data. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Simulated infrared emission spectra of highly excited polyatomic molecules: a detailed model of the PAH-UIR hypothesis

    Science.gov (United States)

    Cook, D. J.; Saykally, R. J.

    1998-01-01

    A detailed description of the polycyclic aromatic hydrocarbon (PAH)/unidentified infrared band (UIR) mechanism is presented in which experimental spectral bandshape functions are used to simulate IR emission spectra for individual molecules. These spectra are additively superimposed to produce a conglomerate spectrum representative of a family of PAH molecules. Ab initio vibrational frequencies and intensities for nine PAHs (neutral and cationic) as large as ovalene are used in conjunction with measured bandshape and temperature-dependent redshift data to simulate the UIR bands. The calculated spectra of cations provide a closer match to the UIRs than do those of the neutrals. However, the PAH cations used in the simulations fail to reproduce the details of the UIR emission spectra. The discrepancies are potentially alleviated if both larger PAHs and a greater number of PAHs were included in the simulation.

  2. Infrared and Raman scattering spectra of layered structured Ga{sub 3}InSe{sub 4} crystals

    Energy Technology Data Exchange (ETDEWEB)

    Isik, M., E-mail: misik@atilim.edu.tr [Department of Electrical and Electronics Engineering, Atilim University, 06836 Ankara (Turkey); Gasanly, N.M. [Department of Physics, Middle East Technical University, 06800 Ankara (Turkey); Korkmaz, F. [Department of Electrical and Electronics Engineering, Atilim University, 06836 Ankara (Turkey)

    2013-03-01

    The infrared reflectivity and transmittance and Raman scattering in Ga{sub 3}InSe{sub 4} layered crystals were investigated in the frequency ranges of 100–400, 400–4000 and 25–500 cm{sup −1}. The refractive and absorption indices, the frequencies of transverse and longitudinal optical modes, high- and low-frequency dielectric constants were obtained from the analysis of the IR reflectivity spectra. The bands observed in IR transmittance spectra were interpreted in terms of two-phonon absorption processes.

  3. Theoretically predicted soft x-ray emission and absorption spectra of graphitic-structured BC2N

    Science.gov (United States)

    Muramatsu, Yasuji

    Theoretical B K, C K and N K x-ray emission/absorption spectra of three possible graphitic-structured BC2N clusters are predicted based on the B2p-, C2p-, and N2p- density-of-states (DOS) calculated by discrete variational (DV)-X[alpha] molecular orbital calculations. Several prominent differences in DOS spectral features among BC2Ns, h-BN, and graphite are confirmed from comparison of calculated B2p-, C2p-, and N2p-DOS spectra. These variations in the spectra allow BC2N structures to be positively identified by high-resolution x-ray emission/absorption spectroscopy in the B K, C K, and N K regions.

  4. Relationship between wine scores and visible-near-infrared spectra of Australian red wines.

    Science.gov (United States)

    Cozzolino, D; Cowey, G; Lattey, K A; Godden, P; Cynkar, W U; Dambergs, R G; Janik, L; Gishen, M

    2008-06-01

    Sensory analysis of wine involves the measurement, interpretation and understanding of human responses to the properties perceived by the senses such as sight, smell and taste. The sensory evaluation of wine is often carried out by wine judges, winemakers and technical staff, and allows characterization of the quality of the wine. However, this method is lengthy, expensive, and its results depend on panel training and the specific vocabulary used by the panel. A robust, rapid, unbiased and inexpensive method to assist in quality assessment purposes will therefore be beneficial for the modern wine industry. This study aims to investigate the relationship between sensory analysis, visible (VIS) and near-infrared (NIR) spectroscopy to assess sensory properties of commercial Australian wine varieties. For the purposes of this study 118 red wine samples (Cabernet Sauvignon, Shiraz, Pinot Noir, Tempranillo, Nebbiolo and blends) graded by a panel of experienced tasters and scored according to the Australian wine show system were scanned in transmission in the VIS and NIR range (400-2,500 nm). Partial least squares regression models were developed between the overall score given by the judges and the combined VIS-NIR spectra, using full cross validation (leave-one-out method). The results showed that NIR spectroscopy was able to predict wine quality scores in red wine samples (R = 0.61 and standard error of prediction of 0.81). The practical implication of this study is that instrumental methods such as VIS-NIR spectroscopy can be used to complement sensory analysis and can facilitate the task at early stages of product development, making high-throughput screening of novel products feasible or maintaining the consistency of the product.

  5. Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations.

    Science.gov (United States)

    Fang, Zongtang; Thanthiriwatte, K Sahan; Dixon, David A; Andrews, Lester; Wang, Xuefeng

    2016-02-15

    Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH)3 and Ce(OH)2 molecules and Ce(OH)2(+) cation as major products. Additional minor products were identified as the Ce(OH)4, HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D2O2, D2, and (18)O2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH)3 and of the Ce(OH)2(+) cation increase on UV (λ > 220 nm) photolysis, while Ce(OH)2, Ce(OH)4, and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH)4, is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most open shell species have the excess spin in the 4f with paired spin in the 5d due to backbonding. The heats of formation of the observed species were derived from the available data from experiment and the calculated reaction energies. The major products in this study are different from similar reactions for Th where the tetrahydroxide was the major species.

  6. Meeting the Cool Neighbors. XII. An Optically Anchored Analysis of the Near-infrared Spectra of L Dwarfs

    Science.gov (United States)

    Cruz, Kelle L.; Núñez, Alejandro; Burgasser, Adam J.; Abrahams, Ellianna; Rice, Emily L.; Reid, I. Neill; Looper, Dagny

    2018-01-01

    Discrepancies between competing optical and near-infrared (NIR) spectral typing systems for L dwarfs have motivated us to search for a classification scheme that ties the optical and NIR schemes together, and addresses complexities in the spectral morphology. We use new and extant optical and NIR spectra to compile a sample of 171 L dwarfs, including 27 low-gravity β and γ objects, with spectral coverage from 0.6–2.4 μm. We present 155 new low-resolution NIR spectra and 19 new optical spectra. We utilize a method for analyzing NIR spectra that partially removes the broad-band spectral slope and reveals similarities in the absorption features between objects of the same optical spectral type. Using the optical spectra as an anchor, we generate near-infrared spectral average templates for L0–L8, L0–L4γ, and L0–L1β type dwarfs. These templates reveal that NIR spectral morphologies are correlated with the optical types. They also show the range of spectral morphologies spanned by each spectral type. We compare low-gravity and field-gravity templates to provide recommendations on the minimum required observations for credibly classifying low-gravity spectra using low-resolution NIR data. We use the templates to evaluate the existing NIR spectral standards and propose new ones where appropriate. Finally, we build on the work of Kirkpatrick et al. to provide a spectral typing method that is tied to the optical and can be used when only H or K band data are available. The methods we present here provide resolutions to several long-standing issues with classifying L dwarf spectra and could also be the foundation for a spectral classification scheme for cloudy exoplanets.

  7. Application of class-modelling techniques to infrared spectra for analysis of pork adulteration in beef jerkys.

    Science.gov (United States)

    Kuswandi, Bambang; Putri, Fitra Karima; Gani, Agus Abdul; Ahmad, Musa

    2015-12-01

    The use of chemometrics to analyse infrared spectra to predict pork adulteration in the beef jerky (dendeng) was explored. In the first step, the analysis of pork in the beef jerky formulation was conducted by blending the beef jerky with pork at 5-80 % levels. Then, they were powdered and classified into training set and test set. The second step, the spectra of the two sets was recorded by Fourier Transform Infrared (FTIR) spectroscopy using atenuated total reflection (ATR) cell on the basis of spectral data at frequency region 4000-700 cm(-1). The spectra was categorised into four data sets, i.e. (a) spectra in the whole region as data set 1; (b) spectra in the fingerprint region (1500-600 cm(-1)) as data set 2; (c) spectra in the whole region with treatment as data set 3; and (d) spectra in the fingerprint region with treatment as data set 4. The third step, the chemometric analysis were employed using three class-modelling techniques (i.e. LDA, SIMCA, and SVM) toward the data sets. Finally, the best result of the models towards the data sets on the adulteration analysis of the samples were selected and the best model was compared with the ELISA method. From the chemometric results, the LDA model on the data set 1 was found to be the best model, since it could classify and predict 100 % accuracy of the sample tested. The LDA model was applied toward the real samples of the beef jerky marketed in Jember, and the results showed that the LDA model developed was in good agreement with the ELISA method.

  8. Theoretical analysis, infrared and structural investigations of energy dissipation in metals under cyclic loading

    International Nuclear Information System (INIS)

    Plekhov, O.A.; Saintier, N.; Palin-Luc, T.; Uvarov, S.V.; Naimark, O.B.

    2007-01-01

    The infrared and structural investigations of energy dissipation processes in metals subjected to cyclic loading have given impetus to the development of a new thermodynamic model with the capability of describing the energy balance under plastic deformation. The model is based on the statistical description of the mesodefect ensemble evolution and its influence on the dissipation ability of the material. Constitutive equations have been formulated for plastic and structural strains, which allow us to describe the stored and dissipated parts of energy under plastic flow. Numerical results indicate that theoretical predictions are in good agreement with the experimentally observed temperature data

  9. Theoretical and Experimental Research in Neutron Spectra and Nuclear Waste Transmutation on Fast Subcritical Assembly with MOX Fuel

    Science.gov (United States)

    Arkhipkin, D. A.; Buttsev, V. S.; Chigrinov, S. E.; Kutuev, R. Kh.; Polanski, A.; Rakhno, I. L.; Sissakian, A.; Zulkarneev, R. Ya.; Zulkarneeva, Yu. R.

    2003-07-01

    The paper deals with theoretical and experimental investigation of transmutation rates for a number of long-lived fission products and minor actinides, as well as with neutron spectra formed in a subcritical assembly driven with the following monodirectional beams: 660-MeV protons and 14-MeV neutrons. In this work, the main objective is the comparison of neutron spectra in the MOX assembly for different external driving sources: a 660-MeV proton accelerator and a 14-MeV neutron generator. The SAD project (JINR, Russia) has being discussed. In the context of this project, a subcritical assembly consisting of a cylindrical lead target surrounded by a cylindrical MOX fuel layer will be constructed. Present conceptual design of the subcritical assembly is based on the core with a nominal unit capacity of 15 kW (thermal). This corresponds to a multiplication coefficient, keff= 0.945, and an accelerator beam power of 0.5 kW. The results of theoretical investigations on the possibility of incinerating long-lived fission products and minor actinides in fast neutron spectrum and formation of neutron spectra with different hardness in subcritical systems based on the MOX subcritical assembly are discussed. Calculated neutron spectra emitted from a lead target irradiated by a 660-MeV protons are also presented.

  10. Strong spin-phonon coupling in infrared and Raman spectra of SrMnO.sub.3./sub..

    Czech Academy of Sciences Publication Activity Database

    Kamba, Stanislav; Goian, Veronica; Skoromets, Volodymyr; Hejtmánek, Jiří; Bovtun, Viktor; Kempa, Martin; Borodavka, Fedir; Vaněk, Přemysl; Belik, A.A.; Lee, J.H.; Pacherová, Oliva; Rabe, K.M.

    2014-01-01

    Roč. 89, č. 6 (2014), "064308-1"-"064308-9" ISSN 1098-0121 R&D Projects: GA MŠk LH13048; GA ČR GAP204/12/1163; GA MŠk LD12026; GA ČR GP14-14122P Institutional support: RVO:68378271 Keywords : multiferroics * spin-phonon coupling * infrared and Raman spectra Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.736, year: 2014

  11. Retrieval of Soil Water Content in Saline Soils from Emitted Thermal Infrared Spectra Using Partial Linear Squares Regression

    Directory of Open Access Journals (Sweden)

    Lu Xu

    2015-11-01

    Full Text Available Timely information of soil water content is urgently required for monitoring ecosystem processes and functions at various scales. Although remote sensing has already provided many practical applications of retrieving soil moisture, it is largely limited to visible/near infrared or microwave domains and few studies have ever been conducted on the thermal infrared. In addition, soil salinization in arid land further complicates the situation when retrieving soil moisture from emitted spectra. In this study, we attempt to fill the knowledge gap by retrieving the soil moisture of saline soils with various salt contents. This was based on lab-controlled experiments for spectroscopy using a Fourier Transform Spectrometer (2–16 µm. Partial least squares regression (PLSR has been applied in analyses based on either original measured or first-order derivative spectra. The results revealed that the PLSR model using first-order derivative spectra, which had a determination coefficient (R2 of 0.71 and a root mean square error (RMSE of 3.3%, should be recommended for soil moisture estimation, judged from several statistical criteria. As thermal infrared wavelengths identified in this study are contained in several current available satellite sensors, the PLSR models should have great potential for large-scale application despite extensive validations are needed in future studies.

  12. VizieR Online Data Catalog: Low-resolution near-infrared stellar spectra from CIBER (Kim+, 2017)

    Science.gov (United States)

    Kim, M. G.; Lee, H. M.; Arai, T.; Bock, J.; Cooray, A.; Jeong, W.-S.; Kim, S. J.; Korngut, P.; Lanz, A.; Lee, D. H.; Lee, M. G.; Matsumoto, T.; Matsuura, S.; Nam, U. W.; Onishi, Y.; Shirahata, M.; Smidt, J.; Tsumura, K.; Yamamura, I.; Zemcov, M.

    2017-06-01

    We present flux-calibrated near-infrared spectra of 105 stars from 0.8{skin, we do not use the first flight data in this work. The star spectral types are determined by fitting known spectral templates to the measured LRS spectra. We use the Infrared Telescope Facility (IRTF) and Pickles 1998 (Cat. J/PASP/110/863) templates for the SED fitting. The SpeX instrument installed on the IRTF observed stars using a medium-resolution spectrograph (R=2000). The template library contains spectra for 210 cool stars (F to M type) with wavelength coverage from 0.8 to 2.5μm (Cushing 2005ApJ...623.1115C; Rayner 2009ApJS..185..289R). The Pickles library is a synthetic spectral library that combines spectral data from various observations to achieve wavelength coverage from the UV (0.115μm) to the near-infrared (2.5μm). It contains 131 spectral templates for all star types (i.e., O to M type) with a uniform sampling interval of 5Å. (6 data files).

  13. FAR-INFRARED LINE SPECTRA OF SEYFERT GALAXIES FROM THE HERSCHEL-PACS SPECTROMETER

    Energy Technology Data Exchange (ETDEWEB)

    Spinoglio, Luigi; Pereira-Santaella, Miguel; Busquet, Gemma [Istituto di Astrofisica e Planetologia Spaziali, INAF, Via Fosso del Cavaliere 100, I-00133 Roma (Italy); Dasyra, Kalliopi M. [Observatoire de Paris, LERMA (CNRS:UMR8112), 61 Av. de l' Observatoire, F-75014, Paris (France); Calzoletti, Luca [Agenzia Spaziale Italiana (ASI) Science Data Center, I-00044 Frascati (Roma) (Italy); Malkan, Matthew A. [Astronomy Division, University of California, Los Angeles, CA 90095-1547 (United States); Tommasin, Silvia, E-mail: luigi.spinoglio@iaps.inaf.it [Weizmann Institute of Science, Department of Neurobiology, Rehovot 76100 (Israel)

    2015-01-20

    We observed the far-IR fine-structure lines of 26 Seyfert galaxies with the Herschel-PACS spectrometer. These observations are complemented with Spitzer Infrared Spectrograph and Herschel SPIRE spectroscopy. We used the ionic lines to determine electron densities in the ionized gas and the [C I] lines, observed with SPIRE, to measure the neutral gas densities, while the [O I] lines measure the gas temperature, at densities below ∼10{sup 4} cm{sup –3}. Using the [O I]145 μm/63 μm and [S III]33/18 μm line ratios, we find an anti-correlation of the temperature with the gas density. Various fine-structure line ratios show density stratifications in these active galaxies. On average, electron densities increase with the ionization potential of the ions. The infrared lines arise partly in the narrow line region, photoionized by the active galactic nucleus (AGN), partly in H II regions photoionized by hot stars, and partly in photo-dissociated regions. We attempt to separate the contributions to the line emission produced in these different regions by comparing our observed emission line ratios to theoretical values. In particular, we tried to separate the contribution of AGNs and star formation by using a combination of Spitzer and Herschel lines, and we found that besides the well-known mid-IR line ratios, the line ratio of [O III]88 μm/[O IV]26 μm can reliably discriminate the two emission regions, while the far-IR line ratio of [C II]157 μm/[O I]63 μm is only able to mildly separate the two regimes. By comparing the observed [C II]157 μm/[N II]205 μm ratio with photoionization models, we also found that most of the [C II] emission in the galaxies we examined is due to photodissociation regions.

  14. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    Energy Technology Data Exchange (ETDEWEB)

    Justino, Licínia L. G., E-mail: liciniaj@ci.uc.pt; Reva, Igor; Fausto, Rui [CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra (Portugal)

    2016-07-07

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N{sub 2}, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  15. [Application study of the thermal infrared emissivity spectra in the estimation of salt content of saline soil].

    Science.gov (United States)

    Xia, Jun; Tashpolat, Tiyip; Mamat, Sawut; Zhang, Fei; Han, Gui-Hong

    2012-11-01

    Studying of soil salinization is of great significance for agricultural production in arid area oasis, thermal infrared remote sensing technology provides a new technology and method in this field. Authors used Fourier transform infrared spectrometer to measure the oasis saline soil in field, employed iterative spectrally smooth temperature/emissivity separation algorithm (ISSTES) to separate temperature and emissivity, and acquired the thermal infrared emissivity data of the saline soil. Through researching the emissivity spectral feature of saline soil, and concluded that soil emissivity will reduce with the increasing of salt content from 8 to 13 microm, so emissivity spectra is more sensitive to salt factor from 8 to 9.5 microm. Then, analyzed the correlation between original emissivity spectra and its first derivative, second derivative and normalized ratio with salt content, the result showed that they have a negative correlation relationship between soil emissivity and salt content, and the correlation between emissivity first derivative and salt content is highest, reach to 0.724 2, the corresponding bands are from 8.370 745-8.390 880 microm. Finally, established the quadratic function regression model, its determination coefficient is 0.741 4, and root mean square error is 0.235 5, the result explained that the approach of using thermal infrared emissivity to retrieve the salt content of saline soil is feasible.

  16. Spectra and structure of gallium compounds. Part IX . Infrared and Raman spectra of trimethylphosphinegallium trichloride and normal coordinate calculations of gallium trichloride and the adduct

    Science.gov (United States)

    Durig, J. R.; Chatterjee, K. K.

    1982-05-01

    The infrared (3200-50 cm -1)and the Raman (3200-30 cm -1) spectra of (CH 3) 3PGaCI 3 have been recorded for the solid state. The spectra are interpreted on the basis of an effective C3v molecular symmetry for the crystalline state and a complete vibrational assignment except for the torsional modes is presented. The frequencies and potential energy distribution for GaCl 3 and those of the adduct have been calculated utilizing a modified valence force field model. A comparison of the calculated potential constants for the adduct with those of the free Lewis acid and base is made and the differences are shown to be consistent with structural changes upon adduct formation and explained in terms of the VSEPR model. Extensive coupling is observed between the GaP stretching mode and the GaCI 3 and the PC 3 stretching and symmetric deformational modes. Various degrees of coupling are also observed between other skeletal modes of vibration, including coupling between the PC 3 and GaCI 3 rocking motions. The value of 2.01 mdyn Å -1 for the GaP stretching force constant is the same as that previously determined for the same constant for (CH 3) 3PGaH 3. Several weak bands, observed in the low frequency region of the infrared and Raman spectra of crystalline (CH 3) 3PGaCl 3, are characterized as lattice modes arising from intermolecular librations. These results are compared to the similar quantities in some corresponding molecules.

  17. Theoretical prediction of S Kβ fine structures in PIXE-induced XRF spectra

    International Nuclear Information System (INIS)

    Uda, M.; Yamamoto, T.; Tatebayashi, T.

    1999-01-01

    Sulfur is one of the most important elements found in air pollutants. A PIXE-induced XRF system equipped with a crystal spectrometer is a candidate to analyze chemical states of S in the pollutants. To aid in the design of the spectrometer for this purpose, fundamental data have been collected by calculating S Kβ spectra by use of the discrete variational Xα (DV-Xα) method for molecular orbital calculations. The calculated spectra have very faithfully reproduced XRF spectra observed for mixtures of Na 2 SO 4 , Na 2 SO 3 and ZnS using a Ge (1 1 1) flat crystal spectrometer, which were used as representative chemical species including SO 4 2- and SO 3 2- , and as an example of sulfides in the air pollutants

  18. Structural and spectroscopic characterization of DMF complexes with nitrogen, carbon dioxide, ammonia and water. Infrared matrix isolation and theoretical studies

    Science.gov (United States)

    Sałdyka, Magdalena; Mielke, Zofia; Haupa, Karolina

    2018-02-01

    An infrared spectroscopic and MP2/6-311++G(2d,2p) study of the complexes between N,N-dimethylformamide (DMF) and nitrogen, carbon dioxide, water, ammonia trapped in solid argon matrices is reported. The 1:1 molecular complexes have been identified in the DMF/B/Ar matrices (B = N2, CO, H2O, NH3); their structures were determined by comparison of the spectra with the results of calculations. The analysis of the experimental and theoretical data indicate that the DMF-N2, CO complexes present in the matrices are stabilized by (C=)O⋯N and (C=)O⋯C van der Waals interactions. In turn, in the DMF-H2O, NH3 complexes the (C=)O⋯H(OH) and (C=)O⋯H(NH2) hydrogen bonding is present in which the carbonyl group of DMF acts as a proton acceptor. In all systems studied the C-H⋯X (X = N, C, O) bonding is a second intermolecular force stabilizing the planar complexes. Some spectral features indicate that for DMF-H2O, DMF-NH3 systems the nonplanar structures with the C=O⋯H interaction are also present. The study demonstrated the strong sensitivity of the CH stretching wavenumber to an involvement of the C-H and/or C=O groups of DMF in an intermolecular interaction.

  19. Experimental and theoretical studies on the characterization of monocrotaline by infrared and Raman spectroscopies

    Science.gov (United States)

    Oliveira, Ramon Prata; Demuner, Antonio Jacinto; Alvarenga, Elson Santiago; Parma, Monica Cropo; Barbosa, Luiz Claudio Almeida; de Moura Guimarães, Luciano; Aguiar, Alex Ramos

    2017-05-01

    The use of plants in folk medicine has a long and ancient history in the treatment of various diseases. Currently, a large proportion of commercial drugs are based on natural products or are synthetic compounds inspired on such natural substances. Therefore, in this communication to aid that research, structural and spectroscopic analysis of the natural pyrrolizidine alkaloid called monocrotaline was carried out. Pyrrolizidine alkaloids that are commonly found in the Boraginaceae and Asteraceae families are among the great diversity of secondary metabolites which are produced by plants to act as a defense mechanism against herbivores and microbes. In the present study, the natural product, monocrotaline, an alkaloid isolated from the leaves of Crotalaria paulina, with potential application in medicine, was characterized by infrared (IR) and Raman spectroscopy with the support of Density Functional Theory (DFT) calculations. IR and Raman spectra of monocrotaline were recorded at room temperature ranging from 4000 to 400 cm-1. DFT calculations with the hybrid functional B3LYP and the basis set 6-31 + G(d,p) were performed with the purpose of obtaining information on the structural and vibrational properties of this structure. A perfect fit between the experimentally measured frequencies of the IR and Raman spectra and the calculated values were observed, and we have performed the complete identification of monocrotaline by these techniques.

  20. An experimental and theoretical study of the valence shell photoelectron spectra of 2-chloropyridine and 3-chloropyridine

    Science.gov (United States)

    Holland, D. M. P.; Powis, I.; Trofimov, A. B.; Menzies, R. C.; Potts, A. W.; Karlsson, L.; Badsyuk, I. L.; Moskovskaya, T. E.; Gromov, E. V.; Schirmer, J.

    2017-10-01

    The valence shell photoelectron spectra of 2-chloropyridine and 3-chloropyridine have been studied both experimentally and theoretically. Synchrotron radiation has been employed to record angle resolved photoelectron spectra in the photon energy range 20-100 eV, and these have enabled anisotropy parameters and branching ratios to be derived. The experimental results have been compared with theoretical predictions obtained using the continuum multiple scattering Xα approach. This comparison shows that the anisotropy parameter associated with the nominally chlorine lone-pair orbital lying in the molecular plane is strongly affected by the atomic Cooper minimum. In contrast, the photoionization dynamics of the second lone-pair orbital, orientated perpendicular to the molecular plane, seem relatively unaffected by this atomic phenomenon. The outer valence ionization has been studied theoretically using the third-order algebraic-diagrammatic construction (ADC(3)) approximation scheme for the one-particle Green's function, the outer valence Green's function method, and the equation-of-motion (EOM) coupled cluster (CC) theory at the level of the EOM-IP-CCSD and EOM-EE-CC3 models. The convergence of the results to the complete basis set limit has been investigated. The ADC(3) method has been employed to compute the complete valence shell ionization spectra of 2-chloropyridine and 3-chloropyridine. The relaxation mechanism for ionization of the nitrogen σ-type lone-pair orbital (σN LP) has been found to be different to that for the corresponding chlorine lone-pair (σCl LP). For the σN LP orbital, π-π* excitations play the main role in the screening of the lone-pair hole. In contrast, excitations localized at the chlorine site involving the chlorine πCl LP lone-pair and the Cl 4p Rydberg orbital are the most important for the σCl LP orbital. The calculated photoelectron spectra have allowed assignments to be proposed for most of the structure observed in the

  1. Near-Infrared Absorption and Scattering Separated by Extended Inverted Signal Correction (EISC): Analysis of Near-Infrared Transmittance Spectra of Single Wheat Seeds

    DEFF Research Database (Denmark)

    Pedersen, Dorthe Kjær; Martens, Harald; Pram Nielsen, Jesper

    2002-01-01

    A new extended method for separating, e.g., scattering from absorbance in spectroscopic measurements, extended inverted signal correction (EISC), is presented and compared to multiplicative signal correction (MSC) and existing modiŽ cations of this. EISC preprocessing is applied to near-infrared...... transmittance (NIT) spectra of single wheat kernels with the aim of improving the multivariate calibration for protein content by partial least-squares regression (PLSR). The primary justiŽ cation of the EISC method is to facilitate removal of spectral artifacts and interferences that are uncorrelated to target...... of the EISC was found to be comparable to a more complex dual-transformation model obtained by Ž rst calculating the second derivative NIT spectra followed by MSC. The calibration model based on EISC preprocessing performed better than models based on the raw data, second derivatives, MSC, and MSC followed...

  2. Investigation of Effect of KBr Matrix on Drift Infrared Spectra of Some ...

    African Journals Online (AJOL)

    Same minerals samples were also run in DRIFT spectroscopy without being dispersed in KBr matrix and their spectra were obtained and analysed. After the investigation it was observed that minerals dispersed in KBr have spectra that are better than those run without KBr in terms of peaks resolution, repeatability and ...

  3. A comparative theoretical study on core-hole excitation spectra of azafullerene and its derivatives

    International Nuclear Information System (INIS)

    Deng, Yunfeng; Gao, Bin; Deng, Mingsen; Luo, Yi

    2014-01-01

    The core-hole excitation spectra—near-edge x-ray absorption spectroscopy (NEXAFS), x-ray emission spectroscopy (XES), and x-ray photoelectron spectroscopy (XPS) shake-up satellites have been simulated at the level of density functional theory for the azafullerene C 59 N and its derivatives (C 59 N) + , C 59 HN, (C 59 N) 2 , and C 59 N–C 60 , in which the XPS shake-up satellites were simulated using our developed equivalent core hole Kohn-Sham (ECH-KS) density functional theory approach [B. Gao, Z. Wu, and Y. Luo, J. Chem. Phys. 128, 234704 (2008)] which aims for the study of XPS shake-up satellites of large-scale molecules. Our calculated spectra are generally in good agreement with available experimental results that validates the use of the ECH-KS method in the present work. The nitrogen K-edge NEXAFS, XES, and XPS shake-up satellites spectra in general can be used as fingerprints to distinguish the azafullerene C 59 N and its different derivatives. Meanwhile, different carbon K-edge spectra could also provide detailed information of (local) electronic structures of different molecules. In particular, a peak (at around 284.5 eV) in the carbon K-edge NEXAFS spectrum of the heterodimer C 59 N–C 60 is confirmed to be related to the electron transfer from the C 59 N part to the C 60 part in this charge-transfer complex

  4. Even-odd alternation of near-infrared spectra of alkane-α,ω-diols in their solid states.

    Science.gov (United States)

    Toyama, Yuta; Murakami, Kohei; Yoshimura, Norio; Takayanagi, Masao

    2018-05-15

    Even-odd alternation of the melting points of α,ω-disubstituted linear alkanes such as alkane-α,ω-diols, alkane-α,ω-dinitriles and α,ω-diaminoalkanes is well known. Melting points for compounds with an even number of carbons in their alkyl chains are systematically higher than those for compounds with an odd number of carbons. In order to clarify the origin of this alternation, near-infrared absorption spectra of linear alkane-α,ω-diols with 3 to 9 carbon atoms in their alkyl chains were measured in the liquid and solid states. The band due to the first overtone of the OH stretching mode was investigated. The temperature-dependent spectra of all alkane-α,ω-diols in their liquid states were found to be similar; no even-odd alternation was observed. In the solid state, however, spectra of alkane-α,ω-diols with even and odd numbers of carbon atoms differed greatly. Spectra of alkane-α,ω-diols with an odd number of carbon atoms in their solid states were similar to those in the liquid states, although the variation of spectra observed upon lowering the temperature of liquid seemed to continue when the liquids were frozen. In contrast, spectra of alkane-α,ω-diols with an even number of carbon atoms in their liquid and solid states were found to be quite different. New bands appeared upon freezing. The observed even-odd alternation of the spectra observed for alkane-α,ω-diols in their solid states is presumably caused by their even-odd alternation of crystal structures. Copyright © 2018 Elsevier B.V. All rights reserved.

  5. Effect of wavelet denoising techniques on the determination of navel orange sugar content with near-infrared spectra

    Science.gov (United States)

    Xie, Lijuan; Huang, Haibo; Ying, Yibin; Lu, Huishan; Fu, Xiaping

    2006-10-01

    Near infrared (NIR) spectroscopy is an ideal analytical method for rapid and nondestrctive measurement of the properties of agriculture products. The efficient use of this method is dependent on multivariate calibration methods determined by the sensitivity to variations. However, fluctuation of background and noise are unavoidable during collecting spectra, which will not only worsen the precision of prediction, but also complicate the multivariate models. Therefore, the first step of a multivariate calibration based on NIR spectra data is often to preprocess the data for the purpose of removing the varying background and noise. In this study, wavelet transform (WT) was used to eliminate the varying background and noise simultaneously in the near infrared spectroscopy signals of 55 navel oranges. Three families of mother wavelets (Symlets, Daubechies and Coiflet), four threshold selection rules (Rigrsure, Heursure, Minimaxi, Fixed form threshold), and two threshold functions (soft and hard) were applied to estimate the performances. The sugar content of intact navel orange was calculated by partial least squares regression (PLSR) with the reconstructed spectra after denoised. The results show that the best denoising performance was reached via the combination of Daubechies 5, "Fixed form" threshold selection rule, and hard threshold function. Based on the optimization parameter, wavelet regression models on sugar content in navel orange were also developed and resulted in a smaller prediction error than a traditional PLSR model.

  6. Noninvasive measurement of blood glucose concentrations by analysing Fourier transform infra-red absorbance spectra through oral mucosa.

    Science.gov (United States)

    Kajiwara, K; Uemura, T; Kishikawa, H; Nishida, K; Hashiguchi, Y; Uehara, M; Sakakida, M; Ichinose, K; Shichiri, M

    1993-07-01

    Whether Fourier transform infra-red spectroscopy with an attenuated total reflection prism could be applied for noninvasive glucose measurement through oral mucosa was evaluated. As a result, the same absorbance peak at 1033 cm-1 as in glucose aqueous solution was found in the absorbance spectra through mucous membrane. However, these glucose specific peaks were interfered with by the baseline drifts owing to prism attachment and the background spectra from body constituents other than glucose. Therefore, to eliminate these interferences, the calibration curve between the second derivatives of the absorbance peak at 1033 cm-1 and those at 2920 cm-1 was calculated (r = 0.910). By using this calibration curve, the spectral changes due to prism attachment were first eliminated. Secondly, by obtaining the second derivative of the difference between the postprandial absorbance peak and the fasting sample as a characteristic of an individual, high correlations between the corrected second derivatives of absorbance spectra through the mucous membrane of the lip at 1033 cm-1 and the increases in blood glucose concentrations above fasting levels were observed (r = 0.910). In conclusion, it was suggested that Fourier transform infra-red spectroscopy could be useful for noninvasive monitoring of glucose through oral mucosa.

  7. Electronic spectra of conjugated polyynes, cumulenes and related systems: A theoretical study

    Czech Academy of Sciences Publication Activity Database

    Zahradník, Rudolf; Srnec, Martin; Havlas, Zdeněk

    2005-01-01

    Roč. 70, - (2005), s. 559-578 ISSN 0010-0765 R&D Projects: GA MŠk LC512 Institutional research plan: CEZ:AV0Z40400503 Keywords : quantum chemical calculations * ab initio calculations * DFT * SAC -CI Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.949, year: 2005

  8. An interpretation of the absorption and emission spectra of the gold dimer using modern theoretical tools

    DEFF Research Database (Denmark)

    Geethalakshmi, K. R.; Ruiperez, F.; Knecht, S.

    2012-01-01

    The excited states of the gold dimer have been investigated using modern theoretical tools including the multiconfigurational exact molecular mean-field intermediate Hamiltonian Fock-space Coupled Cluster, X2Cmmf-IHFSCC, and the complete active space self-consistent field followed by second order...

  9. An interpretation of the absorption and emission spectra of the gold dimer using modern theoretical tools

    NARCIS (Netherlands)

    Geethalakshmi, K R; Ruipérez, Fernando; Knecht, Stefan; Ugalde, Jesus M.; Morse, Michael D.; Infante, Ivan

    2012-01-01

    The excited states of the gold dimer have been investigated using modern theoretical tools including the multiconfigurational exact molecular mean-field intermediate Hamiltonian Fock-space Coupled Cluster, X2Cmmf-IHFSCC, and the complete active space self-consistent field followed by second order

  10. Accurate Theoretical Methane Line Lists in the Infrared up to 3000 K and Quasi-continuum Absorption/Emission Modeling for Astrophysical Applications

    Science.gov (United States)

    Rey, Michael; Nikitin, Andrei V.; Tyuterev, Vladimir G.

    2017-10-01

    Modeling atmospheres of hot exoplanets and brown dwarfs requires high-T databases that include methane as the major hydrocarbon. We report a complete theoretical line list of 12CH4 in the infrared range 0-13,400 cm-1 up to T max = 3000 K computed via a full quantum-mechanical method from ab initio potential energy and dipole moment surfaces. Over 150 billion transitions were generated with the lower rovibrational energy cutoff 33,000 cm-1 and intensity cutoff down to 10-33 cm/molecule to ensure convergent opacity predictions. Empirical corrections for 3.7 million of the strongest transitions permitted line position accuracies of 0.001-0.01 cm-1. Full data are partitioned into two sets. “Light lists” contain strong and medium transitions necessary for an accurate description of sharp features in absorption/emission spectra. For a fast and efficient modeling of quasi-continuum cross sections, billions of tiny lines are compressed in “super-line” libraries according to Rey et al. These combined data will be freely accessible via the TheoReTS information system (http://theorets.univ-reims.fr, http://theorets.tsu.ru), which provides a user-friendly interface for simulations of absorption coefficients, cross-sectional transmittance, and radiance. Comparisons with cold, room, and high-T experimental data show that the data reported here represent the first global theoretical methane lists suitable for high-resolution astrophysical applications.

  11. A theoretical study on the vibrational spectra and thermodynamic properties for the nitro derivatives of phenols.

    Science.gov (United States)

    Wang, Gui-xiang; Gong, Xue-dong; Liu, Yan; Xiao, He-ming

    2009-10-01

    The nitro derivatives of phenols are optimized to obtain their molecular geometries and electronic structures at the DFT-B3LYP/6-31 G* level. Their IR spectra are obtained and assigned by vibrational analysis and are reliable compared with the experimental results. Based on the frequencies scaled by 0.96 and the principle of statistic thermodynamics, the thermodynamic properties are evaluated, which are linearly related with the number of nitro and hydroxy groups as well as the temperature, obviously showing good group additivity.

  12. Infrared, Raman and ultraviolet with circular dichroism analysis and theoretical calculations of tedizolid

    Science.gov (United States)

    Michalska, Katarzyna; Mizera, Mikołaj; Lewandowska, Kornelia; Cielecka-Piontek, Judyta

    2016-07-01

    Tedizolid is the newest antibacterial agent from the oxazolidinone class. For its identification, FT-IR (2000-400 cm-1) and Raman (2000-400 cm-1) analyses were proposed. Studies of the enantiomeric purity of tedizolid were conducted based on ultraviolet-circular dichroism (UV-CD) analysis. Density functional theory (DFT) with the B3LYP hybrid functional and 6-311G(2df,2pd) basis set was used for support of the analysis of the FT-IR and Raman spectra. Theoretical methods made it possible to conduct HOMO and LUMO analysis, which was used to determine the charge transfer for two tedizolid enantiomers. Molecular electrostatic potential maps were calculated with the DFT method for both tedizolid enantiomers. The relationship between the results of ab initio calculations and knowledge about the chemical-biological properties of R- and S-tedizolid enantiomers is also discussed.

  13. Energy Diagnoses of Nine Infrared Luminous Galaxies Based on 3-4 Micron Spectra

    National Research Council Canada - National Science Library

    Imanishi, Masatoshi; Dudley, C. C

    2000-01-01

    .... Assuming that nuclear compact starburst activity in these sources produces the 3.3 micron PAH emission as strongly as that in starburst galaxies with lower far-infrared luminosities, the following results are found...

  14. Algebraic approach to molecular rotation--vibration spectra. III. Infrared intensities

    Energy Technology Data Exchange (ETDEWEB)

    Iachello, F. (Center for Theoretical Physics, Yale University, New Haven, Connecticut 06511 (US)); Leviatan, A. (Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (US)); Mengoni, A. (Ente Nazionale Energie Alternative, 40100, Bologna, (Italy))

    1991-08-01

    We suggest a form of the dipole operator to be used in the analysis of intensities of infrared transitions within the framework of the vibron model. We give the corresponding matrix elements in explicit form and discuss their qualitative features.

  15. Algebraic approach to molecular rotation--vibration spectra. III. Infrared intensities

    International Nuclear Information System (INIS)

    Iachello, F.; Leviatan, A.; Mengoni, A.

    1991-01-01

    We suggest a form of the dipole operator to be used in the analysis of intensities of infrared transitions within the framework of the vibron model. We give the corresponding matrix elements in explicit form and discuss their qualitative features

  16. Visible and Near-Infrared Leaf Reflectance Spectra, 1992-1993 (ACCP)

    Data.gov (United States)

    National Aeronautics and Space Administration — Visible/NIR reflectance spectra data for both fresh and dry leaf samples were collected to determine the relationship of foliar chemical concentrations with...

  17. Laser Raman and infra-red spectra of biomolecule: 5-aminouracil

    Indian Academy of Sciences (India)

    1–4] on substituted biomolecules. These molecules do not occur freely in natural bi- ological metabolism. The understanding of the vibrational spectra of free molecules might be helpful in understanding specific biological processes and in the ...

  18. Theoretical investigations on vibrational spectra of pillar[5]arene-bis(pyridinium) complexes

    Science.gov (United States)

    Peerannawar, Swarada R.; Gejji, Shridhar P.

    2013-03-01

    Electronic structure and vibrational spectra of pillar[5]arene (P5) complexes with bis(pyridinium) derivatives viz., 1,2-ethylenedipyridine (edpy), 1,2-propylenedipyridine (3-pdpy), 1,2-butylenedipyridine (bdpy), 1,2-pentamethylenedipyridine (pdpy) and 1,2-hexamethylenedipyridine (hdpy) are investigated employing density functional theory. B3LYP based density functional calculations predicted that interaction energies for complexation decreases steadily with increasing alkyl chain of bis(pyridinium) guest. The calculations have shown that Osbnd H⋯O hydrogen bonded and non-bonded hydroxyls in the host led to distinct vibrations at the 3515 cm-1 and 3681 cm-1, respectively in the vibrational spectra. Complexation of bis(pyridinium) guest engenders frequency down-shift for aromatic Csbnd Hα vibrations owing to Csbnd H⋯O interactions with P5 portals. Moreover, Csbnd H⋯π interactions are inferred in edpy@P5 and 3-pdpy@P5 complexes which results in frequency up-shift (blue shift) of nearly 22-15 cm-1 for the corresponding Csbnd Hα vibration.

  19. Synthesis and purification of some alkyl phenanthrenes and presentation of their infrared, ultraviolet, nuclear magnetic resonance and mass spectra

    International Nuclear Information System (INIS)

    Persaud, K.

    1965-01-01

    We have carried out the synthesis of: - phenanthrene - its five monomethyl derivatives - three dimethyl derivatives - two trimethyl derivatives. We have then purified these products as well as a certain number of others obtained from various sources. We have been able to obtain in the majority of cases, a purity of 99.5 per cent or over, these figures being obtained by low voltage mass spectrometry. Finally we have recorded the infrared, ultraviolet, nuclear magnetic resonance and mass spectra of these products for which an atlas has been drawn up. (author) [fr

  20. Infrared reflection spectra of multilayer epitaxial heterostructures with embedded InAs and GaAs layers

    International Nuclear Information System (INIS)

    Seredin, P. V.; Domashevskaya, E. P.; Lukin, A. N.; Arsent'ev, I. N.; Vinokurov, D. A.; Tarasov, I. S.

    2008-01-01

    The effect of the thickness of embedded InAs and GaAs layers on the infrared reflection spectra of lattice vibrations for AlInAs/InAs/AlInAs, InGaAs/GaAs/InGaAs, and AlInAs/InGaAs/GaAs/InGaAs/AlInAs multilayer epitaxial heterostructures grown by MOC hydride epitaxy on InP (100) substrates is studied. Relative stresses emerging in the layers surrounding the embedded layers with variation in the number of monolayers from which the quantum dots are formed and with variation the thickness of the layers themselves surrounding the embedded layers are evaluated.

  1. Correlations between near-infrared spectra of wet-stored timber and storage time in relation to the water quality

    International Nuclear Information System (INIS)

    Borga, P.; Hämäläinen, M.; Theander, O.

    1992-01-01

    Near-infrared spectroscopy (NIR) and multivariate calibration using partial least squares regression (PLSR), were used to study the correlation between the storage time of wet-stored timber and NIR spectra of wood, as well as to distinguish between different wood zones (sapwood and heartwood). The wood zones were well distinguishable by NIR in logs of Scots pine (Pinus sylvestris). When wet-stored using recirculating water, between 70 and 92% of the variance was explained, whereas after wet-storage using tap water, less than 50% of the variance in the storage time was explained

  2. Infrared spectra of complex organic molecules in astronomically relevant ice matrices. I. Acetaldehyde, ethanol, and dimethyl ether

    Science.gov (United States)

    Terwisscha van Scheltinga, J.; Ligterink, N. F. W.; Boogert, A. C. A.; van Dishoeck, E. F.; Linnartz, H.

    2018-03-01

    Context. The number of identified complex organic molecules (COMs) in inter- and circumstellar gas-phase environments is steadily increasing. Recent laboratory studies show that many such species form on icy dust grains. At present only smaller molecular species have been directly identified in space in the solid state. Accurate spectroscopic laboratory data of frozen COMs, embedded in ice matrices containing ingredients related to their formation scheme, are still largely lacking. Aim. This work provides infrared reference spectra of acetaldehyde (CH3CHO), ethanol (CH3CH2OH), and dimethyl ether (CH3OCH3) recorded in a variety of ice environments and for astronomically relevant temperatures, as needed to guide or interpret astronomical observations, specifically for upcoming James Webb Space Telescope observations. Methods: Fourier transform transmission spectroscopy (500-4000 cm-1/20-2.5 μm, 1.0 cm-1 resolution) was used to investigate solid acetaldehyde, ethanol and dimethyl ether, pure or mixed with water, CO, methanol, or CO:methanol. These species were deposited on a cryogenically cooled infrared transmissive window at 15 K. A heating ramp was applied, during which IR spectra were recorded until all ice constituents were thermally desorbed. Results: We present a large number of reference spectra that can be compared with astronomical data. Accurate band positions and band widths are provided for the studied ice mixtures and temperatures. Special efforts have been put into those bands of each molecule that are best suited for identification. For acetaldehyde the 7.427 and 5.803 μm bands are recommended, for ethanol the 11.36 and 7.240 μm bands are good candidates, and for dimethyl ether bands at 9.141 and 8.011 μm can be used. All spectra are publicly available in the Leiden Database for Ice.

  3. Evaluation of infrared spectra analyses using a likelihood ratio approach: A practical example of spray paint examination.

    Science.gov (United States)

    Muehlethaler, Cyril; Massonnet, Geneviève; Hicks, Tacha

    2016-03-01

    Depending on the forensic disciplines and on the analytical techniques used, Bayesian methods of evaluation have been applied both as a two-step approach (first comparison, then evaluation) and as a continuous approach (comparison and evaluation in one step). However in order to use the continuous approach, the measurements have to be reliably summarized as a numerical value linked to the property of interest, which occurrence can be determined (e.g., refractive index measurement of glass samples). For paint traces analyzed by Fourier transform infrared spectroscopy (FTIR) however, the statistical comparison of the spectra is generally done by a similarity measure (e.g., Pearson correlation, Euclidean distance). Although useful, these measures cannot be directly associated to frequencies of occurrence of the chemical composition (binders, extenders, pigments). The continuous approach as described above is not possible, and a two-step evaluation, 1) comparison of the spectra and 2) evaluation of the results, is therefore the common practice reported in most of the laboratories. Derived from a practical question that arose during casework, a way of integrating the similarity measure between spectra into a continuous likelihood ratio formula was explored. This article proposes the use of a likelihood ratio approach with the similarity measure of infrared spectra of spray paints based on distributions of sub-populations given by the color and composition of spray paint cans. Taking into account not only the rarity of paint composition, but also the "quality" of the analytical match provides a more balanced evaluation given source or activity level propositions. We will demonstrate also that a joint statistical-expertal methodology allows for a more transparent evaluation of the results and makes a better use of current knowledge. Copyright © 2015 The Chartered Society of Forensic Sciences. Published by Elsevier Ireland Ltd. All rights reserved.

  4. Ab-initio modeling of an iron laser-induced plasma: Comparison between theoretical and experimental atomic emission spectra

    International Nuclear Information System (INIS)

    Colgan, J.; Judge, E.J.; Kilcrease, D.P.; Barefield, J.E.

    2014-01-01

    We report on efforts to model the Fe emission spectrum generated from laser-induced breakdown spectroscopy (LIBS) measurements on samples of pure iron oxide (Fe 2 O 3 ). Our modeling efforts consist of several components. We begin with ab-initio atomic structure calculations performed by solving the Hartree–Fock equations for the neutral and singly ionized stages of Fe. Our energy levels are then adjusted to their experimentally known values. The atomic transition probabilities and atomic collision quantities are also computed in an ab-initio manner. We perform LTE or non-LTE calculations that generate level populations and, subsequently, an emission spectrum for the iron plasma for a range of electron temperatures and electron densities. Such calculations are then compared to the experimental spectrum. We regard our work as a preliminary modeling effort that ultimately strives towards the modeling of emission spectra from even more complex samples where less atomic data are available. - Highlights: • LIBS plasma of iron oxide • Ab-initio theoretical Modeling • Discussion of LTE versus non-LTE criteria and assessment • Boltzmann plots for Fe—determination of when LTE is a valid assumption • Emission spectra for Fe—comparison of theoretical modeling and measurement: good agreement obtained

  5. Visible Photodissociation Spectra of the 1-METHYL and 2-METHYLNAPHTHALENE Cations: Laser Spectroscopy and Theoretical Simulations

    Science.gov (United States)

    Friha, Hela; Feraud, Geraldine; Falvo, Cyril; Parneix, Pascal; Pino, Thomas; Brechignac, Philippe; Troy, Tyler; Schmidt, Timothy; Dhaouadi, Zoubeida

    2014-06-01

    Naphthalene (Np) and its methylated derivatives (1-Me-Np and 2-Me-Np) are prototype molecules for spectroscopists as first members of the polycyclic aromatic hydrocarbons (PAHs) family. High resolution studies are capable to explore the details of the internal rotation of the methyl group. Although this was achieved in neutral PAHs, the task is not the same in cations. Me-Np cations have been probed by resonance-enhanced multiphoton dissociation, showing only very broad and unresolved spectra, while absorption in argon matrix revealed more resolved vibronic bands. The electronic absorption gas phase spectra of 1-Me-Np^+ and 2-Me-Np^+ were measured using an Ar-tagging technique. In both cases, a band system was observed in the visible range and assigned to the D_2← D_0 transition. The 1-Me-Np^+ absorption bands revealed a red shift of 808 cm-1, relative to Np^+ (14 906 cm-1), while for 2-Me-Np^+ a blue shift of 226 cm-1 was found. A short vibrational progression was also observed. Moreover, insights into the internal rotation motion of the CH_3 were inferred, although intrinsic broadening due to intramolecular relaxation was present. These measurements were supported by detailed quantum chemical calculations that allowed exploration of the potential energy curves, along with a complete simulation of the harmonic FC factors using the cumulant Gaussian fluctuations formalism, extended to include the internal rotation. see for instance Baba et al, J.Phys.Chem.A, 2009, 113, 2366 Dunbar et al, J. Am. Chem. Soc. 1976, 98, 7994-7999; J.Phys.Chem. 1985, 89, 3617 Andrews et al, J.Phys.Chem. 1982, 86, 2916 Pino et al, J. Chem. Phys. 1999, 111, 7337-7347

  6. Theoretical photoionization spectra in the UV photon energy range for a Mg-like Al+ ion

    International Nuclear Information System (INIS)

    Kim, Dae-Soung; Kim, Young Soon

    2008-01-01

    In the present work, we report the photoionization cross sections of the Al + ion calculated for the photon energy range 20-26 eV and 30-50 eV. We have expanded our previous calculation (2007 J. Phys. Soc. Japan 76 014302) with an optimized admixture of the initial ground state 3s 21 S and exited states 3s3p 1,3 P, 3s3d 1,3 D and 3s4s 1,3 S, and obtained significantly improved predictions for the main background and autoionizing resonance structures of the reported experimental spectra. The absolute measurements of the photoionization cross sections of the Al + ion in these energy ranges have been performed by West et al (2001 Phys. Rev. A 63 052719), and they reported that the prominent peaks around 21 eV were attributed to the effects of the significant influence of the small fraction of the fourth-order radiation with energies around 84 eV from the synchrotron source. In our previous work, the main shape for these cross sections was calculated assuming an admixture of initial 3s 21 S and 3s3p 3 P states, only with a rough overall estimate for the experimental spectra in the photon energy range 20-26 eV, and without these peaks around 21 eV. The report of the experimental assignment attributes these peaks to the excitation of a 2p electron from the core. However, our present results with the new admixture reveal similar peaks without considering the possibility of the core excitation

  7. Proton location in (CH3)3N-H+-(CH3OH)n: A theoretical and infrared spectroscopic study

    International Nuclear Information System (INIS)

    Bing, Dan; Hamashima, Toru; Tsai, Chen-Wei; Fujii, Asuka; Kuo, Jer-Lai

    2013-01-01

    Highlights: • Preferential location of the excess proton in the trimethylamine-methanol clusters. • Collaboration between DFT calculations and IR spectroscopy. • The excess proton prefers the protonation to the trimethylamine moiety. - Abstract: The dependence of the preferential protonated site in (CH 3 ) 3 N-H + -(CH 3 OH) n on the cluster size was investigated using theoretical calculations and infrared spectroscopy measurements. While simple estimation from the magnitude of proton affinity suggested that the excess proton prefers the methanol site in n ⩾ 4, density functional theory calculations of the stabilization energy indicated the clear preference as protonation of the trimethylamine site, even for n = 9. Infrared spectra of the clusters were observed for n = 3–7. Spectral simulations were also performed using the quantum harmonic superposition approximation. The observed (CH 3 ) 3 N-H + -(CH 3 OH) n spectra were well interpreted by simulations of the isomers with the protonated trimethylamine ion core. It was shown that both the proton affinity and the mutual solvation energy govern the preferential location of the excess proton in binary component clusters

  8. The effects of atmospheric pressure on infrared reflectance spectra of Martian analogs

    Science.gov (United States)

    Bishop, Janice L.; Pieters, Carle M.; Pratt, Stephen F.; Patterson, William

    1993-01-01

    The use of terrestrial samples as analogs of Mars soils are complicated by the Martian atmosphere. Spectral features due to the Martian atmosphere can be removed from telescopic spectra of Mars and ISM spectra of Mars, but this does not account for any spectral differences resulting from atmospheric pressure or any interactions between the atmosphere and the surface. We are examining the effects of atmospheric pressure on reflectance spectra of powdered samples in the laboratory. Contrary to a previous experiment with granite, no significant changes in albedo or the Christiansen feature were observed from 1 bar pressure down to a pressure of 8 micrometers Hg. However, reducing the atmospheric pressure does have a pronounced affect on the hydration features, even for samples retained in a dry environment for years.

  9. Overtone spectra of 1,2-dichloro- and dibromo-ethanes in the near infrared region

    Science.gov (United States)

    Abdul Rasheed, T. M.; Nampoori, V. P. N.; Sathianandan, K.

    1986-10-01

    The vibrational overtone spectra of the liquid phase 1,2-dichloroethane and 1,2-dibromoethane in the spectral regions of the CH stretching local mode overtones corresponding to Δυ CH = 2 to Δυ CH = 5 are reported. The observed spectral features are assigned using the local mode model. Local mode frequencies ω CH and diagonal local model anharmonicities XCH are obtained from an analysis of the spectra. The local-local combinations observed are interpreted on the basis of a coupled CH oscillator model hamiltonian. Local-normal combinations show complex structures and their possible assignments are given.

  10. Comparison of optical and electron spectra in an infra-red free electron laser

    Energy Technology Data Exchange (ETDEWEB)

    MacLeod, A.M.; Gillespie, W.A.; Martin, P.F. [Univ. of Abertay, Dundee (United Kingdom)] [and others

    1995-12-31

    Time-resolved electron and optical spectra recently acquired at the FELIX facility are presented, showing the evolution of the respective macropulses. A comparison is made between the optical power output during the macropulse and the measured power extracted from the electron beam using a simple model of the cavity losses. Data are available for a wide range of operating conditions: the wavelength range is from 9 {mu}m to 28 {mu}m and detuning are between 1/4{lambda} and 2{lambda}. The effect of rapid electron beam energy changes on the optical and electron spectra will also be discussed.

  11. Theoretical investigation of the energy spectra of the oxygen isoelectronic sequences taking into account relativistic corrections

    International Nuclear Information System (INIS)

    Bogdanovich, P.O.; Shadzhyuvene, S.D.; Boruta, I.I.; Rudzikas, Z.B.

    1976-01-01

    A method for calculating energy spectra of atoms and ions having complex electron configurations is developed which takes into account relativistic corrections of the order of magnitude of the square of the structure constant. The corrections included are caused by the dependence of the electron mass on velocity; by orbit-orbit interaction; by contact interaction and by spin-orbit interaction. The method described is realized in the form of universal algorithms and programs which are written in the Fortran 4 in the BESM-6 version. Examples are given of calculating the ground ls 2 2s 2 2p 6 configuration and two excited ls 2 2s 2 2p 3 3s and ls 2 2s2p 5 ones of the isoelectronic oxygen series, both with and without taking into account the relativistic corrections. The value of the nuclear charge varies from Z=8 to Z=80. The contribution of relativistic corrections increases with Z. The effect of relativistic corrections on the distance between the centers of gravity of ground and excited configurations increases with Z. The comparison of the results obtained with experimental data is made

  12. Visible photodissociation spectra of the 1- and 2-methylnaphthalene cations: laser spectroscopy and theoretical simulations.

    Science.gov (United States)

    Friha, Hela; Féraud, Géraldine; Troy, Tyler; Falvo, Cyril; Parneix, Pascal; Bréchignac, Philippe; Dhaouadi, Zoubeida; Schmidt, Timothy W; Pino, Thomas

    2013-12-19

    The electronic absorption spectra of the two methyl derivatives of the naphthalene cation were measured using an argon tagging technique. In both cases, a band system was observed in the visible range and assigned to the D2 ← D0 electronic transition. The 1-methylnaphthalene(+) absorption bands revealed a red shift of 808 cm(-1), relative to those of the naphthalene cation (14,906 cm(-1)), whereas for 2-methylnaphthalene(+) a blue shift of 226 cm(-1) appeared. A short vibrational progression, similar to the naphthalene cation, was also observed for both isomers and found to involve similar aromatic ring skeleton vibrations. Moreover, insights into the internal rotation motion of the methyl group were inferred, although the spectral resolution was not sufficient to fully resolve the substructure. These measurements were supported by detailed quantum chemical calculations. They allowed exploration of the potential energy curves along this internal coordinate, along with a complete simulation of the harmonic Franck-Condon factors using the cumulant Gaussian fluctuations formalism extended to include the internal rotation.

  13. Theoretical study of molecular structures, vibrational and NMR spectra on azobenzene derivatives

    Science.gov (United States)

    Karakaya, M.; Ucun, F.

    2014-02-01

    In this study, we have calculated the most stable tautomeric forms and their ground state conformers of 2,4-dihydroxyazobenzene and 2,4-dihydroxy-6-methyl-4'-nitroazobenzene molecules. Calculations show that the most preferential tautomeric forms of these molecules are azo form for 2,4-dihydroxyazobenzene and hydrazo form for 2,4-dihydroxy-6-methyl-4'-nitroazobenzene. Vibrational frequencies, 1H and 13C NMR shifts of ground state conformers of stable tautomeric forms of the molecules have been calculated by using density functional theory-B3LYP method with 6-311G(d,p) basis set. All assignments of theoretical frequencies have been performed by potential energy distribution analysis. Calculated spectral results are in a good agreement with the corresponding experimental data.

  14. The Infrared Spectra of Diaqua Tetra-m - Formato Dichromium (II): A ...

    African Journals Online (AJOL)

    The infrared spectrum of diaqua tetra- m - formato dichromium (II) complex has been obtained in the frequency range 4000 to 400cm-1. A normal coordinate treatment performed on the 1:1 model of the complex gives calculated frequencies in good agreement with the observed ones. In order to assign bands and to see the ...

  15. Raman spectra of normal and cancerous mouse mammary gland tissue using near infrared excitation energy

    Science.gov (United States)

    Naik, Vaman; Serhatkulu, G. K.; Dai, H.; Shukla, N.; Weber, R.; Thakur, J. S.; Freeman, D. C.; Pandya, A. K.; Auner, G. W.; Naik, R.; Miller, R. F.; Cao, A.; Klein, M. D.; Rabah, R.

    2006-03-01

    Raman spectra of normal mammary gland tissues, malignant mammary gland tumors, and lymph nodes have been recorded using fresh tissue from mice. Tumors were induced in mice by subcutaneously injecting 4T1 BALB/c mammary tumor (a highly malignant) cell line. The Raman spectra were collected using the same tissues that were examined by histopathology for determining the cancerous/normal state of the tissue. Differences in various peak intensities, peak shifts and peak ratios were analyzed to determine the Raman spectral features that differentiate mammary gland tumors from non-tumorous tissue. Tissues that were confirmed by pathology as cancerous (tumors) show several distinctive features in the Raman spectra compared to the spectra of the normal tissues. For example, the cancerous tissues show Raman peaks at 621, 642, 1004, 1032, 1175 and 1208 cm-1 that are assignable to amino acids containing aromatic side-chains such as phenylalanine, tryptophan and tyrosine. Further, the cancerous tissues show a greatly reduced level of phospholipids compared to the normal tissues. The Raman spectral regions that are sensitive to pathologic alteration in the tissue will be discussed.

  16. Infrared and Raman Spectra of and Isotopomers: A DFT-PT2 Anharmonic Study

    Directory of Open Access Journals (Sweden)

    Andrea Alparone

    2013-01-01

    Full Text Available IR and Raman spectra of selenophene and of its perdeuterated isotopomer have been obtained in gas phase through density-functional theory (DFT computations. Vibrational wavenumbers have been calculated using harmonic and anharmonic second-order perturbation theory (PT2 procedures with the B3LYP method and the 6-311 basis set. Anharmonic overtones have been determined by means of the PT2 method. The introduction of anharmonic terms decreases the harmonic wavenumbers, giving a significantly better agreement with the experimental data. The most significant anharmonic effects occur for the C–H and C–D stretching modes, the observed H/D isotopic wavenumber redshifts being satisfactorily reproduced by the PT2 computations within 6–20 cm−1 (1–3%. In the spectral region between 500 cm−1 and 1500 cm−1, the IR spectra are dominated by the out-of-plane C–H (C–D bending transition, whereas the Raman spectra are mainly characterized by a strong peak mainly attributed to the C=C + C–C bonds stretching vibration with the contribution of the in-plane C–H (C–D bending deformation. The current results confirm that the PT2 approach combined with the B3LYP/6-311 level of calculation is a satisfactory choice for predicting vibrational spectra of cyclic molecules.

  17. Far-infrared spectra of yttrium-doped gold clusters Au(n)Y (n=1-9).

    Science.gov (United States)

    Lin, Ling; Claes, Pieterjan; Gruene, Philipp; Meijer, Gerard; Fielicke, André; Nguyen, Minh Tho; Lievens, Peter

    2010-06-21

    The geometric, spectroscopic, and electronic properties of neutral yttrium-doped gold clusters Au(n)Y (n=1-9) are studied by far-infrared multiple photon dissociation (FIR-MPD) spectroscopy and quantum chemical calculations. Comparison of the observed and calculated vibrational spectra allows the structures of the isomers present in the molecular beam to be determined. Most of the isomers for which the IR spectra agree best with experiment are calculated to be the energetically most stable ones. Attachment of xenon to the Au(n)Y cluster can cause changes in the IR spectra, which involve band shifts and band splittings. In some cases symmetry changes, as a result of the attachment of xenon atoms, were also observed. All the Au(n)Y clusters considered prefer a low spin state. In contrast to pure gold clusters, which exhibit exclusively planar lowest-energy structures for small sizes, several of the studied species are three-dimensional. This is particularly the case for Au(4)Y and Au(9)Y, while for some other sizes (n=5, 8) the 3D structures have an energy similar to that of their 2D counterparts. Several of the lowest-energy structures are quasi-2D, that is, slightly distorted from planar shapes. For all the studied species the Y atom prefers high coordination, which is different from other metal dopants in gold clusters.

  18. Near-surface thermal gradients and their effects on mid-infrared emission spectra of planetary surfaces

    Science.gov (United States)

    Henderson, B. G.; Jakosky, B. M.

    1994-01-01

    We model the heat transfer by radiation and conduction in the top few millimeters of a planetary surface to determine the magnitude of near-surface (approximately 100 micrometers) thermal gradients and their effects on mid-infrared emission spectra for a number of planetary environments. The model is one-dimensional and uses a finite difference scheme for approximately 10 micrometers layers. Calculations are peformed for samples heated at the base and from above by sunlight. Our results indicate that near-surface radiative cooling creates significant thermal gradients in the top few hundred microns of surfaces in which radiation is an importamnt heat transfer mechanism. The effect is maximized in evacuated, underdense particulate media with sufficiently high temperatures. Near-surface thermal gradients will be significant in fine-grained particulate surfaces on the Moon (40-60 K/100 micrometers) and Mercury (approximately 80 K/100 micrometers), increasing spectral contrast and creating emission maxima in the transparent regions of the spectra. They will be of lesser importance on the surface of Mars, with a maximum value of around 5 k/100 micrometers in areas of low thermal inertia, and will be negligible on planets with more substantial atmospheres (less than 1 K/100 micrometers). We conclude that the effects that thermal gradients have on mid-IR emission spectra are predictable and do not negate the utility of emission spectroscopy for remote determination of planetary surface composition.

  19. Determination of the predominant minerals in sedimentary rocks by chemometric analysis of infrared spectra

    Czech Academy of Sciences Publication Activity Database

    Ritz, M.; Vaculíková, Lenka; Plevová, Eva; Matýsek, D.; Mališ, J.

    2012-01-01

    Roč. 60, č. 6 (2012), s. 655-665 ISSN 0009-8604 R&D Projects: GA MŠk ED2.1.00/03.0082 Grant - others:GA MŠk(CZ) ED0040/01/01 Institutional support: RVO:68145535 Keywords : infrared spectroscopy * chemometrics * minerals Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.114, year: 2012 http://ccm.geoscienceworld.org/content/60/6/655.full.pdf+html

  20. The infrared optical absorption spectra of the functionalized nanocrystalline diamond surface

    Czech Academy of Sciences Publication Activity Database

    Remeš, Zdeněk; Kromka, Alexander; Kozak, Halyna; Vaněček, Milan; Haenen, K.; Wenmackers, S.

    2009-01-01

    Roč. 18, 5-8 (2009), s. 772-775 ISSN 0925-9635 R&D Projects: GA MŠk LC510; GA AV ČR KJB100100623 Institutional research plan: CEZ:AV0Z10100521 Keywords : nanocrystalline diamond * photochemical functionalization * spin coating * polymer * infrared spectroscopy * fluorescence microscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.822, year: 2009

  1. Calibration model transfer for near-infrared spectra based on canonical correlation analysis.

    Science.gov (United States)

    Fan, Wei; Liang, Yizeng; Yuan, Dalin; Wang, Jiajun

    2008-08-08

    In order to solve the calibration transformation problem in near-infrared (NIR) spectroscopy, a method based on canonical correlation analysis (CCA) for calibration model transfer is developed in this work. Two real NIR data sets were tested. A comparative study between the proposed method and piecewise direct standardization (PDS) was conducted. It is shown that the transfer results obtained with the proposed method based on CCA were better than those obtained by PDS when the subset had sufficient samples.

  2. Matrix-isolation infrared spectra of 2-, 3- and 4-pyridinecarboxaldehyde before and after UV irradiation

    OpenAIRE

    Ohno, Keiichi; Itoh, Takao; Yokota, Chiyumi; Katsumoto, Yukiteru

    2006-01-01

    Three structural isomers of pyridinecarboxaldehydes (2-, 3- and 4-pyridinecarboxaldehyde) have been investigated in detail with matrix-isolation infrared spectroscopy in the 3000.600 cm.1 region, combined with the UV photoexcitation and the density-functional theory (DFT) calculations. Two rotamers (anti and syn) were identified for 2- and 3-pyridinecarboxaldehyde (2- and 3-PCA, respectively) upon the photoexcitation and most of the observed bands of each rotamer have been assigned. Both of t...

  3. Theoretical performance of mid wavelength HgCdTe(1 0 0) heterostructure infrared detectors

    Science.gov (United States)

    Kopytko, M.

    2017-11-01

    The paper presents a theoretical study of the p+BpnN+ design based on HgCdTe(1 0 0) layers, which significantly improves the performance of detectors optimized for the mid-wave infrared spectral range. p+BpnN+ design combines the concept of a high impedance photoconductor with double layer hetero-junction device. Zero valence band offset approximation throughout the p+Bpn heterostructure allows flow of only minority holes generated in the absorber, what in a combination with n-N+ exclusion junction provides the Auger suppression. Modeling shows that by applying a low doping active layer, it is possible to achieve an order of magnitude lower dark current densities than those determined by ;Rule 07;. A key to its success is a reduction of Shockley-Read-Hall centers associated with native defects, residual impurities and misfit dislocations. Reduction of metal site vacancies below 1012 cm-3 and dislocation density to 105 cm-2 allow to achieve a background limited performance at 250 K. If the background radiation can be reduced, operation with a three- or four-stage thermo-electric-cooler may be possible.

  4. In-Line Monitoring of a High-Shear Granulation Process Using the Baseline Shift of Near Infrared Spectra.

    Science.gov (United States)

    Kuriyama, Atsushi; Osuga, Jin; Hattori, Yusuke; Otsuka, Makoto

    2018-02-01

    Although near infrared (NIR) spectra are primarily influenced by undesired variations, i.e., baseline shifts and non-linearity, and many applications of NIR spectroscopy to the real-time monitoring of wet granulation processes have been reported, the granulation mechanisms behind these variations have not been fully discussed. These variations of NIR spectra can be canceled out using appropriate pre-processing techniques prior to spectral analysis. The present study assessed the feasibility of directly using baseline shifts in NIR spectra to monitor granulation processes, because such shifts can reflect changes in the physical properties of the granular material, including particle size, shape, density, and refractive index. Specifically, OPUSGRAN ® , a novel granulation technology, was investigated by in-line NIR monitoring. NIR spectra were collected using a NIR diffuse reflectance fiber optic probe immersed in a high-shear granulator while simultaneously examining the morphology, particle size, density, strength, and Raman images of the mixture during granulation. The NIR baseline shift pattern was found to be characteristic of the OPUSGRAN ® technology and was attributed to variations in the light transmittance, reflection, and scattering resulting from changes in the physicochemical properties of the samples during granulation. The baseline shift also exhibited an inflection point around the completion of granulation, and therefore may be used to determine the endpoint of the process. These results suggest that a specific pattern of NIR baseline shifts are associated with the unique OPUSGRAN ® granulation mechanism and can be applied to monitor the manufacturing process and determine the endpoint.

  5. On the nature of unusual intensity changes in the infrared spectra of the enflurane ... acetone complexes

    Czech Academy of Sciences Publication Activity Database

    Zierkiewicz, W.; Zalesny, R.; Hobza, Pavel

    2013-01-01

    Roč. 15, č. 16 (2013), s. 6001-6007 ISSN 1463-9076 Institutional support: RVO:61388963 Keywords : shifting hydrogen-bonds * center-dot-o * molecular-orbital methods Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.198, year: 2013

  6. Prediction of specialty coffee cup quality based on near infrared spectra of green coffee beans.

    Science.gov (United States)

    Tolessa, Kassaye; Rademaker, Michael; De Baets, Bernard; Boeckx, Pascal

    2016-04-01

    The growing global demand for specialty coffee increases the need for improved coffee quality assessment methods. Green bean coffee quality analysis is usually carried out by physical (e.g. black beans, immature beans) and cup quality (e.g. acidity, flavour) evaluation. However, these evaluation methods are subjective, costly, time consuming, require sample preparation and may end up in poor grading systems. This calls for the development of a rapid, low-cost, reliable and reproducible analytical method to evaluate coffee quality attributes and eventually chemical compounds of interest (e.g. chlorogenic acid) in coffee beans. The aim of this study was to develop a model able to predict coffee cup quality based on NIR spectra of green coffee beans. NIR spectra of 86 samples of green Arabica beans of varying quality were analysed. Partial least squares (PLS) regression method was used to develop a model correlating spectral data to cupping score data (cup quality). The selected PLS model had a good predictive power for total specialty cup quality and its individual quality attributes (overall cup preference, acidity, body and aftertaste) showing a high correlation coefficient with r-values of 90, 90,78, 72 and 72, respectively, between measured and predicted cupping scores for 20 out of 86 samples. The corresponding root mean square error of prediction (RMSEP) was 1.04, 0.22, 0.27, 0.24 and 0.27 for total specialty cup quality, overall cup preference, acidity, body and aftertaste, respectively. The results obtained suggest that NIR spectra of green coffee beans are a promising tool for fast and accurate prediction of coffee quality and for classifying green coffee beans into different specialty grades. However, the model should be further tested for coffee samples from different regions in Ethiopia and test if one generic or region-specific model should be developed. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Simulation of cometary infrared spectra using laboratory extinction data of carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Colangeli, L.; Bussoletti, E.; Papoular, R.; Mennella, V. (Cassino Universita (Italy) Istituto Universitario Navale, Naples (Italy) CEA, Centre d' Etudes Nucleaires de Saclay, Gif-sur-Yvette (France) Osservatorio Astronomico di Capodimonte, Naples (Italy))

    1990-07-01

    Laboratory observations of the behavior of hydrogenated amorphous carbon (HAC) and the vitreous homogeneous organic compound vitrine may furnish a key to the identification of the 3.3-3.4 micron bands encountered in Comet Halley spectra between 3 and 4 microns. When the HAC annealing temperature rises, or when the rank of vitrines increases, a similar change occurs in the structure of these carbonaceous materials from a prevalent aliphatic to a dominant aromatic character. In situ mass spectrometry investigations of CHON particles conducted by Giotto and both Vega 1 and 2 appear to confirm the similarity of physical structure between carbonaceous particles and those observed in the laboratory. 46 refs.

  8. Microscopic surface wettability electrochemical characterization of tight sandstone with infrared spectra testing

    Science.gov (United States)

    Song, L.; Ning, Z. F.; Li, N.; Zhang, B.; Ding, G. Y.

    2017-08-01

    The distribution of charge density on the surface of microscopic tight oil is studied by using Stern double electric layer theory, and the mathematical flow model of polar fluid with micro powers in tight oil reservoir is established. The Fourier transform infrared (FTIR) were used to investigate the interaction of rock surface functional groups with fluids. The results show that: (1) When the external fluid of the polar group passes through the dense micro-nano pore, it will form an electric double layer on the surface of the rock, there will be a certain thickness of the liquid membrane, the fluid migration has a certain Of the electrical viscosity effect, will have a certain flow resistance. (2) The Fourier transform infrared spectroscopy of the Chang 7 tight reservoir rock samples exists and distributes different kinds of peaks. The left peak trend determines the presence of hydroxyl groups. The four fronts and types of the right side can be used to obtain that calcium carbonate CO3 2- exists. (3) There are CO3 2- and hydroxyl functional minerals in the Chang 7 tight sandstone samples. It is consistent with the basic mineral analysis measured by X-ray diffraction. When the external fluid affects the rock surface, the surface will occur in the physical van der Waals force and chemical bond interaction, so it will affect the flow of water on the surface.

  9. Infrared

    Science.gov (United States)

    Vollmer, M.

    2013-11-01

    'Infrared' is a very wide field in physics and the natural sciences which has evolved enormously in recent decades. It all started in 1800 with Friedrich Wilhelm Herschel's discovery of infrared (IR) radiation within the spectrum of the Sun. Thereafter a few important milestones towards widespread use of IR were the quantitative description of the laws of blackbody radiation by Max Planck in 1900; the application of quantum mechanics to understand the rotational-vibrational spectra of molecules starting in the first half of the 20th century; and the revolution in source and detector technologies due to micro-technological breakthroughs towards the end of the 20th century. This has led to much high-quality and sophisticated equipment in terms of detectors, sources and instruments in the IR spectral range, with a multitude of different applications in science and technology. This special issue tries to focus on a few aspects of the astonishing variety of different disciplines, techniques and applications concerning the general topic of infrared radiation. Part of the content is based upon an interdisciplinary international conference on the topic held in 2012 in Bad Honnef, Germany. It is hoped that the information provided here may be useful for teaching the general topic of electromagnetic radiation in the IR spectral range in advanced university courses for postgraduate students. In the most general terms, the infrared spectral range is defined to extend from wavelengths of 780 nm (upper range of the VIS spectral range) up to wavelengths of 1 mm (lower end of the microwave range). Various definitions of near, middle and far infrared or thermal infrared, and lately terahertz frequencies, are used, which all fall in this range. These special definitions often depend on the scientific field of research. Unfortunately, many of these fields seem to have developed independently from neighbouring disciplines, although they deal with very similar topics in respect of the

  10. The application of chemometrics on Infrared and Raman spectra as a tool for the forensic analysis of paints.

    Science.gov (United States)

    Muehlethaler, Cyril; Massonnet, Genevieve; Esseiva, Pierre

    2011-06-15

    The aim of this work is to evaluate the capabilities and limitations of chemometric methods and other mathematical treatments applied on spectroscopic data and more specifically on paint samples. The uniqueness of the spectroscopic data comes from the fact that they are multivariate - a few thousands variables - and highly correlated. Statistical methods are used to study and discriminate samples. A collection of 34 red paint samples was measured by Infrared and Raman spectroscopy. Data pretreatment and variable selection demonstrated that the use of Standard Normal Variate (SNV), together with removal of the noisy variables by a selection of the wavelengths from 650 to 1830 cm(-1) and 2730-3600 cm(-1), provided the optimal results for infrared analysis. Principal component analysis (PCA) and hierarchical clusters analysis (HCA) were then used as exploratory techniques to provide evidence of structure in the data, cluster, or detect outliers. With the FTIR spectra, the Principal Components (PCs) correspond to binder types and the presence/absence of calcium carbonate. 83% of the total variance is explained by the four first PCs. As for the Raman spectra, we observe six different clusters corresponding to the different pigment compositions when plotting the first two PCs, which account for 37% and 20% respectively of the total variance. In conclusion, the use of chemometrics for the forensic analysis of paints provides a valuable tool for objective decision-making, a reduction of the possible classification errors, and a better efficiency, having robust results with time saving data treatments. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  11. Size Effect on the Infrared Spectra of Condensed Media under Conditions of 1D, 2D, and 3D Dielectric Confinement

    KAUST Repository

    Shaganov, Igor I.

    2010-10-07

    The effect of dielectric confinement on the peak position of intramolecular and a lattice vibration in the infrared spectra of various condensed media is investigated. Liquid benzene, carbon disulfide, and chloroform, as well as amorphous SiO2 and microcrystalline MgO particles, were characterized in this study. The absorption spectra of organic liquids and aqueous solutions of a silica submicrometer powder were measured under a variety of dielectric confinement configurations using Fourier transform Infrared spectroscopy. A significant shift of the resonant absorption band of liquid mesoparticles has been observed under dielectric confinement, which is in good agreement with model predictions. A corresponding expression for the dielectric loss spectrum of an absorbing composite medium was obtained using a Maxwell-Garnett generalized equation for the cases of one, two, and three-dimensional dielectric confinement in both ordered and disordered thin layers (disks), rods (wires or needles), and spheres of an absorbing medium. The experimental data on peak positions obtained from the infrared spectra of the organic liquids investigated in this work, as well as from the infrared spectra of amorphous quartz spherical particles and rods, are in good agreement with the calculated data. It is shown using simulations of the absorption spectrum of MgO powder that the approach suggested can be applied under certain conditions to the modeling of the spectra of microcrystalline particles of nonspheroidal shape. © 2010 American Chemical Society.

  12. A multivariate regression model for detection of fumonisins content in maize from near infrared spectra.

    Science.gov (United States)

    Giacomo, Della Riccia; Stefania, Del Zotto

    2013-12-15

    Fumonisins are mycotoxins produced by Fusarium species that commonly live in maize. Whereas fungi damage plants, fumonisins cause disease both to cattle breedings and human beings. Law limits set fumonisins tolerable daily intake with respect to several maize based feed and food. Chemical techniques assure the most reliable and accurate measurements, but they are expensive and time consuming. A method based on Near Infrared spectroscopy and multivariate statistical regression is described as a simpler, cheaper and faster alternative. We apply Partial Least Squares with full cross validation. Two models are described, having high correlation of calibration (0.995, 0.998) and of validation (0.908, 0.909), respectively. Description of observed phenomenon is accurate and overfitting is avoided. Screening of contaminated maize with respect to European legal limit of 4 mg kg(-1) should be assured. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Stratospheric minor constituent distributions from far-infrared thermal emission spectra

    Science.gov (United States)

    Abbas, Mian M.; Traub, Wesley A.

    1992-01-01

    We retrieve mixing ratio profiles of O3, H2(O-16), H2(O-17), H2(O-18), HF, and HCl from far-infrared thermal emission observations of the limb in the 80-220 cm/sec spectral region. The observations were made with a balloon-borne Fourier transform spectrometer as a part of the 1983 Balloon Intercomparison Campaign (BIC-2). A subset of the data was analyzed previously using the method in the work of Traub et al. (1982, 1991); in the present paper we use an alternative method of calibration and analysis, given by Abbas et al. (1985). The retrieved constituent profiles are compared with the measurements made with other instruments on the BIC-2 flights. The results for the concentrations of H2(O-17) and H2(O-18) obtained in this study indicate no isotopic enhancement or depletion with a standard deviation of about 20 percent.

  14. Investigating the fermentation of cocoa by correlating denaturing gradient gel electrophoresis profiles and near infrared spectra

    DEFF Research Database (Denmark)

    Nielsen, Dennis Sandris; Snitkjær, Pia; van der Berg, Franciscus Winfried J

    2008-01-01

    Raw cocoa has an astringent, unpleasant taste and flavour, and has to be fermented, dried and roasted in order to obtain the characteristic cocoa flavour and taste. During the fermentation microbial activity outside the cocoa beans induces biochemical and physical changes inside the beans...... of the beans and the chemical processes inside the beans have been carried out previously. Recently it has been shown that Denaturing Gradient Gel Electrophoresis (DGGE) offers an efficient tool for monitoring the microbiological changes taking place during the fermentation of cocoa. Near Infrared (NIR......) spectroscopy has previously been used to determine various components in cocoa beans, offering a rapid alternative compared to traditional analytical methods for obtaining knowledge about changes in the chemical composition of the cocoa beans during fermentation. During a number of cocoa fermentations bean...

  15. The effect of grain size and phosphorous-doping of polycrystalline 3C-SiC on infrared reflectance spectra

    Energy Technology Data Exchange (ETDEWEB)

    Rooyen, I.J. van, E-mail: Isabella.vanRooyen@inl.gov [Fuel Performance and Design Department, Idaho National Laboratory, Idaho Falls, ID 83415-6188 (United States); Department of Physics, Nelson Mandela Metropolitan University, Port Elizabeth (South Africa); Engelbrecht, J.A.A. [Department of Physics, Nelson Mandela Metropolitan University, Port Elizabeth (South Africa); Henry, A.; Janzen, E. [Department of Physics, Chemistry and Biology, Semiconductor Materials, Linkoeping University, Linkoeping 58183 (Sweden); Neethling, J.H. [Department of Physics, Nelson Mandela Metropolitan University, Port Elizabeth (South Africa); Rooyen, P.M. van [Philip M van Rooyen Network Consultants, Midlands Estates (South Africa)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer IR is investigated as a technique to measure grain size and P-doping of polycrystalline SiC. Black-Right-Pointing-Pointer Infrared plasma minima can be used to determine doping levels in 3C-SiC for doping levels greater than 5 Multiplication-Sign 10{sup 17} cm{sup -3}. Black-Right-Pointing-Pointer A linear relationship is found between FWHM and the inverse of grain size of 3C-SiC irrespective of P-doping level. Black-Right-Pointing-Pointer It is further found that {omega}{sub p} is not influenced by the grain size. Black-Right-Pointing-Pointer P-doping level has no significant effect on the linear relationship between grain size and surface roughness. - Abstract: The effect of P-doping and grain size of polycrystalline 3C-SiC on the infrared reflectance spectra is reported. The relationship between grain size and full width at half maximum (FWHM) suggest that the behavior of the 3C-SiC with the highest phosphorous doping level (of 1.2 Multiplication-Sign 10{sup 19} at. cm{sup -3}) is different from those with lower doping levels (<6.6 Multiplication-Sign 10{sup 18} at. cm{sup -3}). It is also further demonstrated that the plasma resonance frequency ({omega}{sub p}) is not influenced by the grain size.

  16. The effect of grain size and phosphorous-doping of polycrystalline 3C–SiC on infrared reflectance spectra

    International Nuclear Information System (INIS)

    Rooyen, I.J. van; Engelbrecht, J.A.A.; Henry, A.; Janzén, E.; Neethling, J.H.; Rooyen, P.M. van

    2012-01-01

    Highlights: ► IR is investigated as a technique to measure grain size and P-doping of polycrystalline SiC. ► Infrared plasma minima can be used to determine doping levels in 3C–SiC for doping levels greater than 5 × 10 17 cm −3 . ► A linear relationship is found between FWHM and the inverse of grain size of 3C–SiC irrespective of P-doping level. ► It is further found that ω p is not influenced by the grain size. ► P-doping level has no significant effect on the linear relationship between grain size and surface roughness. - Abstract: The effect of P-doping and grain size of polycrystalline 3C–SiC on the infrared reflectance spectra is reported. The relationship between grain size and full width at half maximum (FWHM) suggest that the behavior of the 3C–SiC with the highest phosphorous doping level (of 1.2 × 10 19 at. cm −3 ) is different from those with lower doping levels ( 18 at. cm −3 ). It is also further demonstrated that the plasma resonance frequency (ω p ) is not influenced by the grain size.

  17. Quantitative determination of methanol and ethanol with synthetic calibration spectra in passive Fourier transform infrared remote sensing measurements.

    Science.gov (United States)

    Guo, Qiaohan; Small, Gary W

    2013-08-01

    A spectral synthesis strategy is introduced to help obtain estimates of path-integrated concentrations in passive Fourier transform infrared (FT-IR) remote sensing measurements conducted during field-monitoring experiments. Obtaining quantitative information from passive infrared data is challenging because of the joint effects of temperature and concentration on spectral intensities. The collection of calibration data for use in modeling spectral intensities for a given set of experimental conditions is also costly and labor intensive. In the work presented here, a radiance model is defined for use in synthesizing calibration spectra that serve as inputs to partial least-squares (PLS) models that relate spectral intensities to path-integrated concentrations. The field data for which quantitative estimates are desired are used to estimate the background temperature associated with a given time and set of experimental conditions. Sample temperatures can be obtained through either experimental measurement or by estimating one calibration release. Given these temperatures, calibration data can be synthesized and the PLS model developed. This methodology is tested with stack monitoring data obtained from controlled releases of pure and mixture samples of heated ethanol and methanol. Experiments were conducted across 6 days with stack temperatures of 150 to 200 °C and with path-integrated concentrations in the range of 10 to 300 parts per million meters. Median relative errors in the estimates of path-integrated concentration were typically in the range of 20% or less, with the best results observed at the higher stack temperatures.

  18. Non-parametric analysis of infrared spectra for recognition of glass and glass ceramic fragments in recycling plants.

    Science.gov (United States)

    Farcomeni, Alessio; Serranti, Silvia; Bonifazi, Giuseppe

    2008-01-01

    Glass ceramic detection in glass recycling plants represents a still unsolved problem, as glass ceramic material looks like normal glass and is usually detected only by specialized personnel. The presence of glass-like contaminants inside waste glass products, resulting from both industrial and differentiated urban waste collection, increases process production costs and reduces final product quality. In this paper an innovative approach for glass ceramic recognition, based on the non-parametric analysis of infrared spectra, is proposed and investigated. The work was specifically addressed to the spectral classification of glass and glass ceramic fragments collected in an actual recycling plant from three different production lines: flat glass, colored container-glass and white container-glass. The analyses, carried out in the near and mid-infrared (NIR-MIR) spectral field (1280-4480 nm), show that glass ceramic and glass fragments can be recognized by applying a wavelet transform, with a small classification error. Moreover, a method for selecting only a small subset of relevant wavelength ratios is suggested, allowing the conduct of a fast recognition of the two classes of materials. The results show how the proposed approach can be utilized to develop a classification engine to be integrated inside a hardware and software sorting architecture for fast "on-line" ceramic glass recognition and separation.

  19. DERIVING METALLICITIES FROM THE INTEGRATED SPECTRA OF EXTRAGALACTIC GLOBULAR CLUSTERS USING THE NEAR-INFRARED CALCIUM TRIPLET

    International Nuclear Information System (INIS)

    Foster, Caroline; Forbes, Duncan A.; Proctor, Robert N.; Spitler, Lee R.; Strader, Jay; Brodie, Jean P.

    2010-01-01

    The Ca II triplet (CaT) feature in the near-infrared has been employed as a metallicity indicator for individual stars as well as integrated light of Galactic globular clusters (GCs) and galaxies with varying degrees of success, and sometimes puzzling results. Using the DEIMOS multi-object spectrograph on Keck we obtain a sample of 144 integrated light spectra of GCs around the brightest group galaxy NGC 1407 to test whether the CaT index can be used as a metallicity indicator for extragalactic GCs. Different sets of single stellar population models make different predictions for the behavior of the CaT as a function of metallicity. In this work, the metallicities of the GCs around NGC 1407 are obtained from CaT index values using an empirical conversion. The measured CaT/metallicity distributions show unexpected features, the most remarkable being that the brightest red and blue GCs have similar CaT values despite their large difference in mean color. Suggested explanations for this behavior in the NGC 1407 GC system are (1) the CaT may be affected by a population of hot blue stars, (2) the CaT may saturate earlier than predicted by the models, and/or (3) color may not trace metallicity linearly. Until these possibilities are understood, the use of the CaT as a metallicity indicator for the integrated spectra of extragalactic GCs will remain problematic.

  20. Understanding the interface between silicon-based materials and water: Molecular-dynamics exploration of infrared spectra

    Directory of Open Access Journals (Sweden)

    José A. Martinez-Gonzalez

    2017-11-01

    Full Text Available Molecular-dynamics simulations for silicon, hydrogen- and hydroxyl-terminated silicon in contact with liquid water, at 220 and 300 K, display water-density ‘ordering’ along the laboratory z-axis, emphasising the hydrophobicity of the different systems and the position of this first adsorbed layer. Density of states (DOS of the oxygen and proton velocity correlation functions (VACFs and infrared (IR spectra of the first monolayer of adsorbed water, calculated via Fourier transformation, indicate similarities to more confined, ice-like dynamical behaviour (redolent of ice. It was observed that good qualitative agreement is obtained between the DOS for this first layer in all systems. The DOS for the lower-frequency zone indicates that for the interface studied (i.e., the first layer near the surface, the water molecules try to organise in a similar form, and that this form is intermediate between liquid water and ice. For IR spectra, scrutiny of the position of the highest-intensity peaks for the stretching and bending bands indicate that such water molecules in the first solvating layer are organised in an intermediate fashion between ice and liquid water.

  1. Simulated aging of lubricant oils by chemometric treatment of infrared spectra: potential antioxidant properties of sulfur structures.

    Science.gov (United States)

    Amat, Sandrine; Braham, Zeineb; Le Dréau, Yveline; Kister, Jacky; Dupuy, Nathalie

    2013-03-30

    Lubricant oils are complex mixtures of base oils and additives. The evolution of their performance over time strongly depends on its resistance to thermal oxidation. Sulfur compounds revealed interesting antioxidant properties. This study presents a method to evaluate the lubricant oil oxidation. Two samples, a synthetic and a paraffinic base oils, were tested pure and supplemented with seven different sulfur compounds. An aging cell adapted to a Fourier Transform InfraRed (FT-IR) spectrometer allows the continuous and direct analysis of the oxidative aging of base oils. Two approaches were applied to study the oxidation/anti-oxidation phenomena. The first one leads to define a new oxidative spectroscopic index based on a reduced spectral range where the modifications have been noticed (from 3050 to 2750 cm(-1)). The second method is based on chemometric treatments of whole spectra (from 4000 to 400 cm(-1)) to extract underlying information. A SIMPLe-to-use Interactive Self Modeling Analysis (SIMPLISMA) method has been used to identify more precisely the chemical species produced or degraded during the thermal treatment and to follow their evolution. Pure spectra of different species present in oil were obtained without prior information of their existence. The interest of this tool is to supply relative quantitative information reflecting evolution of the relative abundance of the different products over thermal aging. Results obtained by these two ways have been compared to estimate their concordance. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Homogeneity of Surface Sites in Supported Single-Site Metal Catalysts: Assessment with Band Widths of Metal Carbonyl Infrared Spectra.

    Science.gov (United States)

    Hoffman, Adam S; Fang, Chia-Yu; Gates, Bruce C

    2016-10-06

    Determining and controlling the uniformity of isolated metal sites on surfaces of supports are central goals in investigations of single-site catalysts because well-defined species provide opportunities for fundamental understanding of the surface sites. CO is a useful probe of surface metal sites, often reacting with them to form metal carbonyls, the infrared spectra of which provide insights into the nature of the sites and the metal-support interface. Metals bonded to various support surface sites give broad bands in the spectra, and when narrow bands are observed, they indicate a high degree of uniformity of the metal sites. Much recent work on single-site catalysts has been done with supports that are inherently nonuniform, giving supported metal species that are therefore nonuniform. Herein we summarize values of ν CO data characterizing supported iridium gem-dicarbonyls, showing that the most nearly uniform of them are those supported on zeolites and the least uniform are those supported on metal oxides. Guided by ν CO data of supported iridium gem-dicarbonyls, we have determined new, general synthesis methods to maximize the degree of uniformity of iridium species on zeolites and on MgO. We report results for a zeolite HY-supported iridium gem-dicarbonyl with full width at half-maximum values of only 4.6 and 5.2 cm -1 characterizing the symmetric and asymmetric CO stretches and implying that this is the most nearly uniform supported single-site metal catalyst.

  3. The application of near-infrared spectra micro-image in the imaging analysis of biology samples

    Directory of Open Access Journals (Sweden)

    Dong Wang

    2014-07-01

    Full Text Available In this research, suitable imaging methods were used for acquiring single compound images of biology samples of chicken pectorales tissue section, tobacco dry leaf, fresh leaf and plant glandular hair, respectively. The adverse effects caused by the high water content and the thermal effect of near infrared (NIR light were effectively solved during the experiment procedures and the data processing. PCA algorithm was applied to the NIR micro-image of chicken pectorales tissue. Comparing the loading vector of PC3 with the NIR spectrum of dry albumen, the information of PC3 was confirmed to be provided mainly by protein, i.e., the 3rd score image represents the distribution trend of protein mainly. PCA algorithm was applied to the NIR micro-image of tobacco dry leaf. The information of PC2 was confirmed to be provided by carbohydrate including starch mainly. Compared to the 2nd score image of tobacco dry leaf, the compared correlation image with the reference spectrum of starch had the same distribution trend as the 2nd score image. The comparative correlation images with the reference spectra of protein, glucose, fructose and the total plant alkaloid were acquired to confirm the distribution trend of these compounds in tobacco dry leaf respectively. Comparative correlation images of fresh leaf with the reference spectra of protein, starch, fructose, glucose and water were acquired to confirm the distribution trend of these compounds in fresh leaf. Chemimap imaging of plant glandular hair was acquired to show the tubular structure clearly.

  4. Estimation of leaf water contents from mid- and thermal infrared spectra by coupling genetic algorithm and partial least squares regression

    Science.gov (United States)

    Arshad, Muhammad; Ullah, Saleem; Khurshid, Khurram; Ali, Asad

    2017-10-01

    Leaf Water Content (LWC) is an essential constituent of plant leaves that determines vegetation heath and its productivity. An accurate and on-time measurement of water content is crucial for planning irrigation, forecasting drought and predicting woodland fire. The retrieval of LWC from Visible to Shortwave Infrared (VSWIR: 0.4-2.5 μm) has been extensively investigated but little has been done in the Mid and Thermal Infrared (MIR and TIR: 2.50 -14.0 μm), windows of electromagnetic spectrum. This study is mainly focused on retrieval of LWC from Mid and Thermal Infrared, using Genetic Algorithm integrated with Partial Least Square Regression (PLSR). Genetic Algorithm fused with PLSR selects spectral wavebands with high predictive performance i.e., yields high adjusted-R2 and low RMSE. In our case, GA-PLSR selected eight variables (bands) and yielded highly accurate models with adjusted-R2 of 0.93 and RMSEcv equal to 7.1 %. The study also demonstrated that MIR is more sensitive to the variation in LWC as compared to TIR. However, the combined use of MIR and TIR spectra enhances the predictive performance in retrieval of LWC. The integration of Genetic Algorithm and PLSR, not only increases the estimation precision by selecting the most sensitive spectral bands but also helps in identifying the important spectral regions for quantifying water stresses in vegetation. The findings of this study will allow the future space missions (like HyspIRI) to position wavebands at sensitive regions for characterizing vegetation stresses.

  5. Accurate Theoretical Methane Line Lists in the Infrared up to 3000 K and Quasi-continuum Absorption/Emission Modeling for Astrophysical Applications

    Energy Technology Data Exchange (ETDEWEB)

    Rey, Michael; Tyuterev, Vladimir G. [Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 7331, BP 1039, F-51687, Reims Cedex 2 (France); Nikitin, Andrei V., E-mail: michael.rey@univ-reims.fr [Laboratory of Theoretical Spectroscopy, Institute of Atmospheric Optics, SB RAS, 634055 Tomsk (Russian Federation)

    2017-10-01

    Modeling atmospheres of hot exoplanets and brown dwarfs requires high- T databases that include methane as the major hydrocarbon. We report a complete theoretical line list of {sup 12}CH{sub 4} in the infrared range 0–13,400 cm{sup −1} up to T {sub max} = 3000 K computed via a full quantum-mechanical method from ab initio potential energy and dipole moment surfaces. Over 150 billion transitions were generated with the lower rovibrational energy cutoff 33,000 cm{sup −1} and intensity cutoff down to 10{sup −33} cm/molecule to ensure convergent opacity predictions. Empirical corrections for 3.7 million of the strongest transitions permitted line position accuracies of 0.001–0.01 cm{sup −1}. Full data are partitioned into two sets. “Light lists” contain strong and medium transitions necessary for an accurate description of sharp features in absorption/emission spectra. For a fast and efficient modeling of quasi-continuum cross sections, billions of tiny lines are compressed in “super-line” libraries according to Rey et al. These combined data will be freely accessible via the TheoReTS information system (http://theorets.univ-reims.fr, http://theorets.tsu.ru), which provides a user-friendly interface for simulations of absorption coefficients, cross-sectional transmittance, and radiance. Comparisons with cold, room, and high- T experimental data show that the data reported here represent the first global theoretical methane lists suitable for high-resolution astrophysical applications.

  6. Using late-time optical and near-infrared spectra to constrain Type Ia supernova explosion properties

    Science.gov (United States)

    Maguire, K.; Sim, S. A.; Shingles, L.; Spyromilio, J.; Jerkstrand, A.; Sullivan, M.; Chen, T.-W.; Cartier, R.; Dimitriadis, G.; Frohmaier, C.; Galbany, L.; Gutiérrez, C. P.; Hosseinzadeh, G.; Howell, D. A.; Inserra, C.; Rudy, R.; Sollerman, J.

    2018-03-01

    The late-time spectra of Type Ia supernovae (SNe Ia) are powerful probes of the underlying physics of their explosions. We investigate the late-time optical and near-infrared spectra of seven SNe Ia obtained at the VLT with XShooter at >200 d after explosion. At these epochs, the inner Fe-rich ejecta can be studied. We use a line-fitting analysis to determine the relative line fluxes, velocity shifts, and line widths of prominent features contributing to the spectra ([Fe II], [Ni II], and [Co III]). By focussing on [Fe II] and [Ni II] emission lines in the ˜7000-7500 Å region of the spectrum, we find that the ratio of stable [Ni II] to mainly radioactively-produced [Fe II] for most SNe Ia in the sample is consistent with Chandrasekhar-mass delayed-detonation explosion models, as well as sub-Chandrasekhar mass explosions that have metallicity values above solar. The mean measured Ni/Fe abundance of our sample is consistent with the solar value. The more highly ionised [Co III] emission lines are found to be more centrally located in the ejecta and have broader lines than the [Fe II] and [Ni II] features. Our analysis also strengthens previous results that SNe Ia with higher Si II velocities at maximum light preferentially display blueshifted [Fe II] 7155 Å lines at late times. Our combined results lead us to speculate that the majority of normal SN Ia explosions produce ejecta distributions that deviate significantly from spherical symmetry.

  7. Comparison of various molecular forms of bovine trypsin: Correlation of infrared spectra with X-ray crystal structures

    Energy Technology Data Exchange (ETDEWEB)

    Prestrelski, S.J. (Mount Sinai School of Medicine of the City Univ. of New York (USA)); Byler, D.M. (U.S. Department of Agriculture, Philadelphia, PA (USA)); Liebman, M.N. (AMOCO Technology Corporation, Naperville, IL (USA))

    1991-01-01

    Fourier-transform infrared spectroscopy is a valuable method for the study of protein conformation in solution primarily because of the sensitivity to conformation of the amide I band (1700-1620 cm{sup {minus}1}) which arises from the backbone C{double bond}O stretching vibration. Combined with resolution-enhancement techniques such as derivative spectroscopy and self-deconvolution, plus the application of iterative curve-fitting techniques, this method provides a wealth of information concerning protein secondary structure. Further extraction of conformational information from the amide I band is dependent upon discerning the correlations between specific conformation types and component bands in the amide I region. In this paper the authors report spectra-structure correlations derived from conformational perturbations in bovine trypsin which arise from autolytic processing, zymogen activation, and active-site inhibition. IR spectra were collected for the single-chain ({beta}-trypsin) and once-cleaved, double-chain ({alpha}-trypsin) forms as well as at various times during the course of autolysis and also for zymogen, trypsinogen, and {beta}-trypsin inhibited with diisopropyl fluorophosphate. Spectral differences among the various molecular forms were interpreted in light of previous biochemical studies of autolysis and the known three-dimensional structures of the zymogen, the active enzyme, and the DIP-inhibited form. The spectroscopic results from these proteins in D{sub 2}O imply that certain loop structures may absorb in the region of 1655 cm{sup {minus}1}. They estimate that this approach to data analysis and interpretation is sensitive to changes of 0.01 unit or less in the relative integrated intensities of component bands in spectra whose peaks are well resolved.

  8. Fourier transform infrared and FT-Raman spectra, assignment, ab initio, DFT and normal co-ordinate analysis of 2-chloro-4-methylaniline and 2-chloro-6-methylaniline.

    Science.gov (United States)

    Arjunan, V; Mohan, S

    2009-03-01

    The Fourier transform infrared (FTIR) and FT-Raman spectra of 2-chloro-4-methylaniline and 2-chloro-6-methylaniline have been measured in the range 4000-400 and 4000-100cm(-1), respectively. Utilising the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compounds were carried out. The vibrational frequency which were determined experimentally are compared with those obtained theoretically from ab initio HF and DFT gradient calculations employing the HF/6-31G(d,p) and B3LYP/6-31G(d,p) methods for optimised geometries. The geometries and normal modes of vibration obtained from the HF and DFT methods are in good agreement with the experimental data. The normal co-ordinate analysis was also carried out on the basis of ab initio force fields utilising Wilson's FG matrix method. The manifestations of NH-pi interactions and the influence of bulky chlorine and methyl group on the vibrational modes of the amino group are investigated.

  9. Linear response properties required to simulate vibrational spectra of biomolecules in various media: (R)-phenyloxirane (A comparative theoretical and spectroscopic vibrational study)

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Jürgensen, Vibeke Würtz; Degtyarenko, I.M.

    2005-01-01

    on either the VA and VCD spectra or the Raman and ROA spectra of molecules, since the experimental and theoretical instruments and methods for calculating these quantities are quite distinct. Here we show that the combined analysis gives more information, especially with respect to the electric dipole...... in their native environments. As the physical tools used to observe and study biological processes have evolved, so have the theoretical methods and models to interpret, understand and completely utilize the results of these new measurements. The work on developing methods for modeling amino acids, peptides...

  10. [Study on the function group uniformity of polystyrol sulfonyl chloride resins by infrared spectra].

    Science.gov (United States)

    Lin, Xian; Wei, Rong-Qing; Liu, Xiao-Ning; Zhou, Rui

    2009-07-01

    The reactions of polyvinyl benzene with chlorosulfonic acid were performed under different ratio and reaction time and the results of chloro-sulfonation were detected by infrared spectrometer (380FT-IR). The characteristic peak at 1 601.5 cm(-1) belongs to benzene ring and was selected as the internal standard peak Two characteristic peaks at 1 377.4 and 3 476.8 cm(-1) were selected as reference peaks, and belong to sulfonyl chloride and sulfonic group respectively. According to the Lambert-Beer law, the absorbance at 1 377. 4 and 3 476.8 cm(-1) was detected and compared with absorbance at 1 601.5 cm(-1) respectively. The value of A1 377.4 : A3 476.8 was used to express uniformity of polystyrol sulfonyl chloride resins. The results show that: (a) After 0.5 h, A1 377.4 : A1 60.5 rises quickly with the prolonging of reaction time; and A3 476.8 : A1 601.5 rises too, but descends after 1 h. And the value of A1 377.4 : A3 476.8 rises with the prolonging of reaction time after 1 h. (b) When the ratio of HSOs Cl and PS is less than 1 : 1, A3 476.8 : A1 601.5 rises with the ratio increasing, but when the ratio of HSO3 Cl and PS is more than 1 : 1, A3 476.8 : A1 601.5 descends while A1 377.4 : A1 601.5 appears and increases following the increase in the ratio. As the ratio was 4 : 1, A1 377.4 : A 601.5 and A3 476.8 : A, 601.5 show stabilization. In one step reaction condition, as the ratio of HSO3 Cl and PS is 4 : 1, the reaction can enhance uniformity of PS-SO2 Cl at 60 degrees C for 5 h (the loading of sulfonyl chloride is 4.0 mmol x g(-1)). It was also confirmed that the function group uniformity of polystyrol sulfonyl chloride resins could be determined by infrared spectroscopy conveniently and quickly. Meanwhile, this method could be adopted to determine the function group uniformity practicably and widely.

  11. Study of Perfluoroalkyl Chain-Specific Band Shift in Infrared Spectra on the Chain Length.

    Science.gov (United States)

    Shimoaka, Takafumi; Sonoyama, Masashi; Amii, Hideki; Takagi, Toshiyuki; Kanamori, Toshiyuki; Hasegawa, Takeshi

    2017-11-09

    The CF 2 symmetric stretching vibration (ν s (CF 2 )) band of a perfluoroalkyl (Rf) group in an infrared (IR) spectrum exhibits a unique character, that is, an apparent high wavenumber shift with increasing the chain length, which is an opposite character to that of the CH stretching vibration band of a normal alkyl chain. To reveal the mechanism of the unusual IR band shift, two vibrational characters of an Rf chain are focused: (1) a helical conformation of an Rf chain, (2) the carbon (C) atoms having a smaller mass than the fluorine (F) atom dominantly vibrate as a coupled oscillator leaving F atoms stay relatively unmoved. These indicate that a "coupled oscillation of the skeletal C atoms" of an Rf chain should be investigated considering the helical structure. In the present study, therefore, the coupled oscillation of the Rf chain dependent on the chain length is investigated by Raman spectroscopy, which is suitable for investigating a skeletal vibration. The Raman-active ν s (CF 2 ) band is found to be split into two bands, the splitting is readily explained by considering the helical structure and length with respect to group theory, and the unusual peak shift is concluded to be explained by the helical length.

  12. Near infrared spectra of carbon deposited layers from Tore Supra under plasma particle bombardment

    International Nuclear Information System (INIS)

    Delchambre, E.; Reichle, R.; Loarer, T.

    2003-01-01

    The authors present the results of laboratory investigations that show spectral luminance distributions similar to those emitted by plasma facing components in Tore-Supra experiments. The device used to produce plasma impact on the target is an Helicon source, where the gas is ionised with a 13.56 MHz RF generator. Different targets were tested: highly oriented pyrolytic graphite (HOPG) and pyrolytic graphite sampled from the MPL (modular pump limiter) neutralizer covered with flakes (a loosely attached deposited carbon layer). The target, placed in the centre of the vacuum vessel, was positively biased to ensure an electron bombardment only. NIR (near infra-red) spectral luminance deformation phenomena as observed in Tore-Supra, have been reproduced in the laboratory. Additional NIR luminance, with a maximum around 1.3 μm considering T(1.55 μm) as temperature reference, has shown up on the same carbon deposited layer that actually gave rise to the first reports on the phenomenon but not on HOPG. The phenomenon occurs in Ar and in H 2 when the current collected on the target exceeds 20 or 30 mA/cm 2 respectively. The intensity of the effect increases with growing target temperature and seemingly with growing collected current density and it disappears after electron bombardment with a time constant of 0.34 s. It shows some linear behaviour in Arrhenius plot

  13. Changes in Attenuated Total Reflection Fourier Transform Infrared Spectra as Blood Dries Out.

    Science.gov (United States)

    Zhang, Yinming; Wang, Qi; Li, Bing; Wang, Zhijun; Li, Chengzhi; Yao, Yao; Huang, Ping; Wang, Zhenyuan

    2017-05-01

    The time since deposition (TSD) of a bloodstain is a valuable piece of evidence for forensic scientists to determine the time at which a crime took place. The objective of this study was to determine whether attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy could be used to estimate the TSD of a bloodstain in a relatively early period (from 0 min to the time required for the bloodstain to dry out). For this purpose, we used ATR-FTIR to study the variation in absorbance at certain wavelengths as rat and human blood sample dried out. The absorbance at 3308/cm (A3308) was found to have a close correlation with the TSD during this time period, and the changes in A3308 during the drying of rat and human blood drops under the same controlled conditions showed similar results. The current study indicates that ATR-FTIR spectroscopy has potential as a tool for estimating TSD at early time periods of blood deposition. © 2016 American Academy of Forensic Sciences.

  14. C3 Hydrocarbon Abundance in Titan's Atmosphere with Cassini Infrared Spectra

    Science.gov (United States)

    Lombardo, Nicholas; Nixon, Conor; Achterberg, Richard; Jolly, Antoine; Sung, Keeyoon; Irwin, Patrick; Flasar, F. M.

    2018-01-01

    Titan, the largest moon of the Saturn system, has an astrobiologically important atmosphere. The anoxic nature and high N2 abundance make it a strong analog to the early Earth. The secondary species, CH4, is easily photodissociated, and reactions between its dissociated products give rise to highly complex hydrocarbons and nitriles. The Voyager flyby and 14 year Cassini campaign allowed for the intense study of several of these molecules, enabling scientists to increase our understanding of the chemical pathways present above Titan. In this work, we report abundance profiles of four major C3 gasses expected to occur in Titan’s atmosphere, derived from Cassini/Composite Infrared Spectrometer (CIRS) data, allowing us to fill the gaps in the photochemical zoo that is Titan’s atmosphere.Using the NEMESIS iterative radiative transfer module, we retrieved vertical abundance profiles for propane (C3H8) and propyne (CHCCH3) both initially detected by the Voyager IRIS instrument. Using newly available line data, we were also able to determine the first vertical abundance profiles for propene (C3H6), initially detected in 2013. We present profiles for several latitudes and times and compare to photochemical model predictions and previous observations. We also discuss our ongoing search for allene (CH2CCH2), an isomer of propyne, which has yet to be definitively detected. The abundances we determined will help to further our understanding of the chemical pathways that occur in Titan's atmosphere.

  15. Infrared spectra, methyl group structure and internal rotation in some methy - metal compounds

    Science.gov (United States)

    McKean, D. C.; McQuillan, G. P.; Torto, I.; Morrisson, A. R.

    1986-03-01

    Recent and current work on spectra in the CH and CD stretching regions of methyl-metal compounds is reviewed. Free internal rotation with CH force constant variation is found in MMe 3 (M  Ga, Tl) and MMe(CO) 5 (M  Mn, Re) compounds, studied in the gas phase. From solution measurements, no such rotation occurs in CpMMe(CO) 3 (M  Cr,Mo,W) and Cp 2MMe 2 (M  Ti,Zr,Hf), in most of which each methyl group contains two types of CH bond. In each d-subgroup, ν isCH decreases with increasing atomic number, while δ sCH 3 increases. The reverse occurs from Ga to Tl. r oCH values are predicted. There is evidence for the breakdown of the ν isCH/∠HCH correlation, especially in MeTiCl 3 where several features point to an unusual structure of the methyl group.

  16. Visible to Near Infrared Emission Spectra of Electron-Excited H2

    Science.gov (United States)

    Aguilar, A.; James, G. K.; Ajello, J. M.; Abgrall, H.; Roueff, E.

    2006-01-01

    The electron-impact induced fluorescence spectrum of H2 at 100 eV from 700 nm to 950 nm at a spectral resolution of between 0.2 nm to 0.3 nm has been measured. The laboratory spectrum has been compared with our theoretical simulated spectrum obtained by calculating the lines emission cross sections from the upper states of g symmetry (EF, GK, HH, P, O ; I, R, J, S ) towards the states of u symmetry (B, C, B', D) of H2. The nine above Born-Openheimer g-upper states have been coupled together as well as the four above Born-Openheimer u-lower states. The comparison seems adequate with few minor discrepancies.

  17. Near-infrared diffuse interstellar bands in APOGEE telluric standard star spectra . Weak bands and comparisons with optical counterparts

    Science.gov (United States)

    Elyajouri, M.; Lallement, R.; Monreal-Ibero, A.; Capitanio, L.; Cox, N. L. J.

    2017-04-01

    Aims: Information on the existence and properties of diffuse interstellar bands (DIBs) outside the optical domain is still limited. Additional infra-red (IR) measurements and IR-optical correlative studies are needed to constrain DIB carriers and locate various absorbers in 3D maps of the interstellar matter. Methods: We extended our study of H-band DIBs in Apache Point Observatory Galactic Evolution Experiment (APOGEE) Telluric Standard Star (TSS) spectra. We used the strong λ15273 band to select the most and least absorbed targets. We used individual spectra of the former subsample to extract weaker DIBs, and we searched the two stacked series for differences that could indicate additional bands. High-resolution NARVAL and SOPHIE optical spectra for a subsample of 55 TSS targets were additionally recorded for NIR/optical correlative studies. Results: From the TSS spectra we extract a catalog of measurements of the poorly studied λλ15617, 15653, and 15673 DIBs in ≃300 sightlines, we obtain a first accurate determination of their rest wavelength and constrained their intrinsic width and shape. In addition, we studied the relationship between these weak bands and the strong λ15273 DIB. We provide a first or second confirmation of several other weak DIBs that have been proposed based on different instruments, and we add new constraints on their widths and locations. We finally propose two new DIB candidates. Conclusions: We compared the strength of the λ15273 absorptions with their optical counterparts λλ5780, 5797, 6196, 6283, and 6614. Using the 5797-5780 ratio as a tracer of shielding against the radiation field, we showed that the λ15273 DIB carrier is significantly more abundant in unshielded (σ-type) clouds, and it responds even more strongly than the λ5780 band carrier to the local ionizing field. Full Table 5 is available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc

  18. Infrared Spectra of Protonated Quinoline (1-C_9H_7NH^{+}) in Solid Para-Hydrogen

    Science.gov (United States)

    Tseng, Chih-Yu; Lee, Yuan-Pern

    2017-06-01

    Large protonated polycyclic aromatic hydrocarbons (H^{+}PAH) and polycyclic aromatic nitrogen heterocycles (H^{+}PANH) have been proposed as possible carriers of unidentified infrared (UIR) emission bands from galactic objects. The nitrogen atom in H^{+}PANH is expected to induce a blue shift of the C=C stretching band near 6.2 μm so that their emission bands might agree with the UIR band better than those of H^{+}PAH. In this work, we report the IR spectrum of protonated quinoline and its neutral species measured upon electron bombardment during deposition of a mixture of quinoline and para-hydrogen at 3.2 K. New features were assigned to 1-C_9H_7NH^{+} and 1-C_9H_7NH, indicating that the protonation and hydrogenation occur at the N-atom site. The intensities of features of 1-C_9H_7NH^{+} diminished when the matrix was maintained in darkness for 10 h, whereas those of 1-C_9H_7NH increased. Spectral assignments were made according to comparison of experimental results with anharmonic vibrational wavenumbers and IR intensities calculated with the B3LYP/6-311++G(d,p) method. Although agreement between the observed spectrum of 1-C_9H_7NH^{+} and the UIR emission bands is unsatisfactory, presumably because of the small size of quinoline, we did observe C=C stretching bands at 1641.4, 1598.4, 1562.0 \\wn, blue-shifted from those at 1618.7, 1580.8, 1510.0 \\wn of the corresponding protonated PAH (C_{10}H_{9}^{+}), pointing to the direction of the UIR bands.

  19. Application of the Hybrid Program for Fitting Microwave and Far-Infrared Spectra of Methylamine

    Science.gov (United States)

    Kleiner, Isabelle; Hougen, Jon T.

    2016-06-01

    Last year we presented a new hybrid-model fitting program for methylamine-like molecules, based on an effective Hamiltonian in which the ammonia-like inversion motion is treated using a tunneling formalism, while the internal-rotation motion is treated using an explicit kinetic energy operator and potential energy function. This new hybrid program was successfully applied to 2-methylmalonaldehyde, for which we refit the already published ground state vt = 0 data. This fit, which was of almost the same quality as that obtained using an all-tunneling formalism, removed one of the major puzzles in the isotope-dependence of the internal-rotation tunneling parameters found in the all-tunneling fit. This year we are trying to illustrate a second advantage of the new hybrid formalism, which allows one to carry out global fits of data from two or more torsional states in methylamine-like molecules. We are, in fact, trying to simultaneously fit the vt = 0 and vt = 1 microwave and infrared date on methylamine itself. This data is also in the literature, but the all-tunneling Hamiltonians used could only fit each of the two torsional states separately. At the time of writing this abstract, we have preliminary fits of about 1200 methylamine transitions to 25 or 30 torsion-inversion-rotation parameters, but these hybrid-program fits are not yet at the same level as the all-tunneling-program fits in the literature. We hope to report significant further progress on this work in June. I. Kleiner and J. T. Hougen, J Phys Chem A. 119, 10664-76 (2015)

  20. Potential chlorofluorocarbon replacements: OH reaction rate constants between 250 and 315 K and infrared absorption spectra

    Science.gov (United States)

    Garland, Nancy L.; Medhurst, Laura J.; Nelson, H. H.

    1993-12-01

    We measured the rate constant for reactions of the OH radical with several potential chlorofluorocarbon replacements over the temperature range 251-314 K using laser photolysis laser-induced fluorescence techniques. The compounds studied and Arrhenius parameters determined from fits to the measured rate constants are as follows: CHF2OCHF2 (E 134), k(T) = (5.4 ± 3.5) × 10-13 cm3 s-1 exp [(-3.1 ± 0.4 kcal mol-1)/RT]; CF3CH2CF3 (FC 236fa), k(T) = (2.0 ± 1.0) × 10-14 cm3 s-1 exp [(-1.8 ± 0.3 kcal mol-1)/RT]; CF3CHFCHF2 (FC 236ea), k(T) = (2.0 ± 0.9) × 10-13 cm3 s-1 exp [(-2.0 ± 0.3 kcal mol-1)/RT]; and CF3CF2CH2F (FC 236cb), k(T)= (2.6 ± 1.6) × 10-13 cm3 s-1 exp [(-2.2 ± 0.4 kcal mol-1)/RT]. The measured activation energies (2-3 kcal mol-1) are consistent with a mechanism of H atom abstraction. The tropospheric lifetimes, estimated from the measured OH reaction rates, and measured integrated infrared absorption cross sections over the range 770 to 1430 cm-1 suggest that E 134 and FC 236fa may have significant global warming potential, while FC 236ea and FC 236cb do not.

  1. Matrix infrared spectra and density functional calculations of TiO3 and TiO5 in solid argon.

    Science.gov (United States)

    Gong, Yu; Zhou, Mingfei

    2008-10-09

    The reaction of titanium monoxide molecules and O2 was studied by using matrix isolation infrared spectroscopy as well as theoretical calculations. The titanium monoxide molecule reacts with O2 to form TiO 3 spontaneously on annealing. The TiO3 molecule is characterized to be a side-on bonded peroxo titanium monoxide complex, (eta(2)-O2)TiO, which has a nonplanar Cs symmetry with a 1A' ground state. The (eta(2)-O2)TiO complex can further coordinate another dioxygen to give TiO 5, a disuperoxo titanium monoxide complex, (eta(2)-O2)(2)TiO, which possesses a 3A'' ground state and a nonplanar Cs geometry.

  2. Near-infrared spectra of Penicillium camemberti strains separated by extended multiplicative signal correction improved prediction of physical and chemical variations

    DEFF Research Database (Denmark)

    Decker, Marianne; Nielsen, Per Væggemose; Martens, Harald

    2005-01-01

    signal correction (TWEMSC) preprocessing, whereby three patterns of variation in near-infrared (NIR) log(1/R) spectra of fungal colonies could be separated mathematically: (1) physical light scattering and its wavelength dependency, (2) differences in light absorption of water due to varying sample...

  3. High-accuracy water potential energy surface for the calculation of infrared spectra

    Science.gov (United States)

    Mizus, Irina I.; Kyuberis, Aleksandra A.; Zobov, Nikolai F.; Makhnev, Vladimir Yu.; Polyansky, Oleg L.; Tennyson, Jonathan

    2018-03-01

    Transition intensities for small molecules such as water and CO2 can now be computed with such high accuracy that they are being used to systematically replace measurements in standard databases. These calculations use high-accuracy ab initio dipole moment surfaces and wave functions from spectroscopically determined potential energy surfaces (PESs). Here, an extra high-accuracy PES of the water molecule (H216O) is produced starting from an ab initio PES which is then refined to empirical rovibrational energy levels. Variational nuclear motion calculations using this PES reproduce the fitted energy levels with a standard deviation of 0.011 cm-1, approximately three times their stated uncertainty. The use of wave functions computed with this refined PES is found to improve the predicted transition intensities for selected (problematic) transitions. A new room temperature line list for H216O is presented. It is suggested that the associated set of line intensities is the most accurate available to date for this species. This article is part of the theme issue `Modern theoretical chemistry'.

  4. High-accuracy water potential energy surface for the calculation of infrared spectra.

    Science.gov (United States)

    Mizus, Irina I; Kyuberis, Aleksandra A; Zobov, Nikolai F; Makhnev, Vladimir Yu; Polyansky, Oleg L; Tennyson, Jonathan

    2018-03-13

    Transition intensities for small molecules such as water and CO 2 can now be computed with such high accuracy that they are being used to systematically replace measurements in standard databases. These calculations use high-accuracy ab initio dipole moment surfaces and wave functions from spectroscopically determined potential energy surfaces (PESs). Here, an extra high-accuracy PES of the water molecule (H 2 16 O) is produced starting from an ab initio PES which is then refined to empirical rovibrational energy levels. Variational nuclear motion calculations using this PES reproduce the fitted energy levels with a standard deviation of 0.011 cm -1 , approximately three times their stated uncertainty. The use of wave functions computed with this refined PES is found to improve the predicted transition intensities for selected (problematic) transitions. A new room temperature line list for H 2 16 O is presented. It is suggested that the associated set of line intensities is the most accurate available to date for this species.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  5. Influence of temperature on water and aqueous glucose absorption spectra in the near- and mid-infrared regions at physiologically relevant temperatures

    DEFF Research Database (Denmark)

    Jensen, P.S.; Bak, J.; Andersson-Engels, S.

    2003-01-01

    Near- and mid-infrared absorption spectra of pure water and aqueous 1.0 g/dL glucose solutions in the wavenumber range 8000-950 cm(-1) were measured in the temperature range 30-42 C in steps of 2 degreesC. Measurements were carried out with an FT-IR spectrometer and a variable pathlength...... degreesC water spectrum from the spectra measured at other temperatures. The difference spectra reveal that the effect of temperature is highest in the vicinity of the strong absorption bands, with a number of isosbestic points with no temperature dependence and relatively flat plateaus in between....... The change in water absorption associated with the addition of glucose has also been studied. An estimate of these effects is given and is related to the expected level of infrared signals from glucose in humans....

  6. Theoretical Investigation of the Effect of the Rare Gas Matrices on the Vibrational Spectra of Solvated Molecular Ions: Cu+CO

    Czech Academy of Sciences Publication Activity Database

    Bludský, Ota; Šilhan, Martin; Nachtigall, Petr

    2002-01-01

    Roč. 117, č. 20 (2002), s. 9298-9305 ISSN 0021-9606 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : vibrational spectra * solvated molecular ions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.998, year: 2002

  7. Retrieval of Precise Radial Velocities from Near-infrared High-resolution Spectra of Low-mass Stars

    Science.gov (United States)

    Gao, Peter; Plavchan, P.; Gagné, J.; Furlan, E.; Bottom, M.; Anglada-Escudé, G.; White, R.; Davison, C. L.; Beichman, C.; Brinkworth, C.; Johnson, J.; Ciardi, D.; Wallace, K.; Mennesson, B.; von Braun, K.; Vasisht, G.; Prato, L.; Kane, S. R.; Tanner, A.; Crawford, T. J.; Latham, D.; Rougeot, R.; Geneser, C. S.; Catanzarite, J.

    2016-10-01

    Given that low-mass stars have intrinsically low luminosities at optical wavelengths and a propensity for stellar activity, it is advantageous for radial velocity (RV) surveys of these objects to use near-infrared (NIR) wavelengths. In this work, we describe and test a novel RV extraction pipeline dedicated to retrieving RVs from low-mass stars using NIR spectra taken by the CSHELL spectrograph at the NASA Infrared Telescope Facility, where a methane isotopologue gas cell is used for wavelength calibration. The pipeline minimizes the residuals between the observations and a spectral model composed of templates for the target star, the gas cell, and atmospheric telluric absorption; models of the line-spread function, continuum curvature, and sinusoidal fringing; and a parameterization of the wavelength solution. The stellar template is derived iteratively from the science observations themselves without a need for separate observations dedicated to retrieving it. Despite limitations from CSHELL’s narrow wavelength range and instrumental systematics, we are able to (1) obtain an RV precision of 35 m s-1 for the RV standard star GJ 15 A over a time baseline of 817 days, reaching the photon noise limit for our attained signal-to-noise ratio; (2) achieve ˜3 m s-1 RV precision for the M giant SV Peg over a baseline of several days and confirm its long-term RV trend due to stellar pulsations, as well as obtain nightly noise floors of ˜2-6 m s-1 and (3) show that our data are consistent with the known masses, periods, and orbital eccentricities of the two most massive planets orbiting GJ 876. Future applications of our pipeline to RV surveys using the next generation of NIR spectrographs, such as iSHELL, will enable the potential detection of super-Earths and mini-Neptunes in the habitable zones of M dwarfs.

  8. Comparison of XH2O Retrieved from GOSAT Short-Wavelength Infrared Spectra with Observations from the TCCON Network

    Directory of Open Access Journals (Sweden)

    Eric Dupuy

    2016-05-01

    Full Text Available Understanding the atmospheric distribution of water (H 2 O is crucial for global warming studies and climate change mitigation. In this context, reliable satellite data are extremely valuable for their global and continuous coverage, once their quality has been assessed. Short-wavelength infrared spectra are acquired by the Thermal And Near-infrared Sensor for carbon Observation-Fourier Transform Spectrometer (TANSO-FTS aboard the Greenhouse gases Observing Satellite (GOSAT. From these, column-averaged dry-air mole fractions of carbon dioxide, methane and water vapor (XH 2 O have been retrieved at the National Institute for Environmental Studies (NIES, Japan and are available as a Level 2 research product. We compare the NIES XH 2 O data, Version 02.21, with retrievals from the ground-based Total Carbon Column Observing Network (TCCON, Version GGG2014. The datasets are in good overall agreement, with GOSAT data showing a slight global low bias of −3.1% ± 24.0%, good consistency over different locations (station bias of −1.53% ± 10.35% and reasonable correlation with TCCON (R = 0.89. We identified two potential sources of discrepancy between the NIES and TCCON retrievals over land. While the TCCON XH 2 O amounts can reach 6000–7000 ppm when the atmospheric water content is high, the correlated NIES values do not exceed 5500 ppm. This could be due to a dry bias of TANSO-FTS in situations of high humidity and aerosol content. We also determined that the GOSAT-TCCON differences directly depend on the altitude difference between the TANSO-FTS footprint and the TCCON site. Further analysis will account for these biases, but the NIES V02.21 XH 2 O product, after public release, can already be useful for water cycle studies.

  9. The infrared, Raman, NMR and UV spectra, ab initio calculations and spectral assignments of 2-amino-4-chloro-6-methoxypyrimidine.

    Science.gov (United States)

    Cinar, Z; Karabacak, M; Cinar, M; Kurt, M; Chinna Babu, P; Sundaraganesan, N

    2013-12-01

    The 2-amino-4-chloro-6-methoxypyrimidine abbreviated as ACMP have been investigated by both the experimental and theoretical methods; through this work we provide the essential fact about the structural and vibrational insights. The optimized molecular structure, atomic charges, vibrational frequencies and ultraviolet spectral interpretation of ACMP have been studied by performing DFT/B3LYP/6-311++G(df,pd) level of theory. The FT-IR, FT-Raman spectra were recorded in the region 4000-400 cm(-1) and 4000-50 cm(-1) respectively. The UV absorption spectrum of the compound that dissolved in ethanol and water solution were recorded in the range of 200-400 nm. The scaled wavenumbers are compared with the experimental values. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. Based on the UV spectrum and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. The (1)H, (13)C and DEPT 135 nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated using with the Gauge Including Atomic Orbital (GIAO) method and compared with experimental results. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Polarized matrix infrared spectra of cyclopentadienone: observations, calculations, and assignment for an important intermediate in combustion and biomass pyrolysis.

    Science.gov (United States)

    Ormond, Thomas K; Scheer, Adam M; Nimlos, Mark R; Robichaud, David J; Daily, John W; Stanton, John F; Ellison, G Barney

    2014-01-30

    A detailed vibrational analysis of the infrared spectra of cyclopentadienone (C5H4═O) in rare gas matrices has been carried out. Ab initio coupled-cluster anharmonic force field calculations were used to guide the assignments. Flash pyrolysis of o-phenylene sulfite (C6H4O2SO) was used to provide a molecular beam of C5H4═O entrained in a rare gas carrier. The beam was interrogated with time-of-flight photoionization mass spectrometry (PIMS), confirming the clean, intense production of C5H4═O. Matrix isolation infrared spectroscopy coupled with 355 nm polarized UV for photoorientation and linear dichroism experiments was used to determine the symmetries of the vibrations. Cyclopentadienone has 24 fundamental vibrational modes, Γvib = 9a1 ⊕ 3a2 ⊕ 4b1 ⊕ 8b2. Using vibrational perturbation theory and a deperturbation-diagonalization method, we report assignments of the following fundamental modes (cm(-1)) in a 4 K neon matrix: the a1 modes of X̃ (1)A1 C5H4═O are found to be ν1 = 3107, ν2 = (3100, 3099), ν3 = 1735, ν5 = 1333, ν7 = 952, ν8 = 843, and ν9 = 651; the inferred a2 modes are ν10 = 933, and ν11 = 722; the b1 modes are ν13 = 932, ν14 = 822, and ν15 = 629; the b2 fundamentals are ν17 = 3143, ν18 = (3078, 3076) ν19 = (1601 or 1595), ν20 = 1283, ν21 = 1138, ν22 = 1066, ν23 = 738, and ν24 = 458. The modes ν4 and ν6 were too weak to be detected, ν12 is dipole-forbidden and its position cannot be inferred from combination and overtone bands, and ν16 is below our detection range (calculations, assigned as two quantum transitions, and used to assign some of the weak and infrared inactive fundamental vibrations.

  11. Theoretical luminescence spectra in p-type quantum wells and superlattices based on InGaAsN

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Thiago Freire de; Rodrigues, Sara Cristina Pinto [Universidade Federal Rural de Pernambuco (UFRPE), Recife, PE (Brazil). Dept. de Fisica; Silva Junior, Eronides Felisberto da [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Fisica; Sipahi, Guilherme Matos [Universidade de Sao Paulo (IFSC/USP), Sao Carlos, SP (Brazil). Inst. de Fisica; Scolfaro, Luisa Maria Ribeiro [Texas State University, San Marcos, TX (United States), Dept. of Physics

    2012-07-01

    Full text: In the past few years, the dilute nitride system, InGaAsN, is proposed as a good candidate for several device applications. InGaAsN is considered a promising material for laser devices working at 1:3 or 1:5{mu}m and high-efficiency multijunction solar cells. Incorporation of In and N into GaAs result in a strong redshift of the emission wavelength. Besides, the strain can be minimized since the opposite effect of In and N on the lattice constant enables lattice matching of InGaAsN on GaAs. However, despite their great potential for applications, the understanding of their physical properties is rather incomplete. In particular, the dominant mechanisms of light emission in these alloys and their dependence on the nitrogen composition are not well established. Such information is crucial not only for a better understanding of the optical properties of the nitrogen containing III-V alloys, but also for a better technological control of alloy formation and optimization light emission efficiency. Another point concerns to investigation in p-type doping in InGaAsN. This is of great importance since, for example, can improve the transport in HBT (Heterojunction Bipolar Transistors) devices. In this work we report on theoretical luminescence spectra calculations for p-doped GaAs/InGaAsN quantum wells and superlattices. The calculations are performed within the k-vector.p-vector method by solving the full 8 x 8 Kane Hamiltonian, generalized to treat different materials. Strain effects due the lattice mismatch between InGaAsN and GaAs are taken into account. By varying the acceptor concentration we analyze the effect of exchange-correlation, which plays an important role in profile potential and electronic transition. These results can explain several important aspects about optical properties in these systems. (author)

  12. A comparative study on experimental and theoretical ESR spectra of lactic acid polymers irradiated by gamma rays

    International Nuclear Information System (INIS)

    Kantoglu, Oe.; Oezbey, T.; Gueven, O.

    1998-01-01

    Homo polymers of L-Lactic acid (LLA) and D,L-Lactic acid (DLLA), being biocompatible and absorbable in body iluids have recently found wide applications in the preparation of surgical sutures, controlled drug delivery systems, burn wound coverings etc. For sometime these polymers have also been prepared in the form of plates and screws for mandibular fracture fixation, tissue implants. Their chemical sensitivities against relatively high temperatures and hydrolysis with water make them unsuitable for conventional sterilization techniques like hot water vapor and ethylene oxide. Sterilization of the devices made of these polymers is therefore possible by gamma ray irradiation. This has initiated a number of research works in order to better understand the effects of ionizing radiation on this polymer. The aim of this study is to determine the possible radical types, their location on macromolecular structure and the reasons for peak shifts in the experimental and theoretical ESR spectra. Polymer samples were irradiated in air and in vacuum (10□□ torr) to 25 kGy sterilization dose at the dose rate 0.59 kGy/h and at room temperature by 60 Co γ-irradiator. Despite being chemically the same radical type, some differences were observed in the splitting of peaks of PLLA and PDLLA samples. These differences were determined and compared by means of fitting studies. Firstly, PLLA was characterized and its g and hyperfine splitting values were found as 2.0032±0.0002 and 20.37±0.2. In the characterization study of PDLLA, it was found that one of the nearest two radicals was on the upper and the other one was on the lower plane of PDLLA chain. (author)

  13. Effects of mercury on visible/near-infrared reflectance spectra of mustard spinach plants (Brassica rapa P.)

    Energy Technology Data Exchange (ETDEWEB)

    Dunagan, Sarah C. [Department of Earth and Environmental Sciences, Wesleyan University, 265 Church Street, Middletown, CT 06459 (United States)]. E-mail: sdunagan@wesleyan.edu; Gilmore, Martha S. [Department of Earth and Environmental Sciences, Wesleyan University, 265 Church Street, Middletown, CT 06459 (United States)]. E-mail: mgilmore@wesleyan.edu; Varekamp, Johan C. [Department of Earth and Environmental Sciences, Wesleyan University, 265 Church Street, Middletown, CT 06459 (United States)]. E-mail: jvarekamp@wesleyan.edu

    2007-07-15

    Mustard spinach plants were grown in mercury-spiked and contaminated soils collected in the field under controlled laboratory conditions over a full growth cycle to test if vegetation grown in these soils has discernible characteristics in visible/near-infrared (VNIR) spectra. Foliar Hg concentrations (0.174-3.993 ppm) of the Mustard spinach plants were positively correlated with Hg concentration of soils and varied throughout the growing season. Equations relating foliar Hg concentration to spectral reflectance, its first derivative, and selected vegetation indices were generated using stepwise multiple linear regression. Significant correlations are found for limited wavelengths for specific treatments and dates. Ratio Vegetation Index (RVI) and Red Edge Position (REP) values of plants in Hg-spiked and field-contaminated soils are significantly lower relative to control plants during the early and middle portions of the growth cycle which may be related to lower chlorophyll abundance or functioning in Hg-contaminated plants. - Some spectral characteristics of leaves of Brassica rapa P. may be associated with foliar mercury content.

  14. Classification of dry-cured hams according to the maturation time using near infrared spectra and artificial neural networks.

    Science.gov (United States)

    Prevolnik, M; Andronikov, D; Žlender, B; Font-i-Furnols, M; Novič, M; Škorjanc, D; Čandek-Potokar, M

    2014-01-01

    An attempt to classify dry-cured hams according to the maturation time on the basis of near infrared (NIR) spectra was studied. The study comprised 128 samples of biceps femoris (BF) muscle from dry-cured hams matured for 10 (n=32), 12 (n=32), 14 (n=32) or 16 months (n=32). Samples were minced and scanned in the wavelength range from 400 to 2500 nm using spectrometer NIR System model 6500 (Silver Spring, MD, USA). Spectral data were used for i) splitting of samples into the training and test set using 2D Kohonen artificial neural networks (ANN) and for ii) construction of classification models using counter-propagation ANN (CP-ANN). Different models were tested, and the one selected was based on the lowest percentage of misclassified test samples (external validation). Overall correctness of the classification was 79.7%, which demonstrates practical relevance of using NIR spectroscopy and ANN for dry-cured ham processing control. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Infrared Spectra of the n-PROPYL and i-PROPYL Radicals in Solid Para-Hydrogen

    Science.gov (United States)

    Pullen, Gregory T.; Franke, Peter R.; Douberly, Gary E.; Lee, Yuan-Pern

    2017-06-01

    We report the infrared spectra of the n-propyl and i-propyl radicals measured in solid para-hydrogen (p-H_2) matrices at 3.2 K. n-Propyl and i-propyl radicals were produced via the 248 nm irradiation of matrices formed by co-depositing p-H_2 and either 1-Iodopropane (n-propyl) or 2-Iodopropane (i-propyl). Secondary photolysis was used to group spectral lines all due to the same species. Lines in the C-H stretching region were compared to previous work using the Helium Nanodroplet Isolation (HENDI) technique, and are in excellent agreement. In addition to a few lines previously measured in Ar matrices, we observe many previously unreported bands below 2000 \\wn, which we attribute to the n-propyl and i-propyl radicals. The assignment of features below 2000 \\wn are made via comparisons to anharmonic VPT2+K frequency computations. Peter R. Franke, Daniel P. Tabor, Christopher P. Moradi, Gary E. Douberly, Jay Agarwal, Henry F. Schaefer III, and Edwin L. Sibert III, Journal of Chemical Physics 145, 224304 (2016).

  16. Infrared vibration-rotation spectra of the ClO radical using tunable diode laser spectroscopy. [ozone destruction in stratosphere

    Science.gov (United States)

    Rogowski, R. S.; Bair, C. H.; Wade, W. R.; Hoell, J. M.; Copeland, G. E.

    1978-01-01

    Tunable diode laser spectroscopy is used to measure the infrared vibration-rotation spectra of the ClO radical. The radical is generated in a flow system where a Cl2-He mixture passes through a microwave discharge to dissociate the Cl2. An O3-O2 mixture from an ozone generator is injected into the system downstream of the microwave discharge where O3 combines with Cl to form ClO. By adjusting the gas flow rates to yield an excess of Cl atoms, all the ozone is combined. ClO concentration is measured with UV absorption at 2577 and 2772 A and a deuterium lamp as a continuous source. Total cell pressure is 5.5 torr. The diode laser spectrometer is calibrated with ammonia lines as a reference where possible. The frequency of vibration-rotation lines is expressed as a function of rotational quantum number, fundamental vibrational frequency, and the rotational constants of the upper and lower vibrational states.

  17. Theoretical modeling of infrared emission from neutral and charged polycyclic aromatic hydrocarbons. II.

    NARCIS (Netherlands)

    Bakes, ELO; Tielens, AGGM; Bauschlicher, CW; Hudgins, DM; Allamandola, LJ

    2001-01-01

    The nature of the carriers of the interstellar infrared (IR) emission features between 3.3 and 12.7 mum is complex. We must consider emission from a family of polycyclic aromatic hydrocarbons (PAHs) in a multiplicity of cationic charge states (+1, +2, +3, and so on), along with neutral and anionic

  18. Non-intrusive measurement of emission indices. A new approach to the evaluation of infrared spectra emitted by aircraft engine exhaust gases

    Energy Technology Data Exchange (ETDEWEB)

    Lindermeir, E.; Haschberger, P.; Tank, V. [Deutsche Forschungsanstalt fuer Luft- und Raumfahrt e.V. (DLR), Wessling (Germany). Inst. fuer Optoelektronik

    1997-12-31

    A non-intrusive method is used to determine the emission indices of a research aircraft`s engine in-flight. The principle is based on the Fourier Transform Infrared Spectrometer MIROR which was specifically designed and built for operation aboard aircrafts. This device measures the spectrum of the infrared radiation emitted by the hot exhaust gas under cruise conditions. From these spectra mixing ratios and emission indices can be derived. An extension to previously applied evaluation schemes is proposed: Whereas formerly the plume was assumed a homogeneous layer of gas, temperature and concentration profiles are now introduced to the evaluation procedure. (author) 5 refs.

  19. Infrared and Raman spectra of bicyclic molecules using scaled noncorrelated and correlated {ital ab initio} force fields

    Energy Technology Data Exchange (ETDEWEB)

    Collier, W.B. [Department of Chemistry, Oral Roberts University, Tulsa, Oklahoma 74171 (United States); Magdo, I. [Gedeon Richter Ltd., Molecular Design Unit, P.O. Box 27, H-1475, Budapest (Hungary); Klots, T.D. [Bartlesville Thermodynamic Group, BDM Petroleum Technologies, P.O. Box 2543, Bartlesville, Oklahoma 74005 (United States)

    1999-03-01

    This paper reports the application of a scaled {ital ab initio} calculated harmonic force field to predict the frequencies, infrared intensities, Raman intensities, and depolarization ratios of benzofuran, benzothiophene, indole, benzothiazole, and benzoxazole. The theoretical calculations were made using the Hartree{endash}Fock HF/3-21G{sup {asterisk}} and HF/6-31G{sup {asterisk}} basis sets and density-functional theory (DFT)B3-LYP/6-31G{sup {asterisk}} levels. The equilibrium calculated force constants are scaled according to the method of Pulay and compared with the experimentally determined frequencies, intensities, and depolarization ratios to assess the accuracy and fit of the theoretical calculation. Methods for quantitative comparison of intensities were developed. The double numerical differentiation algorithm of Komornicki and McIver was analyzed and used to calculate the Raman intensities for the (DFT)B3-LYP/6-31G{sup {asterisk}} model. The (DFT)B3-LYP/6-31G{sup {asterisk}} model is approaching the harmonic limit in the planar and nonplanar refinement of these bicyclics with wave number fits of 5 and 4 cm{sup {minus}1}, respectively. It reduces the need for scale factors and increases their transfer accuracy, largely because the scale factors values cluster near unity. The Komornicki and McIver algorithm is still a viable method for calculating Raman intensity information for methods that do not have analytic routines programmed. The main shortcoming to this method may lie in the tighter self-consistent field (SCF) convergence criterion possibly needed to calculate Raman intensities for the totally symmetric modes of large molecules. The (DFT)B3-LYP/6-31G{sup {asterisk}} model was superior for calculating the planar intensities, but equal to the HF methods for predicting the nonplanar intensities. {copyright} {ital 1999 American Institute of Physics.}

  20. Stratospheric and mesospheric pressure-temperature profiles from rotational analysis of CO2 lines in atmospheric trace molecule spectroscopy/ATLAS 1 infrared solar occultation spectra

    Science.gov (United States)

    Stiller, G. P.; Gunson, M. R.; Lowes, L. L.; Abrams, M. C.; Raper, O. F.; Farmer, C. B.; Zander, R.; Rinsland, C. P.

    1995-01-01

    A simple, classical, and expedient method for the retrieval of atmospheric pressure-temperature profiles has been applied to the high-resolution infrared solar absorption spectra obtained with the atmospheric trace molecule spectroscopy (ATMOS) instrument. The basis for this method is a rotational analysis of retrieved apparent abundances from CO2 rovibrational absorption lines, employing existing constituent concentration retrieval software used in the analysis of data returned by ATMOS. Pressure-temperature profiles derived from spectra acquired during the ATLAS 1 space shuttle mission of March-April 1992 are quantitatively evaluated and compared with climatological and meteorological data as a means of assessing the validity of this approach.

  1. Infrared Spectra of the 1-Chloromethyl-1-methylallyl and 1-Chloromethyl-2-methylallyl Radicals Isolated in Solid para-Hydrogen.

    Science.gov (United States)

    Amicangelo, Jay C; Lee, Yuan-Pern

    2017-11-22

    The reaction of chlorine atoms (Cl) with isoprene (2-methyl-1,3-butadiene, C 5 H 8 ) in solid para-hydrogen (p-H 2 ) matrices at 3.2 K was studied using infrared (IR) spectroscopy. Mixtures of C 5 H 8 and Cl 2 were codeposited in p-H 2 at 3.2 K, followed by irradiation with ultraviolet light at 365 nm to induce the photodissociation of Cl 2 and the subsequent reaction of the Cl atoms with C 5 H 8 . Upon 365 nm photolysis, a multitude of new lines appeared in the IR spectrum, and, based on the secondary photolysis behavior, it was determined that the majority of the new lines belong to two distinct chemical species, designated as set A (intense lines at 1237.9, 807.8, and 605.6/608.2 cm -1 , and several other weaker lines) and set B (intense lines at 942.4, 1257.7, 796.7/798.5, 667.9, and 569.7 cm -1 , and several other weaker lines). Quantum-chemical calculations were performed at the B3PW91/6-311++G(2d,2p) level for ·C 5 H 7 and the four possible isomers of the ·C 5 H 8 Cl radicals, produced from the addition of the Cl atom to the four distinct sites of carbon atoms in C 5 H 8 , to determine the relative energetics and predict IR spectra for each radical. The newly observed lines of sets A and B are assigned to the 1-chloromethyl-2-methylallyl radical (addition to carbon 4) and the 1-chloromethyl-1-methylallyl radical (addition to carbon 1) according to comparison with predicted IR spectra of possible products. The 1-chloromethyl-2-methylallyl radical and 1-chloromethyl-1-methylallyl radicals were predicted to be the most stable, with the latter ∼8 kJ mol -1 lower in energy than the former. The ratio of the 1-chloromethyl-1-methylallyl to the 1-chloromethyl-2-methylallyl radicals is estimated to be (1.2 ± 0.5):1.0, indicating that the two radicals are produced in approximately equal amounts. The exclusive production of the radicals involving the addition of the Cl atom to the two terminal carbons of isoprene is analogous to what was previously observed for

  2. Quantitative analysis of the hydration of lithium salts in water using multivariate curve resolution of near-infrared spectra

    International Nuclear Information System (INIS)

    Barba, M. Isabel; Larrechi, M. Soledad; Coronas, Alberto

    2016-01-01

    The hydration process of lithium iodide, lithium bromide, lithium chloride and lithium nitrate in water was analyzed quantitatively by applying multivariate curve resolution alternating least squares (MCR-ALS) to their near infrared spectra recorded between 850 nm and 1100 nm. The experiments were carried out using solutions with a salt mass fraction between 0% and 72% for lithium bromide, between 0% and 67% for lithium nitrate and between 0% and 62% for lithium chloride and lithium iodide at 323.15 K, 333.15 K, 343.15 K and 353.15 K, respectively. Three factors were determined for lithium bromide and lithium iodide and two factors for the lithium chloride and lithium nitrate by singular value decomposition (SVD) of their spectral data matrices. These factors are associated with various chemical environments in which there are aqueous clusters containing the ions of the salts and non-coordinated water molecules. Spectra and concentration profiles of non-coordinated water and cluster aqueous were retrieved by MCR-ALS. The amount of water involved in the process of hydration of the various salts was quantified. The results show that the water absorption capacity increases in the following order LiI < LiBr < LiNO 3  < LiCl. The salt concentration at which there is no free water in the medium was calculated at each one of the temperatures considered. The values ranged between 62.6 and 65.1% for LiBr, 45.5–48.3% for LiCl, 60.4–61.2% for LiI and 60.3–63.7% for LiNO 3 . These values are an initial approach to determining the concentration as from which crystal formation is favored. - Highlights: • Quantitative analysis of the hydration of lithium salts in water. • The absorption capacity of the electrolytes in function of the salt is evaluated. • The lithium salt concentration is estimated when the crystal formation is favored.

  3. Infrared Spectra of Novel NgBeSO2 Complexes (Ng = Ne, Ar, Kr, Xe) in Low Temperature Matrixes.

    Science.gov (United States)

    Yu, Wenjie; Liu, Xing; Xu, Bing; Xing, Xiaopeng; Wang, Xuefeng

    2016-11-03

    The novel noble-gas complexes NgBeSO 2 (Ng = Ne, Ar, Kr, Xe) have been prepared in the laser-evaporated beryllium atom reactions with SO 2 in low-temperature matrixes. Doped with heavier noble gas, the guest (Ar, Kr, Xe) atom can substitute neon to form more stable complex. Infrared spectroscopy and theoretical calculations are used to confirm the band assignment. The dissociation energies are calculated at 0.9, 4.0, 4.7, and 6.0 kcal/mol for NeBeSO 2 , ArBeSO 2 , KrBeSO 2 , and XeBeSO 2 , respectively, at the CCSD(T) level. Quantum chemical calculations demonstrate that the Ng-Be bonds in NgBeSO 2 could be formed by the combination of electron-donation and ion-induced dipole interactions. The Wiberg bond index (WBI) values of Ng-Be bonds and LOL (localized orbital locator) profile indicate that the Ng-Be bond exhibits a gradual increase in covalent character along Ne to Xe.

  4. Infrared spectra reveal box-like structures for a pentamer and hexamer of mixed carbon dioxide-acetylene clusters.

    Science.gov (United States)

    Rezaei, Mojtaba; Norooz Oliaee, J; Moazzen-Ahmadi, N; McKellar, A R W

    2016-01-21

    Except for a few cases like water and carbon dioxide, identification and structural characterization of clusters with more than four monomers is rare. Here, we provide experimental and theoretical evidence for existence of box-like structures for a pentamer and a hexamer of mixed carbon dioxide-acetylene clusters. Two mid-infrared cluster absorption bands are observed in the CO2ν3 band region using a tunable diode laser to probe a pulsed supersonic jet. Each requires the presence of both carbon dioxide and acetylene in the jet, and (from observed rotational spacings) involves clusters containing about 4 to 7 molecules. Structures are predicted for mixed CO2 + C2H2 clusters using a distributed multipole model, and the bands are assigned to a specific pentamer, (CO2)3-(C2H2)2, and hexamer, (CO2)4-(C2H2)2. The hexamer has a box-like structure whose D2d symmetry is supported by observed intensity alternation in the spectrum. The pentamer has a closely related structure which is obtained by removing one CO2 molecule from the hexamer. These are among the largest mixed molecular clusters to be assigned by high-resolution spectroscopy.

  5. NBO, NMR, UV, FT-IR, FT-Raman spectra and molecular structure (monomeric and dimeric structures) investigation of 4-Chloro-3,5-Xylenol: a combined experimental and theoretical study.

    Science.gov (United States)

    Arivazhagan, M; Gayathri, R

    2013-12-01

    In this work, a joint experimental (FTIR and FT-Raman) and theoretical (DFT and ab initio) study on the structure and the vibrations of 4-Chloro-3,5-Xylenol (CXL) are compared and analyzed. CXL is a chlorinated phenolic antiseptic which is a bactericide against most gram-positive bacteria. The first hyperpolarizability (β0) of this novel molecular system and related non-linear properties of CXL are calculated using HF/6-311++G(d,p) method on the finite-field approach. The energy and oscillator strength calculated using absorption spectra (UV-Vis spectrum), this spectral analysis confirms the charge transfer of the molecule. The theoretical (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by Gauge Including Atomic Orbital (GIAO) method, to analyze the molecular environment as well as the delocalization activities of electron clouds. The directly calculated ionization potential (IP), electron affinity (EA), electronegativity (χ), chemical hardness (η), first electron excitation energy (τ) and electrophilicity index (ω) as well as local reactivity (S) analyzed using HOMO and LUMO energies; the energy band gap are also determined. NBO analysis shows that charge in electron density(ED) in the σ(*) and π(*) antibonding orbitals and E((2)) energies confirms the occurrence of ICT (Intramolecular Charge Transfer) within the molecule. Inter molecular hydrogen bonds exist between -OH group, give the evidence for the formation of dimer entities in the title molecule. The influences of chlorine atom, hydroxyl group and methyl group on the geometry of benzene and its normal modes of vibrations (monomer and dimer of CXL) have also been discussed. Finally the calculated results were applied to simulate Infrared and Raman spectra of the title molecule which show good agreement with observed spectra. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. A new Schiff base compound N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone): synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, 1H NMR and 13C NMR spectra.

    Science.gov (United States)

    Saheb, Vahid; Sheikhshoaie, Iran

    2011-10-15

    The Schiff base compound, N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone) (NDHA) is synthesized through the condensation of 2-hydroxylacetophenone and 2,2-dimethyl 1,3-amino propane in methanol at ambient temperature. The yellow crystalline precipitate is used for X-ray single-crystal determination and measuring Fourier transform infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP, PBEPBE and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the FTIR, (1)H NMR and (13)C NMR spectra of the compound. Time-dependent density functional theory (TDDFT) method is used to calculate the UV-visible spectrum of NDHA. Vibrational frequencies are determined experimentally and compared with those obtained theoretically. Vibrational assignments and analysis of the fundamental modes of the compound are also performed. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR and (13)C NMR chemical shifts calculated by all DFT methods are consistent with the experimental data. However, the NMR shielding tensors computed at the B3LYP/6-31+G(d,p) level of theory are in better agreement with experimental (1)H NMR and (13)C NMR spectra. The electronic absorption spectrum calculated at the B3LYP/6-31+G(d,p) level by using TD-DFT method is in accordance with the observed UV-visible spectrum of NDHA. In addition, some quantum descriptors of the molecule are calculated and conformational analysis is performed and the results were compared with the crystallographic data. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. NBO, NMR, UV, FT-IR, FT-Raman spectra and molecular structure (monomeric and dimeric structures) investigation of 4-Chloro-3,5-Xylenol: A combined experimental and theoretical study

    Science.gov (United States)

    Arivazhagan, M.; Gayathri, R.

    2013-12-01

    In this work, a joint experimental (FTIR and FT-Raman) and theoretical (DFT and ab initio) study on the structure and the vibrations of 4-Chloro-3,5-Xylenol (CXL) are compared and analyzed. CXL is a chlorinated phenolic antiseptic which is a bactericide against most gram-positive bacteria. The first hyperpolarizability (β0) of this novel molecular system and related non-linear properties of CXL are calculated using HF/6-311++G(d,p) method on the finite-field approach. The energy and oscillator strength calculated using absorption spectra (UV-Vis spectrum), this spectral analysis confirms the charge transfer of the molecule. The theoretical 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by Gauge Including Atomic Orbital (GIAO) method, to analyze the molecular environment as well as the delocalization activities of electron clouds. The directly calculated ionization potential (IP), electron affinity (EA), electronegativity (χ), chemical hardness (η), first electron excitation energy (τ) and electrophilicity index (ω) as well as local reactivity (S) analyzed using HOMO and LUMO energies; the energy band gap are also determined. NBO analysis shows that charge in electron density(ED) in the σ* and π* antibonding orbitals and E(2) energies confirms the occurrence of ICT (Intramolecular Charge Transfer) within the molecule. Inter molecular hydrogen bonds exist between -OH group, give the evidence for the formation of dimer entities in the title molecule. The influences of chlorine atom, hydroxyl group and methyl group on the geometry of benzene and its normal modes of vibrations (monomer and dimer of CXL) have also been discussed. Finally the calculated results were applied to simulate Infrared and Raman spectra of the title molecule which show good agreement with observed spectra.

  8. A novel tridentate Schiff base dioxo-molybdenum(VI) complex: synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, ¹H NMR and ¹³C NMR spectra.

    Science.gov (United States)

    Saheb, Vahid; Sheikhshoaie, Iran; Stoeckli-Evans, Helen

    2012-09-01

    A new dioxo-molybdenum(VI) complex [MoO(2)(L)(H(2)O)] has been synthesized, using 5-methoxy 2-[(2-hydroxypropylimino)methyl]phenol as tridentate ONO donor Schiff base ligand (H(2)L) and MoO(2)(acac)(2). The yellow crystals of the compound are used for single-crystal X-ray analysis and measuring Fourier Transform Infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the UV-visible, FTIR, (1)H NMR and (13)C NMR spectra of the compound. Vibrational assignments and analysis of the fundamental modes of the compound are performed. Time-dependent density functional theory (TDDFT) method is used to calculate the electronic transitions of the complex. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR shielding tensors computed at the B3LYP/DGDZVP level of theory is in agreement with experimental (1)H NMR spectra. However, the (13)C NMR shielding tensors computed at the B3LYP level, employing a combined basis set of DGDZVP for Mo and 6-31+G(2df,p) for other atoms, are in better agreement with experimental (13)C NMR spectra. The electronic transitions calculated at the B3LYP/DGDZVP level by using TD-DFT method is in accordance with the observed UV-visible spectrum of the compound. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Direct simulations of anharmonic infrared spectra using quantum mechanical/effective fragment potential molecular dynamics (QM/EFP-MD): methanol in water.

    Science.gov (United States)

    Ghosh, Manik Kumer; Lee, Jooyong; Choi, Cheol Ho; Cho, Minhaeng

    2012-09-13

    One of the most stringent tests for chemical accuracy of a hybrid quantum mechanical/molecular mechanical (QM/MM) molecular dynamics simulation method would be to directly compare the calculated vibrational spectra with the corresponding experimental results. Here, the applicability of hybrid QM/effective fragment potential (EFP) to the simulations of methanol infrared spectra is investigated in detail. It is demonstrated that the QM/EFP simulations in combination with time correlation function theory yield not only the fundamental transition bands but also the major overtone and combination bands of methanol dissolved in water in both mid- and near-IR regions. This clearly indicates that the QM/EFP-molecular dynamics can be a viable way of obtaining an anharmonic infrared spectrum that provides information on solvatochromic frequency shifts and fluctuations, solute-solvent interaction-induced dephasing, and anharmonic coupling effects on vibrational spectra of aqueous solutions. We anticipate that the computational protocol developed here can be effectively used to simulate both one- and two-dimensional vibrational spectra of biomolecules and chemically reactive systems in condensed phases.

  10. Rapid, nondestructive estimation of surface polymer layer thickness using attenuated total reflection fourier transform infrared (ATR FT-IR) spectroscopy and synthetic spectra derived from optical principles.

    Science.gov (United States)

    Weinstock, B André; Guiney, Linda M; Loose, Christopher

    2012-11-01

    We have developed a rapid, nondestructive analytical method that estimates the thickness of a surface polymer layer with high precision but unknown accuracy using a single attenuated total reflection Fourier transform infrared (ATR FT-IR) measurement. Because the method is rapid, nondestructive, and requires no sample preparation, it is ideal as a process analytical technique. Prior to implementation, the ATR FT-IR spectrum of the substrate layer pure component and the ATR FT-IR and real refractive index spectra of the surface layer pure component must be known. From these three input spectra a synthetic mid-infrared spectral matrix of surface layers 0 nm to 10,000 nm thick on substrate is created de novo. A minimum statistical distance match between a process sample's ATR FT-IR spectrum and the synthetic spectral matrix provides the thickness of that sample. We show that this method can be used to successfully estimate the thickness of polysulfobetaine surface modification, a hydrated polymeric surface layer covalently bonded onto a polyetherurethane substrate. A database of 1850 sample spectra was examined. Spectrochemical matrix-effect unknowns, such as the nonuniform and molecularly novel polysulfobetaine-polyetherurethane interface, were found to be minimal. A partial least squares regression analysis of the database spectra versus their thicknesses as calculated by the method described yielded an estimate of precision of ±52 nm.

  11. Ab initio MO calculations on the Structure and Raman and Infrared Spectra of the [Al4O2Cl10]2- oxide species in chloroaluminate melts

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    2007-01-01

    system of staggered (approximate D3d symmetry), in analogy with the linear Al-O-Al geometry of the analogous [Al2OF6]2- ion, found previously. The calculations included determination of the vibrational harmonic normal modes and the infrared and Raman spectra, (vibrational band wavenumbers and intensities......), without any empiric adjustments of the harmonic force constants, using constants directly predicted from the Gaussian 03W program. Previously obtained IR absorption and Raman scattering spectra of melts are assigned, by comparing to the ab initio quantum mechanical vibrational analysis results....... It is concluded that the small oxide content commonly found in basic and neutral tetrachloroaluminate melts, most probably consist of [Al4O2Cl10]2- ions and the vibrational spectra are given....

  12. Theoretical Studies of Starburst Infrared Emission: Luminosity Indicators in Dusty Photoionized Environments

    Science.gov (United States)

    Bottorff, Mark; LaMothe, Joseph; Momjian, Emmanuel; Verner, Ekaterina; Vinkovic, Dejan; Ferland, Gary J.

    1998-01-01

    The luminosity of the central source in ionizing radiation is an essential parameter in a photoionized environment and is one of the most fundamental physical quantities one can measure. We outline a method of determining the luminosity for any emission-line region using only infrared data. In dusty environments, grains compete with hydrogen in absorbing continuum radiation. Grains produce infrared emission, and hydrogen produces recombination lines. We have computed a very large variety of photoionization models, using ranges of abundances, grain mixtures, ionizing continua, densities, and ionization parameters. The conditions were appropriate for such diverse objects as H(II) regions, planetary nebulae, starburst galaxies, and the narrow- and broad-line regions of active nuclei. The ratio of the total thermal grain emission relative to H-Beta (IR/H-Beta) is the primary indicator of whether the cloud behaves as a classical Stroemgren sphere (a hydrogen-bounded nebula) or whether grains absorb most of the incident continuum (a dust-bounded nebula). We find two global limits: when IR/H-Beta > 100, the grains act as a bolometer to measure the luminosity.

  13. On a New Theoretical Framework for RR Lyrae Stars. II. Mid-infrared Period–Luminosity–Metallicity Relations

    Energy Technology Data Exchange (ETDEWEB)

    Neeley, Jillian R.; Marengo, Massimo; Trueba, Nicolas [Department of Physics and Astronomy, Iowa State University, Ames, IA 50011 (United States); Bono, Giuseppe; Braga, Vittorio F.; Magurno, Davide [Department of Physics, Università di Roma Tor Vergara, via della Ricerca Scientifica 1, I-00133 Roma (Italy); Dall’Ora, Massimo; Marconi, Marcella [INAF-Osservatorio Astronomico di Capodimonte, Salita Moiarello 16, I-80131 Napoli (Italy); Tognelli, Emanuele; Moroni, Pier G. Prada [Dipartimento di Fisica, Università di Pisa, Lago Bruno Pontecorvo 3, I-56127, Pisa (Italy); Beaton, Rachael L.; Madore, Barry F.; Seibert, Mark [Carnegie Observatories, 813 Santa Barbara Street, Pasadena, CA 91101 (United States); Freedman, Wendy L. [Department of Astronomy and Astrophysics, University of Chicago, Chicago, IL 60637 (United States); Monson, Andrew J. [Department of Astronomy and Astrophysics, The Pennsylvania State University, 525 Davey Lab, University Park, PA 16802 (United States); Scowcroft, Victoria [Department of Physics, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Stetson, Peter B., E-mail: jrneeley@iastate.edu [NRC-Herzberg, Dominion Astrophysical Observatory, 5071 West Saanich Road, Victoria BC V9E 2E7 (Canada)

    2017-06-01

    We present new theoretical period–luminosity–metallicity (PLZ) relations for RR Lyræ stars (RRLs) at Spitzer and WISE wavelengths. The PLZ relations were derived using nonlinear, time-dependent convective hydrodynamical models for a broad range of metal abundances ( Z = 0.0001–0.0198). In deriving the light curves, we tested two sets of atmospheric models and found no significant difference between the resulting mean magnitudes. We also compare our theoretical relations to empirical relations derived from RRLs in both the field and in the globular cluster M4. Our theoretical PLZ relations were combined with multi-wavelength observations to simultaneously fit the distance modulus, μ {sub 0}, and extinction, A {sub V}, of both the individual Galactic RRL and of the cluster M4. The results for the Galactic RRL are consistent with trigonometric parallax measurements from Gaia ’ s first data release. For M4, we find a distance modulus of μ {sub 0} = 11.257 ± 0.035 mag with A {sub V}= 1.45 ± 0.12 mag, which is consistent with measurements from other distance indicators. This analysis has shown that, when considering a sample covering a range of iron abundances, the metallicity spread introduces a dispersion in the PL relation on the order of 0.13 mag. However, if this metallicity component is accounted for in a PLZ relation, the dispersion is reduced to ∼0.02 mag at mid-infrared wavelengths.

  14. Parallel β-sheet vibrational couplings revealed by 2D IR spectroscopy of an isotopically labeled macrocycle: quantitative benchmark for the interpretation of amyloid and protein infrared spectra.

    Science.gov (United States)

    Woys, Ann Marie; Almeida, Aaron M; Wang, Lu; Chiu, Chi-Cheng; McGovern, Michael; de Pablo, Juan J; Skinner, James L; Gellman, Samuel H; Zanni, Martin T

    2012-11-21

    Infrared spectroscopy is playing an important role in the elucidation of amyloid fiber formation, but the coupling models that link spectra to structure are not well tested for parallel β-sheets. Using a synthetic macrocycle that enforces a two stranded parallel β-sheet conformation, we measured the lifetimes and frequency for six combinations of doubly (13)C═(18)O labeled amide I modes using 2D IR spectroscopy. The average vibrational lifetime of the isotope labeled residues was 550 fs. The frequencies of the labels ranged from 1585 to 1595 cm(-1), with the largest frequency shift occurring for in-register amino acids. The 2D IR spectra of the coupled isotope labels were calculated from molecular dynamics simulations of a series of macrocycle structures generated from replica exchange dynamics to fully sample the conformational distribution. The models used to simulate the spectra include through-space coupling, through-bond coupling, and local frequency shifts caused by environment electrostatics and hydrogen bonding. The calculated spectra predict the line widths and frequencies nearly quantitatively. Historically, the characteristic features of β-sheet infrared spectra have been attributed to through-space couplings such as transition dipole coupling. We find that frequency shifts of the local carbonyl groups due to nearest neighbor couplings and environmental factors are more important, while the through-space couplings dictate the spectral intensities. As a result, the characteristic absorption spectra empirically used for decades to assign parallel β-sheet secondary structure arises because of a redistribution of oscillator strength, but the through-space couplings do not themselves dramatically alter the frequency distribution of eigenstates much more than already exists in random coil structures. Moreover, solvent exposed residues have amide I bands with >20 cm(-1) line width. Narrower line widths indicate that the amide I backbone is solvent

  15. An experimental and theoretical investigation of Acenaphthene-5-boronic acid: conformational study, NBO and NLO analysis, molecular structure and FT-IR, FT-Raman, NMR and UV spectra.

    Science.gov (United States)

    Karabacak, Mehmet; Sinha, Leena; Prasad, Onkar; Asiri, Abdullah M; Cinar, Mehmet

    2013-11-01

    The solid state Fourier transform infrared (FT-IR) and FT-Raman spectra of Acenaphthene-5-boronic acid (AN-5-BA), have been recorded in the range 4000-400cm(-1) and 4000-10cm(-1), respectively. Density functional theory (DFT), with the B3LYP functional was used for the optimization of the ground state geometry and simulation of the infrared and Raman spectra of the molecule. The vibrational wave numbers and their assignments were examined theoretically using the Gaussian 09 set of quantum chemistry codes and the normal modes were assigned by a scaled quantum mechanical (SQM) force field approach. Hydrogen-bonded dimer of AN-5-BA, optimized by counterpoise correction, has also been studied by B3LYP at the 6-311++G(d,p) level and the effects of molecular association through O-H⋯O hydrogen bonding have been discussed. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by Gauge-Including Atomic Orbital (GIAO) method. Natural bond orbital (NBO) analysis has been applied to study stability of the molecule arising from charge delocalization. UV spectrum of the title compound was also recorded and the electronic properties, such as frontier orbitals, and band gap energies were measured by TD-DFT approach. The first order hyperpolarizability 〈β〉, its components and associated properties such as average polarizability and anisotropy of the polarizability (α and Δα) of AN-5-BA was calculated using the finite-field approach. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Theoretical approach to surface plasmon scattering microscopy for single nanoparticle detection in near infrared region

    Science.gov (United States)

    Son, Taehwang; Kim, Donghyun

    2015-03-01

    We present a theoretical approach to single nanoparticle detection using surface plasmon scattering microscopy. Through rigorous coupled wave analysis assuming light incidence on a gold coated BK7 glass substrate under total internal reflection condition for a 200-nm polystyrene as targets attached to the gold film, it was found that surface plasmon polariton induced by incident light on the gold thin film is perturbed. As a result, parabolic waves were observed in the reflection plane. By varying angles of incidence and wavelengths, optimum incident conditions for surface plasmon scattering microscopy were obtained.

  17. Spectra-structure correlations of saturated and unsaturated medium-chain fatty acids. Near-infrared and anharmonic DFT study of hexanoic acid and sorbic acid

    Science.gov (United States)

    Grabska, Justyna; Beć, Krzysztof B.; Ishigaki, Mika; Wójcik, Marek J.; Ozaki, Yukihiro

    2017-10-01

    Quantum chemical reproduction of entire NIR spectra is a new trend, enabled by contemporary advances in the anharmonic approaches. At the same time, recent increase of the importance of NIR spectroscopy of biological samples raises high demand for gaining deeper understanding of NIR spectra of biomolecules, i.e. fatty acids. In this work we investigate saturated and unsaturated medium-chain fatty acids, hexanoic acid and sorbic acid, in the near-infrared region. By employing fully anharmonic density functional theory (DFT) calculations we reproduce the experimental NIR spectra of these systems, including the highly specific spectral features corresponding to the dimerization of fatty acids. Broad range of concentration levels from 5 · 10- 4 M in CCl4 to pure samples are investigated. The major role of cyclic dimers can be evidenced for the vast majority of these samples. A highly specific NIR feature of fatty acids, the elevation of spectral baseline around 6500-4000 cm- 1, is being explained by the contributions of combination bands resulting from the vibrations of hydrogen-bonded OH groups in the cyclic dimers. Based on the high agreement between the calculated and experimental NIR spectra, a detailed NIR band assignments are proposed for hexanoic acid and sorbic acid. Subsequently, the correlations between the structure and NIR spectra are elucidated, emphasizing the regions in which clear and universal traces of specific bands corresponding to saturated and unsaturated alkyl chains can be established, thus demonstrating the wavenumber regions highly valuable for structural identifications.

  18. Spectra and concentration profiles throughout the reaction of curing epoxy resins from near-infrared spectroscopy and multivariate curve resolution methods.

    Science.gov (United States)

    Larrechi, M S; Rius, F X

    2004-01-01

    When applied to near-infrared (NIR) data, multivariate curve resolution methods, in particular alternating least squares (ALS), make it possible to calculate the concentration profiles and the spectra of all species involved in the reaction of curing epoxy resins. In this paper, the model reaction between phenyl glicidyl ether and aniline (2:1) was studied at 95 degrees C. A NIR spectrum was recorded every five minutes throughout the eight-hour reaction process. The data display rank deficiency. This problem was overcome by supplying additional information to the system in the form of known spectra of some reactants. The recovered spectra and concentration profiles satisfactorily reproduced the experimental data. In this way, 99.99% of the variance associated with the experimental matrix was reproduced. A value of 0.87% was obtained for lack of fit while the similarity coefficient r between the spectra recovered and the spectra corresponding to the three pure species involved in the reaction were PGE (r = 0.994), aniline (r = 0.994), and tertiary amine (r = 0.999). The maximum and minimum limits associated with the ALS solutions were calculated, which made it possible to limit to a considerable extent the ambiguity that is characteristic of these curve resolution methods.

  19. Mid-Infrared Quantum-Dot Quantum Cascade Laser: A Theoretical Feasibility Study

    Directory of Open Access Journals (Sweden)

    Stephan Michael

    2016-05-01

    Full Text Available In the framework of a microscopic model for intersubband gain from electrically pumped quantum-dot structures we investigate electrically pumped quantum-dots as active material for a mid-infrared quantum cascade laser. Our previous calculations have indicated that these structures could operate with reduced threshold current densities while also achieving a modal gain comparable to that of quantum well active materials. Here, we study the influence of two important quantum-dot material parameters, namely inhomogeneous broadening and quantum-dot sheet density, on the performance of a proposed quantum cascade laser design. In terms of achieving a positive modal net gain, a high quantum-dot density can compensate for moderately high inhomogeneous broadening, but at a cost of increased threshold current density. However, by minimizing quantum-dot density with presently achievable inhomogeneous broadening and total losses, significantly lower threshold densities than those reported in quantum-well quantum-cascade lasers are predicted by our theory.

  20. Atomic polarizations necessary for coherent infrared intensity modeling with theoretical calculations.

    Science.gov (United States)

    Richter, Wagner E; Silva, Arnaldo F; Bruns, Roy E

    2017-04-07

    The inclusion of atomic polarizations for describing molecular electronic structure changes on vibration is shown to be necessary for coherent infrared intensity modeling. Atomic charges from the ChelpG partition scheme and atomic charges and dipoles from Quantum Theory of Atoms in Molecules (QTAIM) were employed within two different models to describe the stretching and bending vibrational intensities of the C-H, C-F, and C=O groups. The model employing the QTAIM parameters was the Charge-Charge Transfer and Dipolar Polarization model (QTAIM/CCTDP), and the model employing the ChelpG charges was the Equilibrium Charge-Charge Flux (ChelpG/ECCF). The QTAIM/CCTDP models result in characteristic proportions of the charge-charge transfer-dipolar polarization contributions even though their sums giving the total intensities do not discriminate between these vibrations. According to the QTAIM/CCTDP model, the carbon monoxide intensity has electronic structure changes similar to those of the carbonyl stretches whereas they resemble those of the CH stretches for the ChelpG/ECCF model.

  1. The complexes between CH3OH and CF4. Infrared matrix isolation and theoretical studies.

    Science.gov (United States)

    Mielke, Z; Coussan, S; Mierzwicki, K; Roubin, P; Sałdyka, M

    2006-04-13

    The complex formed between methanol and tetrafluoromethane has been identified in argon and neon matrixes by help of FTIR spectroscopy. Three fundamentals (nu(OH), nu(FCF), and nu(CO)) were observed for the complex isolated in the two matrixes, and the OH stretch was red shifted in a neon matrix and blue shifted in an argon matrix with respect to the corresponding vibration of the methanol monomer. The theoretical studies of the structure and spectral characteristics of the complexes formed between CH(3)OH and CF(4) were carried out at the MP2 level of theory with the 6-311+G(2df,2pd) basis set. The calculations resulted in three stationary points from which two (I-1, I-2) corresponded to structures involving the O-H...F hydrogen bond and the third one (I-3) to the non-hydrogen-bonded structure. The topological analysis of the distribution of the charge density (AIM theory) confirmed the existence of the hydrogen bond in I-1, I-2 complexes and indicated weak interaction between the oxygen atom of CH(3)OH and three fluorine atoms of CF(4) in the I-3 complex. The comparison of the experimental and theoretical data suggests that in the matrixes only the non-hydrogen-bonded complex I-3 is trapped. The blue/red shift of the complex OH stretching vibration with respect to the corresponding vibration of CH(3)OH in argon/neon matrixes is explained by the different sensitivity of the complex and monomer vibrations to matrix material. The ab initio calculations performed for the ternary CH(3)OH-CF(4)-Ar systems indicated a negligible effect of an argon atom on the binary complex frequencies.

  2. Theoretical UV absorption spectra of hydrodynamically escaping O{sub 2}/CO{sub 2}-rich exoplanetary atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Gronoff, G.; Mertens, C. J.; Norman, R. B. [NASA LaRC, Hampton, VA (United States); Maggiolo, R. [BIRA-IASB, Avenue Circulaire 3, 1180 Brussels (Belgium); Wedlund, C. Simon [Aalto University School of Electrical Engineering Department of Radio Science and Engineering, P.O. Box 13000, FI-00076 Aalto (Finland); Bell, J. [National Institute of Aerospace, Hampton, VA (United States); Bernard, D. [IPAG, Grenoble (France); Parkinson, C. J. [University of Michigan, MI (United States); Vidal-Madjar, A., E-mail: Guillaume.P.Gronoff@nasa.gov [Observatoire de Paris, Paris (France)

    2014-06-20

    Characterizing Earth- and Venus-like exoplanets' atmospheres to determine if they are habitable and how they are evolving (e.g., equilibrium or strong erosion) is a challenge. For that endeavor, a key element is the retrieval of the exospheric temperature, which is a marker of some of the processes occurring in the lower layers and controls a large part of the atmospheric escape. We describe a method to determine the exospheric temperature of an O{sub 2}- and/or CO{sub 2}-rich transiting exoplanet, and we simulate the respective spectra of such a planet in hydrostatic equilibrium and hydrodynamic escape. The observation of hydrodynamically escaping atmospheres in young planets may help constrain and improve our understanding of the evolution of the solar system's terrestrial planets' atmospheres. We use the dependency of the absorption spectra of the O{sub 2} and CO{sub 2} molecules on the temperature to estimate the temperature independently of the total absorption of the planet. Combining two observables (two parts of the UV spectra that have a different temperature dependency) with the model, we are able to determine the thermospheric density profile and temperature. If the slope of the density profile is inconsistent with the temperature, then we infer the hydrodynamic escape. We address the question of the possible biases in the application of the method to future observations, and we show that the flare activity should be cautiously monitored to avoid large biases.

  3. Anhamonic finite temperature effects on the Raman and Infrared spectra to determine the crystal structure phase III of solid molecular hydrogen

    OpenAIRE

    Singh, Ranber; Azadi, Sam; Kühne, Thomas D.

    2013-01-01

    We present theoretical calculations of the Raman and IR spectra, as well as electronic properties at zero and finite temperature to elucidate the crystal structure of phase III of solid molecular hydrogen. We find that anharmonic finite temperature are particularly important and qualitatively influences the main conclusions. While P6$_3$/m is the most likely candidate for phase III at the nuclear ground state, at finite temperature the C2/c structure appears to be more suitable.

  4. [Apply fourier transform infrared spectra coupled with two-dimensional correlation analysis to study the evolution of humic acids during composting].

    Science.gov (United States)

    Bu, Gui-jun; Yu, Jing; Di, Hui-hui; Luo, Shi-jia; Zhou, Da-zhai; Xiao, Qiang

    2015-02-01

    The composition and structure of humic acids formed during composting play an important influence on the quality and mature of compost. In order to explore the composition and evolution mechanism, municipal solid wastes were collected to compost and humic and fulvic acids were obtained from these composted municipal solid wastes. Furthermore, fourier transform infrared spectra and two-dimensional correlation analysis were applied to study the composition and transformation of humic and fulvic acids during composting. The results from fourier transform infrared spectra showed that, the composition of humic acids was complex, and several absorbance peaks were observed at 2917-2924, 2844-2852, 2549, 1662, 1622, 1566, 1454, 1398, 1351, 990-1063, 839 and 711 cm(-1). Compared to humic acids, the composition of fulvci acids was simple, and only three peaks were detected at 1725, 1637 and 990 cm(-1). The appearance of these peaks showed that both humic and fulvic acids comprised the benzene originated from lignin and the polysaccharide. In addition, humic acids comprised a large number of aliphatic and protein which were hardly detected in fulvic acids. Aliphatic, polysaccharide, protein and lignin all were degraded during composting, however, the order of degradation was different between humic and fulvci acids. The result from two-dimensional correlation analysis showed that, organic compounds in humic acids were degraded in the following sequence: aliphatic> protein> polysaccharide and lignin, while that in fulvic acids was as following: protein> polysaccharide and aliphatic. A large number of carboxyl, alcohols and ethers were formed during the degradation process, and the carboxyl was transformed into carbonates. It can be concluded that, fourier transform infrared spectra coupled with two-dimensional correlation analysis not only can analyze the function group composition of humic substances, but also can characterize effectively the degradation sequence of these

  5. Effects of Space Weathering on Thermal Infrared Emissivity Spectra of Bulk Lunar Soils Measured Under Simulated Lunar Conditions

    Science.gov (United States)

    Donaldson Hanna, K. L.; Bowles, N. E.; Pieters, C. M.; Greenhagen, B. T.; Glotch, T. D.; Lucey, P. G.

    2015-11-01

    In this initial study, TIR emissivity spectral measurements are made under lunar-like conditions of two highland soil samples that are similar in composition, but differing maturities to understand the effects of space weathering on TIR spectra.

  6. Small group IIa-VIa clusters and related systems: A theoretical study of physical properties, reactivity, and electronic spectra

    Czech Academy of Sciences Publication Activity Database

    Srnec, Martin; Zahradník, Rudolf

    -, č. 12 (2007), s. 1529-1543 ISSN 1434-1948 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : ab initio calculations * cluster compounds * structural elucidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.597, year: 2007

  7. Savitzky-Golay coupled with digital bandpass filtering as a pre-processing technique in the quantitative analysis of glucose from near infrared spectra.

    Science.gov (United States)

    Patchava, Krishna Chaitanya; Alrezj, Osamah; Benaissa, Mohammed; Behairy, Hatim

    2016-08-01

    This paper proposes a novel pre-processing method based on combining bandpass with Savitzky-Golay filtering to further improve the prediction performance of the linear calibration models Principal Component Regression (PCR) and Partial Least Squares Regression (PLSR) in near infrared spectroscopy. The proposed method is compared to the highly efficient RReliefF pre-processing technique for further evaluation. The developed calibration models have been validated to predict the glucose concentration from near infrared spectra of a mixture of glucose and human serum albumin in a phosphate buffer solution. The results show that the proposed technique improves the prediction performance of both the PCR and PLSR models and achieve better results than the RReliefF technique.

  8. Characterization of Artifacts Introduced by the Empirical Volcano-Scan Atmospheric Correction Commonly Applied to CRISM and OMEGA Near-Infrared Spectra

    Science.gov (United States)

    Wiseman, S.M.; Arvidson, R.E.; Wolff, M. J.; Smith, M. D.; Seelos, F. P.; Morgan, F.; Murchie, S. L.; Mustard, J. F.; Morris, R. V.; Humm, D.; hide

    2014-01-01

    The empirical volcano-scan atmospheric correction is widely applied to Martian near infrared CRISM and OMEGA spectra between 1000 and 2600 nanometers to remove prominent atmospheric gas absorptions with minimal computational investment. This correction method employs division by a scaled empirically-derived atmospheric transmission spectrum that is generated from observations of the Martian surface in which different path lengths through the atmosphere were measured and transmission calculated using the Beer-Lambert Law. Identifying and characterizing both artifacts and residual atmospheric features left by the volcano-scan correction is important for robust interpretation of CRISM and OMEGA volcano scan corrected spectra. In order to identify and determine the cause of spectral artifacts introduced by the volcano-scan correction, we simulated this correction using a multiple scattering radiative transfer algorithm (DISORT). Simulated transmission spectra that are similar to actual CRISM- and OMEGA-derived transmission spectra were generated from modeled Olympus Mons base and summit spectra. Results from the simulations were used to investigate the validity of assumptions inherent in the volcano-scan correction and to identify artifacts introduced by this method of atmospheric correction. We found that the most prominent artifact, a bowl-shaped feature centered near 2000 nanometers, is caused by the inaccurate assumption that absorption coefficients of CO2 in the Martian atmosphere are independent of column density. In addition, spectral albedo and slope are modified by atmospheric aerosols. Residual atmospheric contributions that are caused by variable amounts of dust aerosols, ice aerosols, and water vapor are characterized by the analysis of CRISM volcano-scan corrected spectra from the same location acquired at different times under variable atmospheric conditions.

  9. New Benchmarks from Tokamak Experiments for Theoretical Calculations of the Dielectronic Satellite Spectra of Helium-like Ions

    International Nuclear Information System (INIS)

    Bitter, M.; Gu, M.F.; Vainshtein, L.A.; Beiersdorfer, P.; Bertschinger, G.; Marchuk, O.; Bell, R.; LeBlanc, B.; Hill, K.W.; Johnson, D.; Roquemore, L.

    2003-01-01

    Dielectronic satellite spectra of helium-like argon, recorded with a high-resolution X-ray crystal spectrometer at the National Spherical Torus Experiment, were found to be inconsistent with existing predictions resulting in unacceptable values for the power balance and suggesting the unlikely existence of non-Maxwellian electron energy distributions. These problems were resolved with calculations from a new atomic code. It is now possible to perform reliable electron temperature measurements and to eliminate the uncertainties associated with determinations of non-Maxwellian distributions

  10. OMS, OM(η2-SO), and OM(η2-SO)(η2-SO2) molecules (M = Ti, Zr, Hf): infrared spectra and density functional calculations.

    Science.gov (United States)

    Liu, Xing; Wang, Xuefeng; Wang, Qiang; Andrews, Lester

    2012-07-02

    Infrared spectra of the matrix isolated OMS, OM(η(2)-SO), and OM(η(2)-SO)(η(2)-SO(2)) (M = Ti, Zr, Hf) molecules were observed following laser-ablated metal atom reactions with SO(2) during condensation in solid argon and neon. The assignments for the major vibrational modes were confirmed by appropriate S(18)O(2) and (34)SO(2) isotopic shifts, and density functional vibrational frequency calculations (B3LYP and BPW91). Bonding in the initial OM(η(2)-SO) reaction products and in the OM(η(2)-SO)(η(2)-SO(2)) adduct molecules with unusual chiral structures is discussed.

  11. On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System

    Science.gov (United States)

    Ferguson, Frank T.; Johnson, Natasha M.; Nuth, Joseph A., III

    2015-01-01

    One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the high-resolution transmission molecular absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments.

  12. Experimental and theoretical study on emission spectra of a nitrogen photoionized plasma induced by intense EUV pulses

    Science.gov (United States)

    Saber, Ismail; Bartnik, Andrzej; Skrzeczanowski, Wojciech; Wachulak, Przemyslaw; Jarocki, Roman; Fiedorowicz, Henryk; Limpouch, Jiri

    2018-01-01

    Spectral lines of low-temperature nitrogen photoionized plasma were investigated. The photoionized plasma was created in the result of irradiation N2 gas using laser plasma EUV radiation pulses. The source was based on a 10J/10ns Nd:YAG (λ = 1064 nm) laser system and a gas puff target. The EUV radiation pulses were collected and focused using a grazing incidence multifoil EUV collector. The emission spectra were measured in the ultraviolet and visible (UV/Vis) range. It was found that the plasma emission lines in the lower region of the UV range are relativley weak. Nonetheless, a part of the spectra contains strong molecular band in the 300 - 430 nm originated from second positive and first negative systems band transitions of nitrogen. These molecular band transitions were identified using a code for study the diatomic molecules, LIFBASE. The vibrational band of Δv = 0 and ±1 transitions were significantly populated than of that with Δv = ±2 and 3 transitions. A comparison of the calculated and measured spectrum is presented. With an assumption of a local thermodynamic equilibrium (LTE), the vibrational temperature was determined from the integrated band intensities with the help of the Boltzmann plot method and compared to the temperature predicted by SPECAIR and LIFBASE simulations. A summary of the results and the variations in the vibrational temperatures was discussed.

  13. Experimental and theoretical study on emission spectra of a nitrogen photoionized plasma induced by intense EUV pulses

    Directory of Open Access Journals (Sweden)

    Saber Ismail

    2018-01-01

    Full Text Available Spectral lines of low-temperature nitrogen photoionized plasma were investigated. The photoionized plasma was created in the result of irradiation N2 gas using laser plasma EUV radiation pulses. The source was based on a 10J/10ns Nd:YAG (λ = 1064 nm laser system and a gas puff target. The EUV radiation pulses were collected and focused using a grazing incidence multifoil EUV collector. The emission spectra were measured in the ultraviolet and visible (UV/Vis range. It was found that the plasma emission lines in the lower region of the UV range are relativley weak. Nonetheless, a part of the spectra contains strong molecular band in the 300 - 430 nm originated from second positive and first negative systems band transitions of nitrogen. These molecular band transitions were identified using a code for study the diatomic molecules, LIFBASE. The vibrational band of Δv = 0 and ±1 transitions were significantly populated than of that with Δv = ±2 and 3 transitions. A comparison of the calculated and measured spectrum is presented. With an assumption of a local thermodynamic equilibrium (LTE, the vibrational temperature was determined from the integrated band intensities with the help of the Boltzmann plot method and compared to the temperature predicted by SPECAIR and LIFBASE simulations. A summary of the results and the variations in the vibrational temperatures was discussed.

  14. Infrared Spectroscopic Analyses of Sulfate, Nitrate, and Carbonate-bearing Atacama Desert Soils: Analogs for the Interpretation of Infrared Spectra from the Martian Surface

    Science.gov (United States)

    Dalton, J. B.; Dalton, J. B.; Ewing, S. A.; Amundson, R.; McKay, C. P.

    2005-01-01

    The Atacama Desert of northern Chile is the driest desert on Earth, receiving only a few mm of rain per decade. The Mars climate may, in the past, have been punctuated by short-lived episodes of aqueous activity. The paleo-Martian environment may have had aqueous conditions similar to the current conditions that exist in the Atacama, and Mars soils may have formed with soil chemistry and mineralogy similar to those found in the Atacama. Remote and in-situ analysis of the Martian surface using infrared technology has a long heritage. Future investigations of the subsurface mineralogy are likely to build upon this heritage, and will benefit from real life lessons to be learned from terrestrial analog studies. To that end, preliminary results from a near- and mid-infrared spectroscopic study of Atacama soil profiled at a range of depths are presented.

  15. Spectra and structure of gallium compounds. Part X. Infrared and Raman spectra, vibrational assignment, and normal coordinate calculations for trimethylaminegallium trichloride

    Science.gov (United States)

    Durig, J. R.; Chatterjee, K. K.

    The far IR (450-480 cm-1) and Raman (3200-3230 cm-1) spectra of (CH3)3 NGaCl3 have been recorded in the solid state and interpreted in detail on the basis of C3 molecular symmetry. A modified valence force field model is used to calculate the frequencies and potential energy distribution of the adduct. The calculated force constants of the adduct are compared with those previously reported for the free Lewis acid and the free Lewis base moieties, and the observed differences ascribed to geometrical changes of the uncomplexed species on adduct formation and explained on the basis of the VSEPR model and non-bond interactions. Extensive coupling is observed between the GaN stretching mode and the NC3 symmetric stretching and the NC3 symmetric deformational modes. Strong coupling interaction is also found between the GaCl3 antisymmetric stretch and the NC3 antisymmetric deformation. The calculated value of 2.50 mdyn Å-1 for the GaN stretching force constant in (CH3)3NGaCl3 is larger than any of those previously determined in complexes such as (CH3)3NGaH3 (2.43 mdyn Å-1), (CH3)3NGa(CH3)3 (1.61 mdyn Å-1), and H3NGa(CH3)3 (1.08 mdyn Å-1). The observed variations in the magnitudes of the stretching force constants of the donor-acceptor dative bond is found to be consistent with the estimated relative stabilities of this series of adducts.

  16. Theoretical photoionization spectra in the UV photon energy range for a Mg-like Al{sup +} ion

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dae-Soung [e-Business Department, Kyonggi Institute of Technology, Siheung, Jungwang-Dong 2121-3, Kyonggi-Do 429-792 (Korea, Republic of); Kim, Young Soon [Department of Physics, Myongji University, San 38-2 Namdong, Cheoin-gu, Yongin, Kyonggi-Do 449-728 (Korea, Republic of)], E-mail: dskim@kinst.ac.kr

    2008-08-28

    In the present work, we report the photoionization cross sections of the Al{sup +} ion calculated for the photon energy range 20-26 eV and 30-50 eV. We have expanded our previous calculation (2007 J. Phys. Soc. Japan 76 014302) with an optimized admixture of the initial ground state 3s{sup 21}S and exited states 3s3p{sup 1,3}P, 3s3d{sup 1,3}D and 3s4s{sup 1,3}S, and obtained significantly improved predictions for the main background and autoionizing resonance structures of the reported experimental spectra. The absolute measurements of the photoionization cross sections of the Al{sup +} ion in these energy ranges have been performed by West et al (2001 Phys. Rev. A 63 052719), and they reported that the prominent peaks around 21 eV were attributed to the effects of the significant influence of the small fraction of the fourth-order radiation with energies around 84 eV from the synchrotron source. In our previous work, the main shape for these cross sections was calculated assuming an admixture of initial 3s{sup 21}S and 3s3p{sup 3}P states, only with a rough overall estimate for the experimental spectra in the photon energy range 20-26 eV, and without these peaks around 21 eV. The report of the experimental assignment attributes these peaks to the excitation of a 2p electron from the core. However, our present results with the new admixture reveal similar peaks without considering the possibility of the core excitation.

  17. Vibrational infrared spectra of biuret and its thioanalogs. An ab initio SCF/3-21G study

    Science.gov (United States)

    Sullivan, Richard H.; Kwiatkowski, Józef S.; Leszczyński, Jerzy; Jabalameli, Ali

    1993-05-01

    The results of ab initio SCF/3-21G * calculations are reported for vibrational IR spectra (harmonic wavenumbers, absolute intensities) of biuret, thiobiuret, dithiobiuret and their model systems, formamide and thioformamide. The predicted vibrational spectra of both biurets and model systems compare well with the available experimental data, and the observed shifts of the IR wavenumbers upon deuteration of the molecules are correctly predicted by the calculations. The positions and relative intensities of characteristic IR bands of formamide and thioformamide correlate well with the corresponding data for the biurets.

  18. Influence of spectral resolution, spectral range and signal-to-noise ratio of Fourier transform infra-red spectra on identification of high explosive substances

    Science.gov (United States)

    Banas, Krzysztof; Banas, Agnieszka M.; Heussler, Sascha P.; Breese, Mark B. H.

    2018-01-01

    In the contemporary spectroscopy there is a trend to record spectra with the highest possible spectral resolution. This is clearly justified if the spectral features in the spectrum are very narrow (for example infra-red spectra of gas samples). However there is a plethora of samples (in the liquid and especially in the solid form) where there is a natural spectral peak broadening due to collisions and proximity predominately. Additionally there is a number of portable devices (spectrometers) with inherently restricted spectral resolution, spectral range or both, which are extremely useful in some field applications (archaeology, agriculture, food industry, cultural heritage, forensic science). In this paper the investigation of the influence of spectral resolution, spectral range and signal-to-noise ratio on the identification of high explosive substances by applying multivariate statistical methods on the Fourier transform infra-red spectral data sets is studied. All mathematical procedures on spectral data for dimension reduction, clustering and validation were implemented within R open source environment.

  19. Spectra-structure correlations of saturated and unsaturated medium-chain fatty acids. Near-infrared and anharmonic DFT study of hexanoic acid and sorbic acid.

    Science.gov (United States)

    Grabska, Justyna; Beć, Krzysztof B; Ishigaki, Mika; Wójcik, Marek J; Ozaki, Yukihiro

    2017-10-05

    Quantum chemical reproduction of entire NIR spectra is a new trend, enabled by contemporary advances in the anharmonic approaches. At the same time, recent increase of the importance of NIR spectroscopy of biological samples raises high demand for gaining deeper understanding of NIR spectra of biomolecules, i.e. fatty acids. In this work we investigate saturated and unsaturated medium-chain fatty acids, hexanoic acid and sorbic acid, in the near-infrared region. By employing fully anharmonic density functional theory (DFT) calculations we reproduce the experimental NIR spectra of these systems, including the highly specific spectral features corresponding to the dimerization of fatty acids. Broad range of concentration levels from 5·10 -4 M in CCl 4 to pure samples are investigated. The major role of cyclic dimers can be evidenced for the vast majority of these samples. A highly specific NIR feature of fatty acids, the elevation of spectral baseline around 6500-4000cm -1 , is being explained by the contributions of combination bands resulting from the vibrations of hydrogen-bonded OH groups in the cyclic dimers. Based on the high agreement between the calculated and experimental NIR spectra, a detailed NIR band assignments are proposed for hexanoic acid and sorbic acid. Subsequently, the correlations between the structure and NIR spectra are elucidated, emphasizing the regions in which clear and universal traces of specific bands corresponding to saturated and unsaturated alkyl chains can be established, thus demonstrating the wavenumber regions highly valuable for structural identifications. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. A new tridentate Schiff base Cu(II) complex: synthesis, experimental and theoretical studies on its crystal structure, FT-IR and UV-Visible spectra.

    Science.gov (United States)

    Saheb, Vahid; Sheikhshoaie, Iran; Setoodeh, Nasim; Rudbari, Hadi Amiri; Bruno, Giuseppe

    2013-06-01

    A new Cu(II) complex [Cu(L)(NCS)] has been synthesized, using 1-(N-salicylideneimino)-2-(N,N-methyl)-aminoethane as tridentate ONN donor Schiff base ligand (HL). The dark green crystals of the compound are used for single-crystal X-ray analysis and measuring Fourier Transform Infrared (FT-IR) and UV-Visible spectra. Electronic structure calculations at the B3LYP and MP2 levels of theory are performed to optimize the molecular geometry and to calculate the UV-Visible and FT-IR spectra of the compound. Vibrational assignments and analysis of the fundamental modes of the compound are performed. Time-dependent density functional theory (TD-DFT) method is used to calculate the electronic transitions of the complex. A scaling factor of 1.015 is obtained for vibrational frequencies computed at the B3LYP level using basis sets 6-311G(d,p). It is found that solvent has a profound effect on the electronic absorption spectrum. The UV-Visible spectrum of the complex recorded in DMSO and DMF solution can be correctly predicted by a model in which DMSO and DMF molecules are coordinated to the central Cu atom via their oxygen atoms. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Structure refinement, infrared and Raman spectra of KDyP.sub.4./sub.O.sub.12./sub..

    Czech Academy of Sciences Publication Activity Database

    Horchani, K.; Ferid, M.; Gacon, J. C.; Lecocq, S.; Trabelsi-Ayedi, M.; Gregora, Ivan

    2002-01-01

    Roč. 37, - (2002), s. 1259-1267 ISSN 0025-5408 Institutional research plan: CEZ:AV0Z1010914 Keywords : crystal structure * x-ray diffraction * infrared spectroscopy * Raman spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.892, year: 2002

  2. Structure refinement, infrared and Raman spectra of KDyP.sub.4./sub.O.sub.12./sub..

    Czech Academy of Sciences Publication Activity Database

    Horchani, K.; Ferid, M.; Gacon, J.C.; Lecocq, S.; Trabelsi-Ayedi, M.; Gregora, Ivan

    2002-01-01

    Roč. 37, - (2002), s. 1259-1267 ISSN 0025-5408 Institutional research plan: CEZ:AV0Z1010914 Keywords : crystal structure * X-ray diffraction * infrared spectroscopy * Raman spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.892, year: 2002

  3. Lanthanum trilactate: Vibrational spectroscopic study - infrared/Raman spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Švecová, M.; Novák, Vít; Bartůněk, V.; Člupek, M.

    2016-01-01

    Roč. 87, Nov (2016), s. 123-128 ISSN 0924-2031 Institutional support: RVO:61388963 Keywords : lanthanum trilactate * tris(2-hydroxypropanoato-O1,O2) * lanthanum tris[2-(hydroxy-kappa O)propanoato-kappa O] * Raman spectra * infrared spectra * DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.740, year: 2016

  4. A uniform database of 2.4-45.4 micron spectra from the Infrared Space Observatory Short Wavelength Spectrometer

    NARCIS (Netherlands)

    Sloan, GC; Kraemer, KE; Price, SD; Shipman, RF

    We present a complete set of all valid SWS full-scan 2.4-45.4 mum spectra processed and renormalized in as uniform a manner as possible. The processing produces a single spectrum for each observation from the 288 individual spectral segments, which are the most processed form available from the ISO

  5. Impact effects of gamma irradiation on the optical and FT infrared absorption spectra of some Nd3+-doped soda lime phosphate glasses

    Science.gov (United States)

    Marzouk, M. A.; Elkashef, I. M.; Elbatal, H. A.

    2018-04-01

    The main aim of the present work is to study by two collective optical and FTIR spectral measurements some prepared Nd2O3-doped soda lime phosphate glasses before and after gamma irradiation with dose (9 Mrad). The spectral data reveal two strong UV absorption peaks which are correlated with unavoidable trace iron impurities beside extended additional characteristic bands due to Nd3+ ions. Gamma irradiation on the undoped glass produces slight decrease of the intensity of the UV absorption and the generation of an induced visible band and these effects are controlled with two photochemical reduction of some Fe3+ ions to Fe2+ ions together with the formation of nonbridging oxygen hole center (NBOHC) or phosphorous oxygen hole center (POHC). The impact effect of gamma irradiation on the spectra of Nd2O3-doped glasses is limited due to suggested shielding behavior of neodymium ions. FT-infrared spectra show vibrational modes due to main Q2-Q3 phosphate groups and the response of gamma irradiation of the IR spectra is low and the limited variations are related to suggested changes in some bond angles and bond lengths which cause the observed decrease to the intensities of some IR bands.

  6. Infrared spectra of CF(2)=CHD and CF(2)=CD(2): scaled quantum-chemical force fields and an equilibrium structure for 1,1-difluoroethylene.

    Science.gov (United States)

    McKean, Donald C; Law, Mark M; Groner, Peter; Conrad, Andrew R; Tubergen, Michael J; Feller, David; Moore, Michael C; Craig, Norman C

    2010-09-02

    Infrared (IR) spectra in the gas phase are reported for CF(2)=CHD and CF(2)=CD(2) in the region 350-4000 cm(-1). Ab initio calculations of an harmonic force-field and anharmonicity constants have been made with an MP2/aug-cc-pVTZ model. These enable a number of Fermi resonances in each species to be analyzed and a complete set of "observed" harmonic frequencies to be derived. The latter are combined with similar data for CF(2)=CH(2) in a scaling of the model harmonic force field to both anharmonic and harmonic frequencies. Inspection of the scale factors reveals minor defects of the model, evident in the out-of-plane wagging modes and in the CF stretch/CF stretch interaction force constant. Fermi resonance treatments involved in all isotopomers studied are compatible with the overall force-field refinement results. The treatment leaves a small anomaly in the (13)C shift on nu(1). Improved microwave spectra are reported for five isotopic species, and a semiexperimental equilibrium structure for F(2)C=CH(2) is determined and compared favorably with the structure obtained from new high-level ab initio calculations. Centrifugal distortion constants are predicted for the five isotopic species, and those for F(2)C=CH(2) are compared with values fit to microwave spectra.

  7. Using visible and near-infrared diffuse reflectance spectroscopy for predicting soil properties based on regression with peaks parameters as derived from continuum-removed spectra

    Science.gov (United States)

    Vasat, Radim; Klement, Ales; Jaksik, Ondrej; Kodesova, Radka; Drabek, Ondrej; Boruvka, Lubos

    2014-05-01

    Visible and near-infrared diffuse reflectance spectroscopy (VNIR-DRS) provides a rapid and inexpensive tool for simultaneous prediction of a variety of soil properties. Usually, some sophisticated multivariate mathematical or statistical methods are employed in order to extract the required information from the raw spectra measurement. For this purpose especially the Partial least squares regression (PLSR) and Support vector machines (SVM) are the most frequently used. These methods generally benefit from the complexity with which the soil spectra are treated. But it is interesting that also techniques that focus only on a single spectral feature, such as a simple linear regression with selected continuum-removed spectra (CRS) characteristic (e.g. peak depth), can often provide competitive results. Therefore, we decided to enhance the potential of CRS taking into account all possible CRS peak parameters (area, width and depth) and develop a comprehensive methodology based on multiple linear regression approach. The eight considered soil properties were oxidizable carbon content (Cox), exchangeable (pHex) and active soil pH (pHa), particle and bulk density, CaCO3 content, crystalline and amorphous (Fed) and amorphous Fe (Feox) forms. In four cases (pHa, bulk density, Fed and Feox), of which two (Fed and Feox) were predicted reliably accurately (0.50 0.80). Acknowledgment: Authors acknowledge the financial support of the Ministry of Agriculture of the Czech Republic (grant No. QJ1230319).

  8. Infrared photoluminescence spectra of PbS nanoparticles prepared by Langmuir-Blodgett and laser ablation methods

    Czech Academy of Sciences Publication Activity Database

    Remeš, Zdeněk; Novák, T.; Stuchlík, Jiří; Stuchlíková, The-Ha; Dřínek, Vladislav; Fajgar, Radek; Zhuravlev, K.

    2014-01-01

    Roč. 54, č. 6 (2014), s. 426-429 ISSN 1210-2709 R&D Projects: GA ČR(CZ) GA14-05053S; GA MŠk(CZ) LD14011; GA MŠk LH12236 Institutional support: RVO:68378271 ; RVO:67985858 Keywords : infrared photoluminescence * PbS * Langmuir –Blodgett * laser ablation Subject RIV: BM - Solid Matter Physics ; Magnetism

  9. Processing of phase pure and dense bulk EuTiO.sub.3./sub. ceramics and their infrared reflectivity spectra

    Czech Academy of Sciences Publication Activity Database

    Kachlik, M.; Máca, K.; Goian, Veronica; Kamba, Stanislav

    2012-01-01

    Roč. 74, MAY (2012), s. 16-18 ISSN 0167-577X R&D Projects: GA ČR GD202/09/H041; GA ČR(CZ) GA202/09/0682 Grant - others:GAUK(CZ) SVV-2011-263303 Institutional research plan: CEZ:AV0Z10100520 Keywords : functional ceramics, * europium titanate * sintering * infrared reflectivity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.224, year: 2012

  10. Transition probabilities of Ce I obtained from Boltzmann analysis of visible and near-infrared emission spectra

    Science.gov (United States)

    Nitz, D. E.; Curry, J. J.; Buuck, M.; DeMann, A.; Mitchell, N.; Shull, W.

    2018-02-01

    We report radiative transition probabilities for 5029 emission lines of neutral cerium within the wavelength range 417-1110 nm. Transition probabilities for only 4% of these lines have been previously measured. These results are obtained from a Boltzmann analysis of two high resolution Fourier transform emission spectra used in previous studies of cerium, obtained from the digital archives of the National Solar Observatory at Kitt Peak. The set of transition probabilities used for the Boltzmann analysis are those published by Lawler et al (2010 J. Phys. B: At. Mol. Opt. Phys. 43 085701). Comparisons of branching ratios and transition probabilities for lines common to the two spectra provide important self-consistency checks and test for the presence of self-absorption effects. Estimated 1σ uncertainties for our transition probability results range from 10% to 18%.

  11. Terrestrial analogs for interpretation of infrared spectra from the Martian surface and subsurface: Sulfate, nitrate, carbonate, and phyllosilicate-bearing Atacama Desert soils

    Science.gov (United States)

    Sutter, B.; Dalton, J. B.; Ewing, S. A.; Amundson, R.; McKay, C. P.

    2007-10-01

    Hyperarid (Mars soils have similar sulfate concentrations; possess phyllosilicates (e.g., smectite) and minor carbonate. Nitrate has not been detected on Mars, but its presence has been proposed. The similar compositions of Atacama and Mars soils have prompted the visible-infrared (0.35-25 μm) investigation of Atacama soils as Mars analogs. Results from this work determined the best infrared features for detecting sulfate, nitrate, carbonate, and phyllosilicate on Mars. The fundamental region (>6.5 μm) was not suited for salt and phyllosilicate detection because of overlapping spectra from primary silicates (e.g., feldspar), water and carbon dioxide. The visible near-infrared (0.35-2.5 μm) region was suited for detecting carbonate, nitrate, gypsum water of hydration, and phyllosilicate hydroxyls without interference from primary silicates. However, gypsum water of hydration features can obscure phyllosilicate hydroxyl, carbonate and nitrate, features if gypsum levels are high. Overtone/combination absorption features in the midinfrared were determined to be the best indicators of sulfate (4.48-4.70 μm), nitrate (4.12 μm), and carbonate (3.98 μm) because interferences from overlapping primary silicate and water features are not present in this region. Interferences from CO2 and thermal emission effects in the overtone/combination region are possible but may be minimized by corrective techniques. Infrared analysis of Atacama Desert soils can provide insight into the spectral search of sulfate, nitrate, carbonate, and phyllosilicate containing soils on Mars.

  12. Ultraviolet and infrared absorption spectra of Cr2O3 doped-sodium metaphosphate, lead metaphosphate and zinc metaphosphate glasses and effects of gamma irradiation: a comparative study.

    Science.gov (United States)

    Marzouk, M A; ElBatal, F H; Abdelghany, A M

    2013-10-01

    The effects of gamma irradiation on spectral properties of Cr2O3-doped phosphate glasses of three varieties, namely sodium metaphosphate, lead metaphosphate and zinc metaphosphate have been investigated. Optical spectra of the undoped samples reveal strong UV absorption bands which are attributed to the presence of trace iron impurities in both the sodium and zinc phosphate glasses while the lead phosphate glass exhibits broad UV near visible bands due to combined absorption of both trace iron impurities and divalent lead ions. The effect of chromium oxide content has been investigated. The three different Cr2O3-doped phosphate glasses reveal spectral visible bands varying in their position and intensity and splitting due to the different field strengths of the Na(+), Pb(2+), Zn(2+) cations, together with the way they are housed in the network and their effects on the polarisability of neighboring oxygens ligands. The effects of gamma irradiation on the optical spectral properties of the various glasses have been compared. The different effects for lead and zinc phosphate are related to the ability of Pb(2+), and Zn(2+) to form additional structural units causing stability of the network towards gamma irradiation. Also, the introduction of the transition metal chromium ions reveals some shielding behavior towards irradiation. Infrared absorption spectra of the three different base phosphate glasses show characteristic vibrations due to various phosphate groups depending on the type of glass and Cr2O3 is observed to slightly affect the IR spectra. Gamma irradiation causes minor variations in some of the intensities of the IR spectra but the main characteristic bands due to phosphate groups remain in their number and position. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Excitation and propagation of X-ray fluorescence through thin devices with hollowed ordered structures: comparison of experimental and theoretical spectra.

    Science.gov (United States)

    Mazuritskiy, M I; Dabagov, S B; Marcelli, A; Lerer, A M; Dziedzic-Kocurek, K

    2016-01-01

    The lack of models describing the propagation of X-rays in waveguides and the interference mechanism between incident and reflected radiation waves hamper the understanding and the control of wave propagation phenomena occurring in many real systems. Here, experimental spectra collected at the exit of microchannel plates (MCPs) under the total X-ray reflection condition are presented. The results are discussed in the framework of a theoretical model in which the wave propagation is enhanced by the presence of a transition layer at the surface. The angular distributions of the propagating radiation at the exit of these MCPs with microchannels of ∼3 µm diameter will also be presented and discussed. These spectra show contributions associated with the reflection of the primary monochromatic beam and with the fluorescence radiation originating from the excitation of atoms composing the surface of the microchannel. The soft X-ray fluorescence spectra collected at the exit of microcapillaries were analyzed in the framework of a wave approximation while diffraction contributions observed at the exit of these hollow X-ray waveguides have been calculated using the Fraunhofer diffraction model for waves in the far-field domain. Data collected at the Si L-edge show that in glassy MCPs the fluorescence radiation can be detected only when the energy of the primary monochromatic radiation is above the absorption edge for grazing angles higher than half of the critical angle of the total reflection phenomenon. Experimental data and simulations of the propagating radiation represent a clear experimental confirmation of the channeling phenomenon of the excited fluorescence radiation inside a medium and point out that a high transmission can be obtained in waveguide optics for parameters relevant to X-ray imaging.

  14. Effect of CdSe nanoparticles on the fluorescence spectra of conjugate polymer P3HT: An experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Mastour, Nouha, E-mail: mastournouha@yahoo.fr; Bouchriha, Habib

    2016-11-25

    In this work we have investigated the effect of CdSe nanoparticles (Nps) on the fluorescence spectra of conjugate polymer Poly(3-hexylthiophene-2,5-diyl) (P3HT). The fluorescence intensity is significantly decreased in both solution and solid films by the incorporation of CdSe Nps. This observed effect in the nanocomposite P3HT-CdSe is analyzed by using the Franck–Condon theory which reproduces correctly the decrease of the fluorescence with the Nps concentration and permits to reach the Huang–Rhys factor and the relaxation energy which are shown efficient to explain the fluorescence quenching. - Highlights: • The effects of CdSe nanoparticles concentration on the fluorescence spectra of conjugate polymer P3HT are investigated. • Theoretical approach based on Franck–Condon analysis is proposed. • The Huang–Rhys factor and the relaxation energy as a function of the CdSe Nps are determined. • The fluorescence quenching has been explained.

  15. Effect of CdSe nanoparticles on the fluorescence spectra of conjugate polymer P3HT: An experimental and theoretical study

    International Nuclear Information System (INIS)

    Mastour, Nouha; Bouchriha, Habib

    2016-01-01

    In this work we have investigated the effect of CdSe nanoparticles (Nps) on the fluorescence spectra of conjugate polymer Poly(3-hexylthiophene-2,5-diyl) (P3HT). The fluorescence intensity is significantly decreased in both solution and solid films by the incorporation of CdSe Nps. This observed effect in the nanocomposite P3HT-CdSe is analyzed by using the Franck–Condon theory which reproduces correctly the decrease of the fluorescence with the Nps concentration and permits to reach the Huang–Rhys factor and the relaxation energy which are shown efficient to explain the fluorescence quenching. - Highlights: • The effects of CdSe nanoparticles concentration on the fluorescence spectra of conjugate polymer P3HT are investigated. • Theoretical approach based on Franck–Condon analysis is proposed. • The Huang–Rhys factor and the relaxation energy as a function of the CdSe Nps are determined. • The fluorescence quenching has been explained.

  16. Near-surface temperature gradients and their effects on thermal-infrared emission spectra of particulate planetary surfaces

    Science.gov (United States)

    Henderson, B. G.; Jakosky, B. M.

    1993-01-01

    The infrared energy emitted from a planetary surface is generated within a finite depth determined by the material's absorption skin depth. This parameter varies significantly with wavelength in the infrared but has an average value of around 50 microns for most geologic materials. In solid rock, heat transfer is efficient enough so that this 50 micron zone of the near surface from which the radiation emanates will be more or less isothermal. In particulate materials, however, heat transfer is more complicated and occurs via a combination of mechanisms, including solid conduction within grains and across grain contacts, conduction through the interstitial gas, and thermal radiation within individual particles and across the void spaces in between grains. On planets with substantial atmospheres, the gas component dominates the heat transfer and tends to mitigate near-surface thermal gradients. However, on airless bodies, the gas component is absent and heat transfer occurs via solid conductions and radiation. If the particles are small relative to the average absorption skin depth, then the top 50-100 microns or so of the surface will be cooled by radiation to space allowing the creation of significant near-surface thermal gradients. In those regions of the spectrum where the absorption coefficient is low, the emission will come from the deeper, warmer parts of the medium, whereas in regions of high absorption, the emission will emanate from shallower, cooler parts of the medium. The resulting emission spectrum will show non-compositional features as a result of the thermal structure in the material. We have modeled the heat transfer in a particulate medium in order to determine the magnitude of near-surface thermal gradients for surfaces on airless bodies and on Mars. We use the calculated thermal structure to determine the effects it has on the infrared emission spectrum of the surface.

  17. Identification of the absorbed infrared spectra of 1700 cm-1 in the radiation solid phase polymerization of aisotactic polyacrylonitrile

    International Nuclear Information System (INIS)

    Minagawa, M.; Umehara, R.; Matsuyama, T.; Sato, N.

    2004-01-01

    The monomer (AN) was mixed with gamma ray irradiation urea, and slight precipitation was obtained when methanol was poured out and collected after several months at low temperature. It was shown that this precipitation is the polymer, which the monomer combined with urea. Moreover, it was shown clearly from the measurement results of an infrared absorption spectrum and a NMR spectrum that it was the aisotactic polyacrylonitrile (PAN). The spectrum of 1700cm -1 seen with IR absorption spectrum of this polymer is from a carbonyl band (C=O), and it became clear that it is the spectrum of the urea origin. (H. Katsuta)

  18. Theoretical Time Dependent Thermal Neutron Spectra and Reaction Rates in H{sub 2}O and D{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Purohit, S.N.

    1966-04-15

    The early theoretical and experimental time dependent neutron thermalization studies were limited to the study of the transient spectrum in the diffusion period. The recent experimental measurements of the time dependent thermal neutron spectra and reaction rates, for a number of moderators, have generated considerable interest in the study of the time dependent Boltzmann equation. In this paper we present detailed results for the time dependent spectra and the reaction rates for resonance detectors using several scattering models of H{sub 2}O and D{sub 2}O. This study has been undertaken in order to interpret the integral time dependent neutron thermalization experiments in liquid moderators which have been performed at the AB Atomenergi. The proton gas and the deuteron gas models are inadequate to explain the measured reaction rates in H{sub 2}O and D{sub 2}O. The bound models of Nelkin for H{sub 2}O and of Butler for D{sub 2}O give much better agreement with the experimental results than the gas models. Nevertheless, some disagreement between theoretical and experimental results still persists. This study also indicates that the bound model of Butler and the effective mass 3. 6 gas model of Brown and St. John give almost identical reaction rates. It is also surprising to note that the calculated reaction rate for Cd for the Butler model appears to be in better agreement with the experimental results of D{sub 2}O than of the Nelkin model with H{sub 2}O experiments. The present reaction rate studies are sensitive enough so as to distinguish between the gas model and the bound model of a moderator. However, to investigate the details of a scattering law (such as the effect of the hindered rotations in H{sub 2}O and D{sub 2}O and the weights of different dynamical modes) with the help of these studies would require further theoretical as well as experimental investigations. Theoretical results can be further improved by improving the source for thermal neutrons, the

  19. Infrared absorption spectra of t-HNOH radicals generated on VUV irradiation of NO in solid hydrogen.

    Science.gov (United States)

    Wu, Yu-Jong; Lin, Meng-Yeh; Hsu, Sheng-Chuan; Cheng, Bing-Ming

    2009-04-14

    Photoproduct signature: Irradiation of solid hydrogen near 3 K containing NO with vacuum-UV light from synchrotron radiation yields new infrared absorption lines at 1241.7, 1063.6 and 726.2 cm(-1) (see figure). These new lines are assigned to vibrational modes of t-HNOH. This photoproduct is formed from electronically excited NO reacting with neighboring hydrogen in the solid sample.Irradiation of solid H(2) near 3 K containing NO with vacuum-ultraviolet light from a synchrotron yields new infrared absorption lines at 1241.7, 1063.6 and 726.2 cm(-1). The structures of four possible structural isomers: H(2)NO, t-HNOH, c-HNOH and NOH(2), their vibrational wavenumbers, IR intensities and D-isotopic shifts are calculated with density-functional theory according to B3LYP and PW91PW91/aug-cc-pVTZ methods. Based on the results of those calculations and of experiments with deuterium labeling, we assign the new lines to nu(4) (cis bending), nu(5) (N==O stretching) and nu(6) (out-of-plane deformation) modes, respectively, of t-HNOH. This photoproduct is formed through reaction of electronically excited NO with neighboring H(2) in the solid sample.

  20. Detection of Melamine in Soybean Meal Using Near-Infrared Microscopy Imaging with Pure Component Spectra as the Evaluation Criteria

    Directory of Open Access Journals (Sweden)

    Zengling Yang

    2016-01-01

    Full Text Available Soybean meal was adulterated with melamine with the purpose of boosting the protein content for unlawful interests. In recent years, the near-infrared (NIR spectroscopy technique has been widely used for guaranteeing food and feed security for its fast, nondestructive, and pollution-free characteristics. However, there are problems with using near-infrared (NIR spectroscopy for detecting samples with low contaminant concentration because of instrument noise and sampling issues. In addition, methods based on NIR are indirect and depend on calibration models. NIR microscopy imaging offers the opportunity to investigate the chemical species present in food and feed at the microscale level (the minimum spot size is a few micrometers, thus avoiding the problem of the spectral features of contaminants being diluted by scanning. The aim of this work was to investigate the feasibility of using NIR microscopy imaging to identify melamine particles in soybean meal using only the pure component spectrum. The results presented indicate that using the classical least squares (CLS algorithm with the nonnegative least squares (NNLS algorithm, without needing first to develop a calibration model, could identify soybean meal that is both uncontaminated and contaminated with melamine particles at as low a level as 50 mg kg−1.

  1. Differentiating between long and short range disorder in infra-red spectra: on the meaning of "crystallinity" in silica.

    Science.gov (United States)

    Asscher, Yotam; Dal Sasso, Gregorio; Nodari, Luca; Angelini, Ivana; Boffa Ballaran, Tiziana; Artioli, Gilberto

    2017-08-16

    Local atomic disorder and crystallinity are structural properties that influence greatly the resulting chemical and mechanical properties of inorganic solids, and are used as indicators for different pathways of material formation. Here, these structural properties are assessed in the crystals of quartz based on particle-size-related scattering processes in transmission infra-red spectroscopy. Independent determinations of particle size distributions in the range 2-100 μm of a single crystal of quartz and defective quartz with highly anisotropic micro-crystallites show that particle sizes below the employed wavelength (approx 10 μm) exhibit asymmetric narrowing of absorption peak widths, due to scattering processes that depend on the intra-particle structural defects and long range crystallinity. In particular, we observe that the 1079 cm -1 peak could be used to assess crystallinity, because it shows an asymmetric peak shape shift toward a higher wavelength, depending on the crystallite size. We observe that the 694 cm -1 peak could be used to assess local atomic disorder as it does not show scattering and peak shape changes when absorption effects dominate, below 2 μm. We propose coupling particle size assessments with infra-red peak shape analysis as a method to characterize crystallinity and short range order for studying recrystallization in natural silica, as well as defectivity in many different types of silicas used for industrial and technological applications.

  2. Matrix photoionization and radiolysis of the fluorobromomethanes. Infrared spectra and photochemistry of CFBr2+, CF2Br+, CF3+, and the parent cations

    International Nuclear Information System (INIS)

    Prochaska, F.T.; Andrews, L.

    1978-01-01

    The molecules CFBr 3 , CF 2 Br 2 , CF 3 Br, and C-13 enriched CF 3 Br have been subjected to matrix radiolysis and argon resonance photoionization during condensation with excess argon at 15 K. Infrared spectra showed stable and free radical products and new absorptions due to charged species. The molecular ion bands exhibited different behavior on filtered high-pressure mercury arc photolysis. Absorptions reduced by 220 to 1000-nm light are assigned to CFBr 2 + , CF 2 Br + , and CF 3 + ; other bands destroyed by photolysis are assigned to the parent cations. Li and Na atom reactions with the fluorobromomethane molecules confirmed the identification of the CFBr 2 and CF 2 Br free radicals. Other product bands destroyed by mercury arc light, some of which were generated upon photolysis of the sodium-fluorobromomethane samples, are assigned to molecular anions. 5 figures, 6 tables

  3. Near infrared spectra indicate specific mutant endosperm genes and reveal a new mechanism for substituting starch with (1-->3,1-->4)-[beta]-glucan in barley

    DEFF Research Database (Denmark)

    Munck, L.; Møller, B.; Jacobsen, Susanne

    2004-01-01

    Near Infrared Reflectance spectroscopy was tested as a screening method to characterise high lysine mutants from a barley collection by classification through Principal Component Analysis (PCA). Mean spectra of the samples within each cluster identified gene-specific patterns in the 2270-2360 nm......-->3,1-->4)-[beta]-glucan (up to 15-20%), thus, maintaining a constant production of polysaccharides at 50-55%, within the range of normal barley.The spectral tool was tested by an independent data set with six mutants with unknown polysaccharide composition. Spectral data from four of these were classified within...... the phenotype by chemometric classification of a spectral library, representing the digitised phenome from a barley gene bank....

  4. The conformational stability, solvation and the assignments of the experimental infrared, Raman, 1H and 13C NMR spectra of the local anesthetic drug lidocaine

    Science.gov (United States)

    Badawi, Hassan M.; Förner, Wolfgang; Ali, Shaikh A.

    2015-05-01

    The structure, vibrational and 1H and 13C NMR spectra of the local anesthetic drug lidocaine were investigated by the B3LYP/6-311G∗∗ calculations. The molecule was predicted to have the non-planar cis (NCCN ∼ 0°) structures being about 2-6 kcal/mol lower in energy than the corresponding trans (NCCN ∼ 180°) forms. The calculated NCCN (9.6°) and CNCC (-132.2°) torsional angles were in a good qualitative agreement with the reported X-ray angles (3.1 and 13.0°, -102.67 and -77.9°, respectively, for H-bonded dimers). The Gibbs energy of solution of lidocaine in formamide, water, dimethylsulfoxide, acetonitrile, methanol, ethanol and chloroform solutions was estimated at the B3LYP level. The predicted affinity of lidocaine toward the alcohols, acetonitrile and chloroform solutions was in excellent agreement with the reported experimental solubility of the drug in organic solvents. The analysis of the observed vibrational spectra is consistent with the presence of lidocaine in only one conformation at room temperature. The 1H and 13C NMR spectra of lidocaine were interpreted by experimental and DFT calculated chemical shifts of the drug. The RMSD between experimental and theoretical 1H and 13C chemical shifts for lidocaine is 0.47 and 8.26 ppm, respectively.

  5. Finding signal in the noise: Analyzing low signal-to-noise galaxy spectra & optimizing the Robert Stobie Spectrograph's Near InfraRed detector system

    Science.gov (United States)

    Mosby, Gregory, Jr.

    Ground-based optical and near infrared observational astronomy is naturally limited by the Earth's atmosphere and the vast distances of the objects to be studied. Technically, we are also limited by the precision and accuracy of our instrumentation. In this thesis, I describe strategies to move observational astronomy forward in light of these limitations. Specifically, I present a method of stellar population analysis that is precise and accurate in the limit of low signal-to-noise with an emphasis on faint quasar host galaxy spectra. I present an investigation and test of a simple model of persistence in HgCdTe detector arrays aimed at the removal of this spurious signal from data. Finally, I present an overview of the Robert Stobie Spectrograph Near InfraRed (RSS-NIR) instrument's detector system that I have optimized for low read noise and background limited performance. The advancement of observational astronomy will always be limited by our ability to efficiently detect the signals we need. This thesis reviews the progress made to enhance ground-based astronomy capability.

  6. Energetics of the rearrangement of neutral and ionized perfluorocyclopropane to perfluoropropylene. Use of infrared multiphoton dissociation spectra to identify structural isomers of molecular ions

    International Nuclear Information System (INIS)

    Bomse, D.S.; Berman, D.W.; Beauchamp, J.L.

    1981-01-01

    Infrared photodissociation spectroscopy is used to compare the structure of gas-phase C 3 F 6 + ions obtained by electron-impact ionization of two isomeric precursors: perfluoropropylene and perfluorocyclopropane. Photodissociation spectra are obtained by observing the extent of multiphoton dissociation as the CO 2 laser is tuned across the 925 to 1080 cm -1 wavelength range. Ions are formed, stored, and detected with the use of techniques of ion cyclotron resonance spectroscopy. Infrared multiphoton excitation is effected by using low-power, continuous-wave laser radiation. The fingerprint spectrum of the molecular ion of perfluorocyclopropane is identical with that obtained from perfluoropropylene, indicating rearrangement of the former to the latter. Photodissociation kinetics indicate that the entire perfluorocyclopropane molecular ion population isomerizes to the more stable perfluoropropylene structure. Thermochemistry of C 3 F 6 and C 3 F 6 + isomers is discussed. Comparisons are made with the analogous C 3 H 6 system. Photoionization mass spectroscopy results yield ΔH/sub f/(c-C 3 F 6 ) = -233.8 kcal/mol. 4 figures

  7. Near-infrared spectra and rovibrational dynamics on a four-dimensional ab initio potential energy surface of (HBr)2.

    Science.gov (United States)

    Castillo-Chará, J; McIntosh, A L; Wang, Z; Lucchese, R R; Bevan, J W

    2004-06-08

    Supersonic jet investigations of the (HBr)(2) dimer have been carried out using a tunable diode laser spectrometer to provide accurate data for comparison with results from a four-dimensional (4-D) ab initio potential energy surface (PES). The near-infrared nu(1) (+/-), nu(2) (+/-), and (nu(1)+nu(4))(-) bands of (H (79)Br)(2), (H (79)Br-H (81)Br), and (H (81)Br)(2) isotopomers have been recorded in the range 2500-2600 cm(-1) using a CW slit jet expansion with an upgraded near-infrared diode laser spectrometer. The 4-D PES has been calculated for (HBr)(2) using second-order Møller-Plesset perturbation theory with an augmented and polarized 6-311G basis set. The potential is characterized by a global minimum occurring at the H bond structure with the distance between the center of masses (CM) of the monomer being R(CM)=4.10 A with angles theta(A)=10 degrees, theta(B)=100 degrees and a well depth of 692.2 cm(-1), theta(A) is the angle the HBr bond of monomer A makes with the vector from the CM of A to the CM of B, and theta(B) is the corresponding angle monomer B makes with the same CM-CM vector. The barrier for the H interchange occurs at the closed C(2h) structure for which R(CM)=4.07 A, theta(A)=45 degrees, theta(B)=135 degrees, and the barrier height is 73.9 cm(-1). The PES was fitted using a linear-least squares method and the rovibrational energy levels of the complex were calculated by a split pseudospectral method. The spectroscopic data provide accurate molecular parameters for the dimer that are then compared with the results predicted on the basis of the 4-D ab initio PES. (c) 2004 American Institute of Physics.

  8. Upper limits for stratospheric H2O2 and HOCl from high resolution balloon-borne infrared solar absorption spectra

    Science.gov (United States)

    Larsen, J. C.; Rinsland, C. P.; Goldman, A.; Murcray, D. G.; Murcray, F. J.

    1985-01-01

    Solar absorption spectra from two stratospheric balloon flights have been analyzed for the presence of H2O2 and HOCl absorption in the 1230.0 to 1255.0 per cm region. The data were recorded at 0.02 per cm resolution during sunset with the University of Denver interferometer system on October 27, 1978 and March 23, 1981. Selected spectral regions were analyzed with the technique of nonlinear least squares spectral curve fitting. Upper limits of 0.33 ppbv for H2O2 and 0.36 ppbv for HOCl near 28 km are derived from the 1978 flight data while upper limits of 0.44 ppbv for H2O2 and 0.43 ppbv for HOCl at 29.5 km are obtained from the 1981 flight data.

  9. Diffuse Reflectance Spectroscopy of Hidden Objects, Part I: Interpretation of the Reflection-Absorption-Scattering Fractions in Near-Infrared (NIR) Spectra of Polyethylene Films.

    Science.gov (United States)

    Pomerantsev, Alexey L; Rodionova, Oxana Ye; Skvortsov, Alexej N

    2017-08-01

    Investigation of a sample covered by an interfering layer is required in many fields, e.g., for process control, biochemical analysis, and many other applications. This study is based on the analysis of spectra collected by near-infrared (NIR) diffuse reflectance spectroscopy. Each spectrum is a composition of a useful, target spectrum and a spectrum of an interfering layer. To recover the target spectrum, we suggest using a new phenomenological approach, which employs the multivariate curve resolution (MCR) method. In general terms, the problem is very complex. We start with a specific problem of analyzing a system, which consists of several layers of polyethylene (PE) film and underlayer samples with known spectral properties. To separate information originating from PE layers and the target, we modify the system versus both the number of the PE layers as well as the reflectance properties of the target sample. We consider that the interfering spectrum of the layer can be modeled using three components, which can be tentatively called transmission, absorption, and scattering contributions. The novelty of our approach is that we do not remove the reflectance and scattering effects from the spectra, but study them in detail aiming to use this information to recover the target spectrum.

  10. Acquisition of reproducible transmission near-infrared (NIR) spectra of solid samples with inconsistent shapes by irradiation with isotropically diffused radiation using polytetrafluoroethylene (PTFE) beads.

    Science.gov (United States)

    Lee, Jinah; Duy, Pham Khac; Yoon, Jihye; Chung, Hoeil

    2014-06-21

    A bead-incorporated transmission scheme (BITS) has been demonstrated for collecting reproducible transmission near-infrared (NIR) spectra of samples with inconsistent shapes. Isotropically diffused NIR radiation was applied around a sample and the surrounding radiation was allowed to interact homogeneously with the sample for transmission measurement. Samples were packed in 1.40 mm polytetrafluoroethylene (PTFE) beads, ideal diffusers without NIR absorption, and then transmission spectra were collected by illuminating the sample-containing beads using NIR radiation. When collimated radiation was directly applied, a small portion of the non-fully diffused radiation (NFDR) propagated through the void space of the packing and eventually degraded the reproducibility. Pre-diffused radiation was introduced by placing an additional PTFE disk in front of the packing to diminish NFDR, which produced more reproducible spectral features. The proposed scheme was evaluated by analyzing two different solid samples: density determination for individual polyethylene (PE) pellets and identification of mining locality for tourmalines. Because spectral collection was reproducible, the use of the spectrum acquired from one PE pellet was sufficient to accurately determine the density of nine other pellets with different shapes. The differentiation of tourmalines, which are even more dissimilar in appearance, according to their mining locality was also feasible with the help of the scheme.

  11. Infrared spectra of two isomers of protonated carbonyl sulfide (HOCS+and HSCO+) and t-HOCS in solid para-hydrogen.

    Science.gov (United States)

    Tsuge, Masashi; Lee, Yuan-Pern

    2016-10-28

    We report infrared (IR) spectra of HOCS + , HSCO + , t-HOCS, and other species produced on electron bombardment of a mixture of carbonyl sulfide (OCS) and para-hydrogen (p-H 2 ) during deposition at 3.2 K. After maintenance of the matrix in darkness for 15 h, the intensities of absorption features of HOCS + at 2945.9 (ν 1 ), 1875.3 (ν 2 ), and 1041.9 (ν 3 ) cm -1 and those of HSCO + at 2506.9 (ν 1 ) and 2074.2 (ν 2 ) cm -1 decreased through neutralization with trapped electrons. Lines observed at 3563.4, 1394.8, and 1199.0 cm -1 , which decreased slightly in intensity after maintenance in darkness and were nearly depleted after irradiation at 373 nm, are assigned to a t-HOCS radical. The corresponding spectra of their 13 C- and D-isotopologues were observed. The IR spectra of HSCO + and t-HOCS and those of modes ν 2 and ν 3 of HOCS + are new. The assignments were made according to the expected chemical behavior and a comparison of experimental and calculated wavenumbers and 13 C- and D-isotopic shifts. The wavenumber of the OH stretching mode (2945.9 cm -1 ) of HOCS + in solid p-H 2 is significantly red-shifted from that (3435.16 cm -1 ) reported for gaseous HOCS + ; this shift is attributed to partial sharing of a proton between OCS and H 2 . The corresponding p-H 2 induced shift is small in HSCO + because of a much weaker interaction between HSCO + and H 2 .

  12. ON THE VIABILITY OF THE PAH MODEL AS AN EXPLANATION OF THE UNIDENTIFIED INFRARED EMISSION FEATURES

    International Nuclear Information System (INIS)

    Zhang, Yong; Kwok, Sun

    2015-01-01

    Polycyclic aromatic hydrocarbon (PAH) molecules are widely considered the preferred candidate for the carrier of the unidentified infrared emission bands observed in the interstellar medium and circumstellar envelopes. In this paper, we report the results of fitting a variety of non-PAH spectra (silicates, hydrogenated amorphous carbon, coal, and even artificial spectra) using the theoretical infrared spectra of PAHs from the NASA Ames PAH IR Spectroscopic Database. We show that these non-PAH spectra can be well fitted by PAH mixtures. This suggests that a general match between astronomical spectra and those of PAH mixtures does not necessarily provide definitive support for the PAH hypothesis

  13. Arrangement of Fibril Side Chains Studied by Molecular Dynamics and Simulated Infrared and Vibrational Circular Dichroism Spectra

    Czech Academy of Sciences Publication Activity Database

    Kessler, Jiří; Kiederling, T. A.; Bouř, Petr

    2014-01-01

    Roč. 118, č. 24 (2014), s. 6937-6945 ISSN 1520-6106 R&D Projects: GA ČR GAP208/11/0105; GA MŠk(CZ) LH11033 Grant - others:MŠMT(CZ) LM2010005; AV ČR(CZ) M200550902; MŠMT(CZ) ED3.2.00/08.0144 Institutional support: RVO:61388963 Keywords : insulin amyloid superstructures * DFT * VCD * molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.302, year: 2014

  14. Improving the analysis of near-infrared spectroscopy data with multivariate classification of hemodynamic patterns: A theoretical formulation and validation.

    Science.gov (United States)

    Gemignani, Jessica; Middell, Eike; Barbour, Randall L; Graber, Harry L; Blankertz, Benjamin

    2018-04-04

    The statistical analysis of Functional Near Infrared Spectroscopy (fNIRS) data based on the General Linear Model (GLM) is often made difficult by serial correlations, high inter-subject variability of the hemodynamic response, and the presence of motion artifacts. In this work we propose to extract information on the pattern of hemodynamic activations without using any a priori model for the data, by classifying the channels as "active" or "not active" with a multivariate classifier based on Linear Discriminant Analysis (LDA). This work is developed in two steps. First we compared the performance of the two analyses, using a synthetic approach in which simulated hemodynamic activations were combined with either simulated or real resting-state fNIRS data. This procedure allowed for exact quantification of the classification accuracies of GLM and LDA. In the case of real resting-state data, the correlations between classification accuracy and demographic characteristics were investigated by means of a Linear Mixed Model. In the second step, to further characterize the reliability of the newly proposed analysis method, we conducted an experiment in which participants had to perform a simple motor task and data were analyzed with the LDA-based classifier as well as with the standard GLM analysis. The results of the simulation study show that the LDA-based method achieves higher classification accuracies than the GLM analysis, and that the LDA results are more uniform across different subjects and, in contrast to the accuracies achieved by the GLM analysis, have no significant correlations with any of the demographic characteristics. Findings from the real-data experiment are consistent with the results of the real-plus-simulation study, in that the GLM-analysis results show greater inter-subject variability than do the corresponding LDA results. The results obtained suggest that the outcome of GLM analysis is highly vulnerable to violations of theoretical assumptions

  15. Characterization of ionizing radiation effects on bone using Fourier Transform Infrared Spectroscopy and multivariate analysis of spectra

    Energy Technology Data Exchange (ETDEWEB)

    Castro, Pedro Arthur Augusto de; Dias, Derly Augusto; Zezell, Denise Maria, E-mail: zezell@usp.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2017-11-01

    Ionizing radiation has been used as an important treatment and diagnostic method for several diseases. Optical techniques provides an efficient clinical diagnostic to support an accurate evaluation of the interaction of radiation with molecules. Fourier-transform infrared spectroscopy coupled with attenuated total reflectance (ATR-FTIR) is a label-free and nondestructive optical technique that can recognize functional groups in biological samples. In this work, 30 fragments of bone were collected from bovine femur diaphysis. Samples were cut and polished until 1 cm x 1 cm x 1 mm, which were then stored properly in the refrigerated environment. Samples irradiation was performed with a Cobalt-60 Gammacell Irradiator source at doses of 0.1 kGy, 1 kGy, whereas the fragments exposed to dose of 15 kGy was irradiated in a multipurpose irradiator of Cobalt-60. Spectral data was submitted to principal component analysis followed by linear discriminant analysis. Multivariate analysis was performed with Principal component analysis(PCA) followed by Linear Discriminant Analysis(LDA) using MATLAB R2015a software (The Mathworks Inc., Natick, MA, USA). We demonstrated the feasibility of using ATR-FTIR spectroscopy associated with PCA-LDA multivariate technique to evaluate the molecular changes in bone matrix caused by different doses: 0.1 kGy, 1 kGy and 15 kGy. These alterations between the groups are mainly reported in phosphate region. Our results open up new possibilities for protein monitoring relating to dose responses. (author)

  16. Characterization of ionizing radiation effects on bone using Fourier Transform Infrared Spectroscopy and multivariate analysis of spectra

    International Nuclear Information System (INIS)

    Castro, Pedro Arthur Augusto de; Dias, Derly Augusto; Zezell, Denise Maria

    2017-01-01

    Ionizing radiation has been used as an important treatment and diagnostic method for several diseases. Optical techniques provides an efficient clinical diagnostic to support an accurate evaluation of the interaction of radiation with molecules. Fourier-transform infrared spectroscopy coupled with attenuated total reflectance (ATR-FTIR) is a label-free and nondestructive optical technique that can recognize functional groups in biological samples. In this work, 30 fragments of bone were collected from bovine femur diaphysis. Samples were cut and polished until 1 cm x 1 cm x 1 mm, which were then stored properly in the refrigerated environment. Samples irradiation was performed with a Cobalt-60 Gammacell Irradiator source at doses of 0.1 kGy, 1 kGy, whereas the fragments exposed to dose of 15 kGy was irradiated in a multipurpose irradiator of Cobalt-60. Spectral data was submitted to principal component analysis followed by linear discriminant analysis. Multivariate analysis was performed with Principal component analysis(PCA) followed by Linear Discriminant Analysis(LDA) using MATLAB R2015a software (The Mathworks Inc., Natick, MA, USA). We demonstrated the feasibility of using ATR-FTIR spectroscopy associated with PCA-LDA multivariate technique to evaluate the molecular changes in bone matrix caused by different doses: 0.1 kGy, 1 kGy and 15 kGy. These alterations between the groups are mainly reported in phosphate region. Our results open up new possibilities for protein monitoring relating to dose responses. (author)

  17. [Quantitative prediction of soil salinity content with visible-near infrared hyper-spectra in northeast China].

    Science.gov (United States)

    Zhang, Xiao-guang; Huang, Biao; Ji, Jun-feng; Hu, Wen-you; Sun, Wei-xia; Zhao, Yong-cun

    2012-08-01

    Studying the spectral property of salinized soil is an important work, for it is the base of monitoring soil salinization by remote sense. To investigate the spectral property of salinized soil and the relationship between the soil salinity and the hyperspectral data, the field soil samples were collected in the region of Northeast China and then reflectance spectra were measured. The partial least squares regression (PLSR) model was established based on the statistical analysis of the soil salinity content and the reflectance of hyperspectra. The feasibility of soil salinity prediction by hyperspectra was decided by analyzed calibration model and independent validation. Models accuracy was also analyzed, which was established in the conditions of different treatment methods and different re-sampling intervals. The results showed that it was feasible to predict soil salinity content based on measured reflectance spectrum. The results also revealed that it was necessary to smooth measured hyperspectra for spectral prediction accuracy to be improved significantly after smoothing. The best model was established based on smoothed and log(l/x) transformed hyperspectra with high determination coefficients (R2) of 0.6677 and RPD = 1.61, which showed that this math transformation could eliminate noise effectively and so as to improve the prediction accuracy. The largest re-sampling interval is 8 nm that could meet the accuracy of the soil salinity prediction. Therefore, it provided scientific reference of monitoring soil salinization by remote sensing from satellite platform.

  18. Supramolecular structures for determination and identification of the bond lengths in novel uranyl complexes from their infrared spectra

    Science.gov (United States)

    El-Sonbati, A. Z.; Diab, M. A.; Morgan, Sh. M.; Seyam, H. A.

    2018-02-01

    Novel dioxouranium (VI) heterochelates with neutral bidentate compounds (Ln) have been synthesized. The ligands and the heterochelates [UO2(Ln)2(O2NO)2] were confirmed and characterized by elemental analysis, 1H NMR, UV.-Vis, IR, mass spectroscopy, X-ray diffraction and thermogravimetric analysis (TGA). IR spectral data suggest that the molecules of the Schiff base are coordinated to the central uranium atom (ON donor). The nitrato groups are coordinated as bidentate ligands. The thermodynamic parameters were calculated using Coats-Redfern and Horowitz-Metzger methods. The ligands (Ln) and their complexes (1-3) showed the υ3 frequency of UO22+ has been shown to be an excellent molecular probe for studying the coordinating power of the ligands. The values of υ3 of the prepared complexes containing UO22+ were successfully used to calculate the force constant, FUO (1n 10-8N/Å) and the bond length RUO (Å) of the Usbnd O bond. A strategy based upon both theoretical and experimental investigations has been adopted. The theoretical aspects are described in terms of the well-known theory of 5d-4f transitions. Wilson's, matrix method, Badger's formula, and Jones and El-Sonbati equations were used to calculate the Usbnd O bond distances from the values of the stretching and interaction force constants. The most probable correlation between Usbnd O force constant to Usbnd O bond distance were satisfactorily discussed in term of Badger's rule and the equations suggested by Jones and El-Sonbati. The effect of Hammett's constant is also discussed.

  19. Predicting ambient aerosol thermal-optical reflectance (TOR) measurements from infrared spectra: extending the predictions to different years and different sites

    Science.gov (United States)

    Reggente, Matteo; Dillner, Ann M.; Takahama, Satoshi

    2016-02-01

    Organic carbon (OC) and elemental carbon (EC) are major components of atmospheric particulate matter (PM), which has been associated with increased morbidity and mortality, climate change, and reduced visibility. Typically OC and EC concentrations are measured using thermal-optical methods such as thermal-optical reflectance (TOR) from samples collected on quartz filters. In this work, we estimate TOR OC and EC using Fourier transform infrared (FT-IR) absorbance spectra from polytetrafluoroethylene (PTFE Teflon) filters using partial least square regression (PLSR) calibrated to TOR OC and EC measurements for a wide range of samples. The proposed method can be integrated with analysis of routinely collected PTFE filter samples that, in addition to OC and EC concentrations, can concurrently provide information regarding the functional group composition of the organic aerosol. We have used the FT-IR absorbance spectra and TOR OC and EC concentrations collected in the Interagency Monitoring of PROtected Visual Environments (IMPROVE) network (USA). We used 526 samples collected in 2011 at seven sites to calibrate the models, and more than 2000 samples collected in 2013 at 17 sites to test the models. Samples from six sites are present both in the calibration and test sets. The calibrations produce accurate predictions both for samples collected at the same six sites present in the calibration set (R2 = 0.97 and R2 = 0.95 for OC and EC respectively), and for samples from 9 of the 11 sites not included in the calibration set (R2 = 0.96 and R2 = 0.91 for OC and EC respectively). Samples collected at the other two sites require a different calibration model to achieve accurate predictions. We also propose a method to anticipate the prediction error; we calculate the squared Mahalanobis distance in the feature space (scores determined by PLSR) between new spectra and spectra in the calibration set. The squared Mahalanobis distance provides a crude method for assessing the

  20. A COMPARISON OF NEAR-INFRARED PHOTOMETRY AND SPECTRA FOR Y DWARFS WITH A NEW GENERATION OF COOL CLOUDY MODELS

    Energy Technology Data Exchange (ETDEWEB)

    Leggett, S. K. [Gemini Observatory, Northern Operations Center, 670 North A' ohoku Place, Hilo, HI 96720 (United States); Morley, Caroline V.; Fortney, Jonathan J. [Department of Astronomy and Astrophysics, University of California, Santa Cruz, CA 95064 (United States); Marley, M. S. [NASA Ames Research Center, Mail Stop 245-3, Moffett Field, CA 94035 (United States); Saumon, D. [Los Alamos National Laboratory, P.O. Box 1663, MS F663, Los Alamos, NM 87545 (United States); Visscher, Channon, E-mail: sleggett@gemini.edu [Southwest Research Institute, Boulder, CO 80302 (United States)

    2013-02-15

    We present YJHK photometry, or a subset, for the six Y dwarfs discovered in Wide-field Infrared Survey Explorer (WISE) data by Cushing et al. The data were obtained using the Near-Infrared Imager on the Gemini North telescope; YJHK were obtained for WISEP J041022.71+150248.5, WISEP J173835.52+273258.9, and WISEPC J205628.90+145953.3; YJH for WISEPC J140518.40+553421.5 and WISEP J154151.65225025.2; and YJK for WISEP J182831.08+265037.8. We also present a far-red spectrum obtained using GMOS-North for WISEPC J205628.90+145953.3. We compare the data to Morley et al. models, which include cloud decks of sulfide and chloride condensates. We find that the models with these previously neglected clouds can reproduce the energy distributions of T9 to Y0 dwarfs quite well, other than near 5 {mu}m where the models are too bright. This is thought to be because the models do not include departures from chemical equilibrium caused by vertical mixing, which would enhance the abundance of CO and CO{sub 2}, decreasing the flux at 5 {mu}m. Vertical mixing also decreases the abundance of NH{sub 3}, which would otherwise have strong absorption features at 1.03 {mu}m and 1.52 {mu}m that are not seen in the Y0 WISEPC J205628.90+145953.3. We find that the five Y0 to Y0.5 dwarfs have 300 {approx}< T {sub eff} K {approx}< 450, 4.0 {approx}< log g {approx}< 4.5, and f {sub sed} Almost-Equal-To 3. These temperatures and gravities imply a mass range of 5-15 M {sub Jupiter} and ages around 5 Gyr. We suggest that WISEP J182831.08+265037.8 is a binary system, as this better explains its luminosity and color. We find that the data can be made consistent with observed trends, and generally consistent with the models, if the system is composed of a T {sub eff} Almost-Equal-To 325 K and log g {approx}< 4.5 primary, and a T {sub eff} Almost-Equal-To 300 K and log g {approx}> 4.0 secondary, corresponding to masses of 10 and 7 M {sub Jupiter} and an age around 2 Gyr. If our deconvolution is correct

  1. Effects of anisotropic interaction-induced properties of hydrogen-rare gas compounds on rototranslational Raman scattering spectra: Comprehensive theoretical and numerical analysis.

    Science.gov (United States)

    Głaz, Waldemar; Bancewicz, Tadeusz; Godet, Jean-Luc; Gustafsson, Magnus; Haskopoulos, Anastasios; Maroulis, George

    2016-07-21

    A comprehensive study is presented of many aspects of the depolarized anisotropic collision induced (CI) component of light scattered by weakly bound compounds composed of a dihydrogen molecule and a rare gas (Rg) atom, H2-Rg. The work continues a series of earlier projects marking the revival of interest in linear light scattering following the development of new highly advanced tools of quantum chemistry and other theoretical, computational, and experimental means of spectral analyses. Sophisticated ab initio computing procedures are applied in order to obtain the anisotropic polarizability component's dependence on the H2-Rg geometry. These data are then used to evaluate the CI spectral lines for all types of Rg atoms ranging from He to Xe (Rn excluded). Evolution of the properties of CI spectra with growing polarizability/masses of the complexes studied is observed. Special attention is given to the heaviest, Kr and Xe based, scatterers. The influence of specific factors shaping the spectral lines (e.g., bound and metastable contribution, potential anisotropy) is discussed. Also the share of pressure broadened allowed rotational transitions in the overall spectral profile is taken into account and the extent to which it is separable from the pure CI contribution is discussed. We finish with a brief comparison between the obtained results and available experimental data.

  2. Theoretical studies of the optical and EPR spectra for VO{sup 2+} in MgKPO{sub 4}·6H{sub 2}O single crystal

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hua-Ming, E-mail: huamingzhang66@gmail.com [Key Laboratory of Nondestructive Testing, Ministry of Education, Nanchang Hangkong University, Nanchang 330063 (China); Xiao, Wen-Bo [Key Laboratory of Nondestructive Testing, Ministry of Education, Nanchang Hangkong University, Nanchang 330063 (China); Wan, Xiong [Key Laboratory of Nondestructive Testing, Ministry of Education, Nanchang Hangkong University, Nanchang 330063 (China); Key Laboratory of Space Active Opto-Electronics Technology, Shanghai Institute of Technical Physics of the Chinese Academy of Sciences, Shanghai 200083 (China)

    2014-09-15

    The optical absorption and electron paramagnetic resonance (EPR) parameters (g factors g{sub ||}, g{sub ⊥} and hyperfine structure constants A{sub ||}, A{sub ⊥}) of a tetragonal V{sup 4+} center in MgKPO{sub 4}·6H{sub 2}O (MPPH) crystal are theoretically investigated using the perturbation formulas for a 3d{sup 1} ion in tetragonally compressed octahedra. In these formulas, the contributions from the s- and p-orbitals as well as the spin–orbit coupling coefficient of the O{sup 2−} ligand are taken into account based on the cluster approach. The calculated results are in good agreement with the observed values. The local structure parameters of the [VO{sub 6}]{sup 8−} cluster are obtained from the calculation. The magnitudes of the metal–ligand distances parallel and perpendicular to the C{sub 4}-axis are, respectively, R||≈1.846 Å and R{sub ⊥}≈2.032 Å. The validity of the calculated results has also been discussed. - Highlights: • The tetragonal field parameters are associated with the local structures of the impurity V{sup 4+} center. • Ligand contributions are taken into account from the cluster approach. • EPR and optical spectra are analyzed for the impurity V{sup 4+} center in the MPPH crystal.

  3. CRIRES-POP: a library of high resolution spectra in the near-infrared. II. Data reduction and the spectrum of the K giant 10 Leonis

    Science.gov (United States)

    Nicholls, C. P.; Lebzelter, T.; Smette, A.; Wolff, B.; Hartman, H.; Käufl, H.-U.; Przybilla, N.; Ramsay, S.; Uttenthaler, S.; Wahlgren, G. M.; Bagnulo, S.; Hussain, G. A. J.; Nieva, M.-F.; Seemann, U.; Seifahrt, A.

    2017-02-01

    Context. High resolution stellar spectral atlases are valuable resources to astronomy. They are rare in the 1-5 μm region for historical reasons, but once available, high resolution atlases in this part of the spectrum will aid the study of a wide range of astrophysical phenomena. Aims: The aim of the CRIRES-POP project is to produce a high resolution near-infrared spectral library of stars across the H-R diagram. The aim of this paper is to present the fully reduced spectrum of the K giant 10 Leo that will form the basis of the first atlas within the CRIRES-POP library, to provide a full description of the data reduction processes involved, and to provide an update on the CRIRES-POP project. Methods: All CRIRES-POP targets were observed with almost 200 different observational settings of CRIRES on the ESO Very Large Telescope, resulting in a basically complete coverage of its spectral range as accessible from the ground. We reduced the spectra of 10 Leo with the CRIRES pipeline, corrected the wavelength solution and removed telluric absorption with Molecfit, then resampled the spectra to a common wavelength scale, shifted them to rest wavelengths, flux normalised, and median combined them into one final data product. Results: We present the fully reduced, high resolution, near-infrared spectrum of 10 Leo. This is also the first complete spectrum from the CRIRES instrument. The spectrum is available online. Conclusions: The first CRIRES-POP spectrum has exceeded our quality expectations and will form the centre of a state-of-the-art stellar atlas. This first CRIRES-POP atlas will soon be available, and further atlases will follow. All CRIRES-POP data products will be freely and publicly available online. The spectrum is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/598/A79

  4. Structural changes of mitochondrial creatine kinase upon binding of ADP, ATP, or Pi, observed by reaction-induced infrared difference spectra.

    Science.gov (United States)

    Granjon, T; Vacheron, M J; Vial, C; Buchet, R

    2001-03-06

    Structural modifications of rabbit heart mitochondrial creatine kinase induced by the binding of its nucleotide substrates and Pi were investigated. Reaction-induced difference spectra (RIDS), resulting from the difference between infrared spectra recorded before and after the photorelease of a caged ligand, allow us to detect very small variations in protein structure. Our results indicated that the protein secondary structure remained relatively stable during nucleotide binding. Indeed, this binding to creatine kinase affected only a few amino acids, and caused small peptide backbone deformations and alterations of the carbonyl side chains of aspartate or glutamate, reflecting modifications within preexisting elements rather than a net change in secondary structure. Nonetheless, MgADP and MgATP RIDS were distinct, whereas the MgPi RIDS presented some similarities with the MgATP one. The difference between MgADP and MgATP RIDS could reflect a distinct configuration of the two metal-nucleotide complexes inducing a different positioning and/or a distinct binding mode to the creatine kinase active site. Comparison of the MgATP and MgPi RIDS suggests that Pi binding took place at the same binding site as the gamma-phosphoryl group of ATP. Thus, the difference between MgADP and MgATP RIDS would mainly be due to the effect of the gamma-P of ATP. The differences observed when comparing the RIDS resulting from the binding of nucleotides to octameric mitochondrial creatine kinase or dimeric cytosolic isoform could reflect the distinct oligomerization states and physicochemical or kinetic properties of the two isoenzymes.

  5. Within tree variation of lignin, extractives, and microfibril angle coupled with the theoretical and near infrared modeling of microfibril angle

    Science.gov (United States)

    Brian K. Via; chi L. So; Leslie H. Groom; Todd F. Shupe; michael Stine; Jan. Wikaira

    2007-01-01

    A theoretical model was built predicting the relationship between microfibril angle and lignin content at the Angstrom (A) level. Both theoretical and statistical examination of experimental data supports a square root transformation of lignin to predict microfibril angle. The experimental material used came from 10 longleaf pine (Pinus palustris)...

  6. Infrared spectra of HSCS+, c-HSCS, and HCS2-produced on electron bombardment of CS2in solid para-hydrogen.

    Science.gov (United States)

    Tsuge, Masashi; Lee, Yuan-Pern

    2017-04-05

    We report infrared (IR) spectra of HSCS + , c-HSCS, HCS 2 - , and other species produced on electron bombardment of a mixture of CS 2 and para-hydrogen (p-H 2 ) during deposition at 3.2 K. After maintenance of the deposited matrix in darkness for 12 h, the intensities of the absorption lines of HSCS + at 2477.2 (ν 1 ), 1525.6 (ν 2 ), and 919.6 cm -1 (ν 3 ) decreased through neutralization of HSCS + with trapped electrons. During this period, the intensities of the lines of HCS 2 - at 2875.7 (ν 1 ), 1249.9 (ν 5 ), 1003.2 (ν 6 ), and 814.3 cm -1 (ν 4 ) increased due to reaction between H and CS 2 - . The intensities of the lines observed at 2312.7 and 889.0 cm -1 , which are assigned to the c-HSCS radical, increased after maintenance in darkness and greatly diminished after irradiation at 373 nm. The IR spectra of HSCS + , HCS 2 - , and c-HSCS are reported for the first time. The IR absorption lines of the t-HSCS radical, t-HC(S)SH, and c-HC(S)SH were also identified; their wavenumbers are similar to those reported for these species in an Ar matrix. The corresponding spectra of the 13 C, 34 S, and D isotopic variants of these species were observed. The assignments were made according to the expected chemical behavior, predicted potential energies of associated reactions, and a comparison of observed and predicted wavenumbers and their 13 C, 34 S, and D isotopic ratios. In contrast to the observed significant red shifts of the OH-stretching wavenumbers of HOCO + and HOCS + in solid p-H 2 compared to those in the gaseous phase due to proton sharing with H 2 , the wavenumber of the HS-stretching mode of HSCS + in solid p-H 2 (2477.2 cm -1 ) is similar to the anharmonic wavenumber of HSCS + (2424 cm -1 ) predicted with the B3LYP/aug-cc-pVTZ method, indicating that the sharing of a proton between HSCS + and neighboring H 2 molecules is insignificant.

  7. Infrared spectra of ovalene (C32H14) and hydrogenated ovalene (C32H15˙) in solid para-hydrogen.

    Science.gov (United States)

    Tsuge, Masashi; Bahou, Mohammed; Wu, Yu-Jong; Allamandola, Louis; Lee, Yuan-Pern

    2016-10-19

    We report the infrared (IR) spectra of ovalene (C 32 H 14 ) and hydrogenated ovalene (C 32 H 15 ˙) in solid para-hydrogen (p-H 2 ). The hydrogenated ovalene and protonated ovalene were generated from electron bombardment of a mixture of ovalene and p-H 2 during deposition of a matrix at 3.2 K. The features that decreased with time have been previously assigned to 7-C 32 H 15 + , the most stable isomer of protonated ovalene (Astrophys. J., 2016, 825, 96). The spectral features that increased with time are assigned to the most stable isomer of hydrogenated ovalene (7-C 32 H 15 ˙) based on the expected chemistry and on a comparison with the vibrational wavenumbers and IR intensities predicted by the B3PW91/6-311++G(2d,2p) method. The mechanism of formation of 7-C 32 H 15 ˙ is discussed according to the observed changes in intensity and calculated energetics of possible reactions of H + C 32 H 14 and isomerization of C 32 H 15 ˙. The formation of 7-C 32 H 15 ˙ is dominated by the reaction H + C 32 H 14 → 7-C 32 H 15 ˙, implying that, regardless of the presence of a barrier, the hydrogenation of polycyclic aromatic hydrocarbons occurs even at 3.2 K.

  8. Application of the Polynomial-Based Least Squares and Total Least Squares Models for the Attenuated Total Reflection Fourier Transform Infrared Spectra of Binary Mixtures of Hydroxyl Compounds.

    Science.gov (United States)

    Shan, Peng; Peng, Silong; Zhao, Yuhui; Tang, Liang

    2016-03-01

    An analysis of binary mixtures of hydroxyl compound by Attenuated Total Reflection Fourier transform infrared spectroscopy (ATR FT-IR) and classical least squares (CLS) yield large model error due to the presence of unmodeled components such as H-bonded components. To accommodate these spectral variations, polynomial-based least squares (LSP) and polynomial-based total least squares (TLSP) are proposed to capture the nonlinear absorbance-concentration relationship. LSP is based on assuming that only absorbance noise exists; while TLSP takes both absorbance noise and concentration noise into consideration. In addition, based on different solving strategy, two optimization algorithms (limited-memory Broyden-Fletcher-Goldfarb-Shanno (LBFGS) algorithm and Levenberg-Marquardt (LM) algorithm) are combined with TLSP and then two different TLSP versions (termed as TLSP-LBFGS and TLSP-LM) are formed. The optimum order of each nonlinear model is determined by cross-validation. Comparison and analyses of the four models are made from two aspects: absorbance prediction and concentration prediction. The results for water-ethanol solution and ethanol-ethyl lactate solution show that LSP, TLSP-LBFGS, and TLSP-LM can, for both absorbance prediction and concentration prediction, obtain smaller root mean square error of prediction than CLS. Additionally, they can also greatly enhance the accuracy of estimated pure component spectra. However, from the view of concentration prediction, the Wilcoxon signed rank test shows that there is no statistically significant difference between each nonlinear model and CLS. © The Author(s) 2016.

  9. Technical note: Characterization of lipid constitution in Fourier transform infrared spectra and spectroscopic discrimination of animal-derived feedstuffs from different species.

    Science.gov (United States)

    Gao, F; Han, L; Yang, Z; Xu, L; Liu, X

    2017-06-01

    The objective of the current work was to assess the capability of Fourier transform infrared (FT-IR) spectroscopy in combination with chemometric methods to discriminate animal-derived feedstuffs from different origins based on the lipid characteristics. A total of 82 lipid samples extracted from animal-derived feedstuffs, comprising porcine, poultry, bovine, ovine, and fish samples, were investigated by gas chromatography and FT-IR. The relationship between the lipid constitutions and the responding FT-IR spectral characteristics were explored. Results indicated that high correlations ( > 0.900) were found between the contents of MUFA and PUFA and FT-IR spectral data. In addition, the peak intensity at about 1,116 and 1,098 cm-1 showed a significant difference ( < 0.05) between ruminant and nonruminant animals; the change of peak ratio (1,116:1,098) was proved consistent with the degree of unsaturation of lipid from different animal species. Successful discrimination was further achieved among porcine, poultry, bovine, and ovine meat and bone meal (MBM) and fishmeal based on lipid characteristics by applying the FT-IR spectra coupled with chemometrics, for which the values of sensitivity and specificity were close to 1 and classification error were almost equal to 0.

  10. Infrared spectra of the CH3-MX and CH2-MHX complexes formed by reactions of laser-ablated group 3 metal atoms with methyl halides.

    Science.gov (United States)

    Cho, Han-Gook; Andrews, Lester

    2007-04-05

    Reactions of laser-ablated group 3 metal atoms with methyl halides have been carried out in excess of Ar during condensation and the matrix infrared spectra studied. The metals are as effective as other early transition metals in providing insertion products (CH3-MX) and higher oxidation state methylidene complexes (CH2-MHX) (X = F, Cl, Br) following alpha-hydrogen migration. Unlike the cases of the group 4-6 metals, the calculated methylidene complex structures show little evidence for agostic distortion, consistent with the previously studied group 3 metal methylidene hydrides, and the C-M bond lengths of the insertion and methylidene complexes are comparable to each other. However, the C-Sc bond lengths are 0.013, 0.025, and 0.029 A shorter for the CH2-ScHX complexes, respectively, and the spin densities are consistent with weak C(2p)-Sc(3d) pi bonding. The present results reconfirm that the number of valence electrons on the metal is important for agostic interaction in simple methylidene complexes.

  11. The SpeX Prism Library: 1000+ low-resolution, near-infrared spectra of ultracool M, L, T and Y dwarfs

    Science.gov (United States)

    Burgasser, Adam J.

    The SpeX Prism Library (SPL) is a uniform compilation of low-resolution (λ/Δλ ≈ 75-120), near-infrared (0.8--2.5 μm) spectra spanning a decade of observations with the IRTF SpeX spectrograph. Primarily containing ultracool M, L, T and Y dwarfs, this spectral library has been used in over 100 publications to date, facilitating a broad range of science on low mass stars, exoplanets, high redshift sources and instrument/survey design. I summarize the contents of the SPL and highlight a few of the key scientific results that have made use of this resource, as well as applications in education, outreach and art. I also outline the future plans of the SPL, which include a reanalysis of early data, better integration and dissemination of source and spectral metadata, conversion to Virtual Observatory formats, development of a Python software package for community analysis, and a design for a node-based visual programming platform that can facilitate citizen science and project-based learning in stellar spectroscopy. http://www.browndwarfs.org/spexprism

  12. Infrared absorption spectra of gaseous HD. II. Collision-induced fundamental band of HD in HD--Ne and HD--Ar mixtures at room temperature

    International Nuclear Information System (INIS)

    Prasad, R.D.G.; Reddy, S.P.

    1976-01-01

    The collision-induced infrared absorption spectra of the fundamental band of HD in binary mixtures of HD with Ne and Ar at room temperature have been studied with an absorption path length of 105.2 cm for different base densities of HD in the range 8--20 amagat and a number of total gas densities up to 175 amagat. The observed features of the profiles of the enhancement of absorption in these mixtures resemble closely those of the corresponding profiles of the fundamental band of H 2 in binary mixtures with Ne and Ar. The binary absorption coefficients of the band obtained from the measured integrated intensities are (1.84 +- 0.06) x 10 -35 and (4.41 +- 0.06) x 10 -35 cm 6 s -1 for HD--Ne and HD--Ar, respectively. The characteristic half-width parameters, delta/subd/ and delta/subc/ of the overlap transitions and delta/subq/ (and delta/subq//sub prime/) of the quadrupolar transitions, are obtained from an analysis of the profiles of the enhancement of absorption in both these mixtures. The quantity delta/subc/ which is the half-width of the intercollisional interference dip of the Q branch increases with the density of the perturbing gas Ne or Ar, and for HD--Ne it varies in a manner similar to that for HD--He as described in Paper I of this series

  13. The Infrared Spectra of Polycyclic Aromatic Hydrocarbons with Excess Peripheral H Atoms (H(sub n)-PAHs) and their Relation to the 3.4 and 6.9 Micrometer PAH Emission Features

    Science.gov (United States)

    Sandford, Scott A.; Bernstein, Max P.; Materese, Christopher K.

    2013-01-01

    A population of polycyclic aromatic hydrocarbons (PAHs) and related materials are thought to be responsible for the family of infrared emission features that are seen towards a wide variety of astrophysical environments. A potentially important subclass of these materials are polycyclic aromatic hydrocarbons whose edges contain excess H atoms (H(sub n)-PAHs). While it has been suggested that this type of compound may be present in the interstellar population, it has been difficult to properly assess this possibility because of a lack of suitable infrared laboratory spectra to assist with analysis of the astronomical data. We present the 4000-500 cm(exp -1) (2.5-20 micrometers) infrared spectra of 23 H(sub n)-PAHs and related molecules isolated in argon matrices, under conditions suitable for use in the interpretation of astronomical data. The spectra of molecules with mixed aromatic and aliphatic domains show unique characteristics that distinguish them from their fully aromatic PAH equivalents. We discuss the changes to the spectra of these types of molecules as they transition from fully aromatic to fully aliphatic forms. The implications for the interpretation of astronomical spectra are discussed with specific emphasis on the 3.4 and 6.9 micrometer features. Laboratory data is compared with emission spectra from IRAS 21282+5050, an object with normal PAH emission features, in addition to IRAS 22272+5435 and IRAS 0496+3429, two protoplanetary nebulae with abnormally large 3.4 micrometer features. We show that 'normal' PAH emission objects contain relatively few H(sub n)-PAHs in their emitter populations, but less evolved protoplanetary nebulae may contain significant abundances of these molecules.

  14. INFRARED SPECTRA, THERMOGRAVIMETRIC ANALYSIS AND ...

    African Journals Online (AJOL)

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    methyl- quinazolinone in coordination and the formation of a bond between the oxygen of L with the central metal ions, and that nitrogen atom was not the donor atom. For. [Cu(CH3COO)2(L)3]⋅2H2O complex the stretching asymmetric (νas) of ...

  15. Theoretical evaluation of accuracy in position and size of brain activity obtained by near-infrared topography

    International Nuclear Information System (INIS)

    Kawaguchi, Hiroshi; Hayashi, Toshiyuki; Kato, Toshinori; Okada, Eiji

    2004-01-01

    Near-infrared (NIR) topography can obtain a topographical distribution of the activated region in the brain cortex. Near-infrared light is strongly scattered in the head, and the volume of tissue sampled by a source-detector pair on the head surface is broadly distributed in the brain. This scattering effect results in poor resolution and contrast in the topographic image of the brain activity. In this study, a one-dimensional distribution of absorption change in a head model is calculated by mapping and reconstruction methods to evaluate the effect of the image reconstruction algorithm and the interval of measurement points for topographic imaging on the accuracy of the topographic image. The light propagation in the head model is predicted by Monte Carlo simulation to obtain the spatial sensitivity profile for a source-detector pair. The measurement points are one-dimensionally arranged on the surface of the model, and the distance between adjacent measurement points is varied from 4 mm to 28 mm. Small intervals of the measurement points improve the topographic image calculated by both the mapping and reconstruction methods. In the conventional mapping method, the limit of the spatial resolution depends upon the interval of the measurement points and spatial sensitivity profile for source-detector pairs. The reconstruction method has advantages over the mapping method which improve the results of one-dimensional analysis when the interval of measurement points is less than 12 mm. The effect of overlapping of spatial sensitivity profiles indicates that the reconstruction method may be effective to improve the spatial resolution of a two-dimensional reconstruction of topographic image obtained with larger interval of measurement points. Near-infrared topography with the reconstruction method potentially obtains an accurate distribution of absorption change in the brain even if the size of absorption change is less than 10 mm

  16. CCSD(T) Study of CD3-O-CD3 and CH3-O-CD3 Far-Infrared Spectra

    Science.gov (United States)

    Senent, M. L.; Dominguez-Gomez, R.; Carvajal, M.; Villa, M.

    2012-06-01

    From a vibrationally corrected 3D potential energy surface determined with highly correlated ab initio calculations (CCSD(T)), the lowest vibrational energies of two dimethyl-ether isotopologues, (12)CH(3)-(16)O-(12)CD(3) (DME-d(3)) and (12)CD(3)-(16)O-(12)CD(3) (DME-d(6)), are computed variationally. The levels that can be populated at very low temperatures correspond to the COC-bending and the two methyl torsional modes. Molecular symmetry groups are used for the classification of levels and torsional splittings. DME-d(6) belongs to the G(36) group, as the most abundant isotopologue (12)CH(3)-(16)O-(12)CH(3) (DME-h(6)), while DME-d(3) is a G(18) species. Previous assignments of experimental Raman and far-infrared spectra are discussed from an effective Hamiltonian obtained after refining the ab initio parameters. Because a good agreement between calculated and experimental transition frequencies is reached, new assignments are proposed for various combination bands corresponding to the two deuterated isotopologues and for the 020 → 030 transition of DME-d(6). Vibrationally corrected potential energy barriers, structural parameters, and anharmonic spectroscopic parameters are provided. For the 3N - 9 neglected vibrational modes, harmonic and anharmonic fundamental frequencies are obtained using second-order perturbation theory by means of CCSD and MP2 force fields. Fermi resonances between the COC-bending and the torsional modes modify DME-d(3) intensities and the band positions of the torsional overtones.

  17. Laser-Ablated U Atom Reactions with (CN)2 to Form UNC, U(NC)2, and U(NC)4: Matrix Infrared Spectra and Quantum Chemical Calculations.

    Science.gov (United States)

    Fang, Zongtang; Garner, Edward B; Dixon, David A; Gong, Yu; Andrews, Lester; Liebov, Benjamin

    2018-01-18

    Laser-ablated U atoms react with (CN) 2 in excess argon and neon during codeposition at 4 K to form UNC, U(NC) 2 , and U(NC) 4 as the major uranium-bearing products, which are identified from their matrix infrared spectra using cyanogen substituted with 13 C and 15 N and from quantum chemical calculations. The 12/13 CN and C 14/15 N isotopic frequency ratios computed for the U(NC) 1,2,4 molecules agree better with the observed values than those calculated for the U(CN) 1,2,4 isomers. Multiplets using mixed isotopic cyanogens reveal the stoichiometries of these products, and the band positions and quantum chemical calculations confirm the isocyanide bonding arrangements, which are 14 and 51 kJ/mol more stable than the cyanide isomers for UNC and U(NC) 2 , respectively, and 62 kJ/mol for U(NC) 4 in the isolated gas phase at the CCSD(T)/CBS level. The studies further demonstrate that the isocyano nitrogen is a better π donor, so it interacts with U(VI) better than carbon. Although the higher isocyanides are more stable than the corresponding cyanides, U(NC) 5 and U(NC) 6 were not observed here most likely because unfavorable or endothermic routes are required for their production from U(NC) 4 . The computed U-NC bond dissociation energies decrease from 581 kJ/mol for 4 [UNC] to 168 kJ/mol for 1 [U(NC) 6 ]. The ionic nature of U(NC) n decreases as the number of isocyano groups increases.

  18. Probing the spin multiplicity of gas-phase polycyclic aromatic hydrocarbons through their infrared emission spectrum: a theoretical study.

    Science.gov (United States)

    Falvo, Cyril; Calvo, Florent; Parneix, Pascal

    2012-08-14

    The anharmonic infrared emission spectrum following an optical excitation has been calculated for a variety of polycyclic aromatic hydrocarbon molecules in their ground singlet electronic state or in their triplet state. The computational protocol relies on second-order perturbation theory and involves a quartic vibrational Hamiltonian, the vibrational quantum numbers being sampled according to a Monte Carlo procedure. In the case of neutral naphthalene, the IR spectrum obtained in the (ground) singlet state differs significantly from the spectrum in the triplet state, especially for out-of-plane CH bending modes. Although not as prominent, spectral differences in larger molecules are still observable.

  19. Theoretical Research on Ellipsoidal Structure Methane Gas Detection Based on Near Infrared Light Sources of PbSe Quantum Dots

    Directory of Open Access Journals (Sweden)

    Xiaoxue Xing

    2017-01-01

    Full Text Available To improve the precision and sensitivity of the detection in near infrared gas detection system, the selection of light source and design of gas chamber structure are two key links. In this paper, the near infrared (NIR light sources fabricated with PbSe quantum dots (QDs and a new gas cell structure using an ellipsoid reflector were designed to test the concentration of methane (CH4. The double wavelengths differential detection method was used in the paper. The signal wavelength is 1.665 μm from the NIR QD-based light source with 5.1 nm PbSe QDs. The reference wavelength is 1.943 μm from the NIR QD-based light source with 6.1 nm PbSe QDs. The experimental results show that the differential gain signal could be enhanced 80 times when the major axis, the focus, and the open length of the ellipsoid reflector are 4.18 cm, 3.98 cm, and 0.36 cm, respectively. The structure will be convenient for the signal amplifying, AD converting, and other process in the latter circuits, and therefore both the detection sensitivity and precision can be improved.

  20. Thermodynamics of reversible gas adsorption on alkali-metal exchanged zeolites - the interplay of infrared spectroscopy and theoretical calculations

    Czech Academy of Sciences Publication Activity Database

    Otero Areán, C.; Nachtigallová, Dana; Nachtigall, Petr; Garrone, E.; Rodríguez Delgado, M.

    2007-01-01

    Roč. 9, č. 12 (2007), s. 1421-1437 ISSN 1463-9076 R&D Projects: GA MŠk LC512; GA ČR GA203/06/0324 Grant - others: UIB (ES) MAT2006-05350 Institutional research plan: CEZ:AV0Z40550506 Keywords : adsorption * zeolites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.343, year: 2007

  1. Infrared Optical Response of Metallic Graphene Nanoribbons

    Directory of Open Access Journals (Sweden)

    Zigang Duan

    2010-01-01

    Full Text Available We investigate theoretically the infrared optical response characteristics of metallic armchair/zigzag-edge graphene nanoribbons (A/ZGNRs to an external longitudinally polarized electromagnetic field at low temperatures. Within the framework of linear response theory at the perturbation regime, we examine the optical infrared absorption threshold energy, absorption power, dielectric function, and electron energy loss spectra near the neutrality points of the systems. It is demonstrated that, by some numerical examples, the photon-assisted direct interband absorptions for AGNR exist with different selection rules from those for ZGNR and single-walled carbon nanotube at infrared regime. This infrared optical property dependence of GNRs on field frequency may be used to design graphene-based nanoscale optoelectronic devices for the detection of infrared electromagnetic irradiations.

  2. Anharmonic Theoretical Vibrational Spectroscopy of Polypeptides.

    Science.gov (United States)

    Panek, Paweł T; Jacob, Christoph R

    2016-08-18

    Because of the size of polypeptides and proteins, the quantum-chemical prediction of their vibrational spectra presents an exceptionally challenging task. Here, we address one of these challenges, namely, the inclusion of anharmonicities. By performing the expansion of the potential energy surface in localized-mode coordinates instead of the normal-mode coordinates, it becomes possible to calculate anharmonic vibrational spectra of polypeptides efficiently and reliably. We apply this approach to calculate the infrared, Raman, and Raman optical activity spectra of helical alanine polypeptides consisting of up to 20 amino acids. We find that while anharmonicities do not alter the band shapes, simple scaling procedures cannot account for the different shifts found for the individual bands. This closes an important gap in theoretical vibrational spectroscopy by making it possible to quantify the anharmonic contributions and opens the door to a first-principles calculation of multidimensional vibrational spectra.

  3. Predicting enteric methane emission of dairy cows with milk Fourier-transform infrared spectra and gas chromatography-based milk fatty acid profiles.

    Science.gov (United States)

    van Gastelen, S; Mollenhorst, H; Antunes-Fernandes, E C; Hettinga, K A; van Burgsteden, G G; Dijkstra, J; Rademaker, J L W

    2018-03-14

    The objective of the present study was to compare the prediction potential of milk Fourier-transform infrared spectroscopy (FTIR) for CH 4 emissions of dairy cows with that of gas chromatography (GC)-based milk fatty acids (MFA). Data from 9 experiments with lactating Holstein-Friesian cows, with a total of 30 dietary treatments and 218 observations, were used. Methane emissions were measured for 3 consecutive days in climate respiration chambers and expressed as production (g/d), yield (g/kg of dry matter intake; DMI), and intensity (g/kg of fat- and protein-corrected milk; FPCM). Dry matter intake was 16.3 ± 2.18 kg/d (mean ± standard deviation), FPCM yield was 25.9 ± 5.06 kg/d, CH 4 production was 366 ± 53.9 g/d, CH 4 yield was 22.5 ± 2.10 g/kg of DMI, and CH 4 intensity was 14.4 ± 2.58 g/kg of FPCM. Milk was sampled during the same days and analyzed by GC and by FTIR. Multivariate GC-determined MFA-based and FTIR-based CH 4 prediction models were developed, and subsequently, the final CH 4 prediction models were evaluated with root mean squared error of prediction and concordance correlation coefficient analysis. Further, we performed a random 10-fold cross validation to calculate the performance parameters of the models (e.g., the coefficient of determination of cross validation). The final GC-determined MFA-based CH 4 prediction models estimate CH 4 production, yield, and intensity with a root mean squared error of prediction of 35.7 g/d, 1.6 g/kg of DMI, and 1.6 g/kg of FPCM and with a concordance correlation coefficient of 0.72, 0.59, and 0.77, respectively. The final FTIR-based CH 4 prediction models estimate CH 4 production, yield, and intensity with a root mean squared error of prediction of 43.2 g/d, 1.9 g/kg of DMI, and 1.7 g/kg of FPCM and with a concordance correlation coefficient of 0.52, 0.40, and 0.72, respectively. The GC-determined MFA-based prediction models described a greater part of the observed variation in CH 4 emission than did the

  4. Patterns of energy levels and spectra for polyatomic molecules

    International Nuclear Information System (INIS)

    Harter, W.G.

    1983-01-01

    Laser spectroscopy has revealed a remarkable intricacy in the rotational, vibrational, and electronic energy levels for polyatomic molecules. The infrared spectra of SF 6 , CF 4 , and related molecules contain several levels of structure on top of structure which resembles a fractal in some ways. The purpose of this article will be to exhibit some of this structure and introduce the simplest theoretical interpretations of it which are presently available

  5. The Infrared Spectra of Polycyclic Aromatic Hydrocarbons with Excess Peripheral H Atoms (Hn-PAHs) and their Relation to the 3.4 and 6.9 µm PAH Emission Features.

    Science.gov (United States)

    Sandford, Scott A; Bernstein, Max P; Materese, Christopher K

    Polycyclic aromatic hydrocarbons (PAHs) are likely responsible for the family of infrared emission features seen in a wide variety of astrophysical environments. A potentially important subclass of these materials are PAHs whose edges contain excess H atoms (H n -PAHs). This type of compound may be present in space, but it has been difficult to assess this possibility because of a lack of suitable laboratory spectra to assist with analysis of astronomical data. We present 4000-500 cm -1 (2.5-20 µm) infrared spectra of 23 H n -PAHs and related molecules isolated in argon matrices under conditions suitable for interpretation of astronomical data. Spectra of molecules with mixed aromatic and aliphatic domains show characteristics that distinguish them from fully aromatic PAH equivalents. Two major changes occur as PAHs become more hydrogenated: (1) aromatic C-H stretching bands near 3.3 µm weaken and are replaced with stronger aliphatic bands near 3.4 µm, and (2) aromatic C-H out-of-plane bending mode bands in the 11-15 µm region shift and weaken concurrent with growth of a strong aliphatic -CH 2 -deformation mode near 6.9 µm. Implications for interpreting astronomical spectra are discussed with emphasis on the 3.4 and 6.9 µm features. Laboratory data is compared with emission spectra from IRAS 21282+5050, an object with normal PAH emission features, and IRAS 22272+5435 and IRAS 0496+3429, two protoplanetary nebulae with abnormally large 3.4 µm features. We show that 'normal' PAH emission objects contain relatively few H n -PAHs in their emitter populations, but less evolved protoplanetary nebulae may contain significant abundances of these molecules.

  6. Theoretical modeling of Comptonized X-ray spectra of super-Eddington accretion flow: Origin of hard excess in ultraluminous X-ray sources

    Science.gov (United States)

    Kitaki, Takaaki; Mineshige, Shin; Ohsuga, Ken; Kawashima, Tomohisa

    2017-12-01

    X-ray continuum spectra of super-Eddington accretion flow are studied by means of Monte Carlo radiative transfer simulations based on the radiation hydrodynamic simulation data, in which both thermal- and bulk-Compton scatterings are taken into account. We compare the calculated spectra of accretion flow around black holes with masses of MBH = 10, 102, 103, and 104 M⊙ for a fixed mass injection rate (from the computational boundary at 103 rs) of 103 LEdd/c2 (with rs, LEdd, and c being the Schwarzschild radius, the Eddington luminosity, and the speed of light, respectively). The soft X-ray spectra exhibit mass dependence in accordance with the standard-disk relation; the maximum surface temperature is scaled as T ∝ M_{ BH}^{ -1/4}. The spectra in the hard X-ray band, by contrast with soft X-ray, look to be quite similar among different models, if we normalize the radiation luminosity by MBH. This reflects that the hard component is created by thermal- and bulk-Compton scatterings of soft photons originating from an accretion flow in the overheated and/or funnel regions, the temperatures of which have no dependence on mass. The hard X-ray spectra can be reproduced by a Wien spectrum with the temperature of T ˜ 3 keV accompanied by a hard excess at photon energy above several keV. The excess spectrum can be fitted well with a power law with a photon index of Γ ˜ 3. This feature is in good agreement with that of the recent NuSTAR observations of ULXs (ultra-luminous X-ray sources).

  7. Theoretical predictions of the two-dimensional solid-state NMR spectra: a case study of the 13C-1H correlations in metergoline

    Czech Academy of Sciences Publication Activity Database

    Czernek, Jiří; Brus, Jiří

    2013-01-01

    Roč. 586, 24 October (2013), s. 56-60 ISSN 0009-2614 Institutional support: RVO:61389013 Keywords : NMR * shielding * metergoline Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.991, year: 2013

  8. Improved quantitative analysis of spectra using a new method of obtaining derivative spectra based on a singular perturbation technique.

    Science.gov (United States)

    Li, Zhigang; Wang, Qiaoyun; Lv, Jiangtao; Ma, Zhenhe; Yang, Linjuan

    2015-06-01

    Spectroscopy is often applied when a rapid quantitative analysis is required, but one challenge is the translation of raw spectra into a final analysis. Derivative spectra are often used as a preliminary preprocessing step to resolve overlapping signals, enhance signal properties, and suppress unwanted spectral features that arise due to non-ideal instrument and sample properties. In this study, to improve quantitative analysis of near-infrared spectra, derivatives of noisy raw spectral data need to be estimated with high accuracy. A new spectral estimator based on singular perturbation technique, called the singular perturbation spectra estimator (SPSE), is presented, and the stability analysis of the estimator is given. Theoretical analysis and simulation experimental results confirm that the derivatives can be estimated with high accuracy using this estimator. Furthermore, the effectiveness of the estimator for processing noisy infrared spectra is evaluated using the analysis of beer spectra. The derivative spectra of the beer and the marzipan are used to build the calibration model using partial least squares (PLS) modeling. The results show that the PLS based on the new estimator can achieve better performance compared with the Savitzky-Golay algorithm and can serve as an alternative choice for quantitative analytical applications.

  9. Infrared absorption spectra of partially deuterated methoxy radicals CH2DO and CHD2O isolated in solid para-hydrogen.

    Science.gov (United States)

    Haupa, Karolina A; Johnson, Britta A; Sibert, Edwin L; Lee, Yuan-Pern

    2017-10-21

    The investigation of partially deuterated methoxy radicals is important because the symmetry lowering from C 3v to C s provides new insights into the couplings between rovibronic states via Jahn-Teller and spin-orbit interactions. The vibrational spectrum of the partially deuterated methoxy radical CH 2 DO in a matrix of p-H 2 has been recorded. This species was prepared by irradiating a p-H 2 matrix containing deuterated d 1 -nitritomethane (CH 2 DONO) at 3.3 K with laser light at 355 nm. The identification of the radical is based on the photochemical behavior of the precursor and comparison of observed vibrational wavenumbers and infrared (IR) intensities with those predicted from a refined quartic, curvilinear, internal coordinate force field calculated with the coupled-cluster singles and doubles with perturbative triples/cc-pVTZ method. CH 2 DO reacts with H 2 with a rate coefficient (3.5 ± 1.0) × 10 -3 s -1 . Predominantly c-CHDOH and a negligibly small amount of t-CHDOH were produced. This stereoselectivity results from the reaction H + C s -CH 2 DOH, which was demonstrated by an additional experiment on irradiation of a CH 2 DOH/Cl 2 /p-H 2 matrix with ultraviolet and IR light to induce the H + CH 2 DOH reaction; only c-CHDOH was observed from this experiment. Even though the energies of transition states and products for the formation of c-CHDOH and t-CHDOH differ by only ∼10 cm -1 , the selective formation of c-CHDOH can be explained by tunneling of the hydrogen atom via an optimal tunneling path. Similarly, the vibronic spectrum for the partially deuterated specie d 2 -methoxy radical (CHD 2 O) was obtained upon irradiation of d 2 -nitritomethane (CHD 2 ONO) at 355 nm. Lines associated with the fundamental vibrational modes were observed and assigned; line positions agree with theoretically predicted vibrational wavenumbers. CHD 2 O reacts with H 2 with a rate coefficient (6.0 ± 1.4) × 10 -3 s -1 ; CD 2 OH was produced as a major product because

  10. THEORETICAL SPECTRA OF THE AM CANUM VENATICORUM BINARY SYSTEM SDSS J0926+3624: EFFECTS OF IRRADIATION ONTO THE DONOR STAR

    International Nuclear Information System (INIS)

    Sengupta, Sujan; Taam, Ronald E.

    2011-01-01

    Taking into account a range of parameters determined from evolutionary models and available observational data, the detailed non-LTE spectrum for the primary star and the irradiated donor star in the AM Canum Venaticorum system SDSS J0926+3624 are constructed based on the TLUSTY stellar atmosphere code. The combined spectrum of the primary and the donor stars along with a multicolor blackbody spectrum of the accretion disk that reproduces a detailed numerical model is compared to the Sloan Digital Sky Survey optical spectrum of the system. The photometric flux of the primary star inferred from eclipse observations is compared with the synthetic spectrum. The model fit of the two independent observations provides an upper limit on the distance of the system for different effective temperatures of the primary. In addition, an upper limit on the combined flux of the disk and the donor in the infrared region wherein the contribution of the primary is negligible is also determined. It is shown that the spectrum of a sufficiently cool donor can exhibit emission lines due to irradiation from a hot primary and the emission features should be detectable in the infrared even though the contribution of the flux from the disk dominates. Thus, it is pointed out that infrared observations of the system would provide important information on the thermal state of the donor as well as useful insight into the thermal properties of the primary star and the accretion disk.

  11. Gas Phase Infrared Multiple Photon Dissociation Spectra of Positively Charged Sodium Bis(2-ethylhexyl)sulfosuccinate Reverse Micelle-like Aggregates

    NARCIS (Netherlands)

    Giorgi, G.; Ceraulo, L.; G. Berden,; Oomens, J.; Liveri, V. T.

    2011-01-01

    The capability of infrared multiple photon dissociation (IRMPD) spectroscopy to gain structural information on surfactant-based supramolecular aggregates has been exploited to elucidate intermolecular interactions and local organization of positively charged sodium bis(2-ethylhexyl)sulfosuccinate

  12. A perturbation theoretic approach to the Riccati equation for the Floquet energies, spectral intensities, and cutoff energy of harmonic generation in photon emission from nonadiabatic electron-transfer dynamics driven by infrared CW laser fields

    Science.gov (United States)

    Mizuno, Yuta; Arasaki, Yasuki; Takatsuka, Kazuo

    2016-01-01

    A complicated yet interesting induced photon emission can take place by a nonadiabatic intramolecular electron transfer system like LiF under an intense CW laser [Y. Arasaki, S. Scheit, and K. Takatsuka, J. Chem. Phys. 138, 161103 (2013)]. Behind this phenomena, the crossing point between two potential energy curves of covalent and ionic natures in diabatic representation is forced to oscillate, since only the ionic potential curve is shifted significantly up and down repeatedly (called the Dynamical Stark effect). The wavepacket pumped initially to the excited covalent potential curve frequently encounters such a dynamically moving crossing point and thereby undergoes very complicated dynamics including wavepacket bifurcation and deformation. Intramolecular electron transfer thus driven by the coupling between nonadiabatic state-mixing and laser fields induces irregular photon emission. Here in this report we discuss the complicated spectral features of this kind of photon emission induced by infrared laser. In the low frequency domain, the photon emission is much more involved than those of ultraviolet/visible driving fields, since many field-dressed states are created on the ionic potential, which have their own classical turning points and crossing points with the covalent counterpart. To analyze the physics behind the phenomena, we develop a perturbation theoretic approach to the Riccati equation that is transformed from coupled first-order linear differential equations with periodic coefficients, which are supposed to produce the so-called Floquet states. We give mathematical expressions for the Floquet energies, frequencies, and intensities of the photon emission spectra, and the cutoff energy of their harmonic generation. Agreement between these approximate quantities and those estimated with full quantum calculations is found to be excellent. Furthermore, the present analysis provides with notions to facilitate deeper understanding for the physical and

  13. Differentiation of perirenal and omental fat quality of suckling lambs according to the rearing system from Fourier transforms mid-infrared spectra using partial least squares and artificial neural networks analysis.

    Science.gov (United States)

    Osorio, M T; Zumalacárregui, J M; Alaiz-Rodríguez, R; Guzman-Martínez, R; Engelsen, S B; Mateo, J

    2009-09-01

    Fourier transform mid-infrared (FT-IR) spectroscopy was evaluated as a tool to discriminate between carcasses of suckling lambs according to the rearing system. Fat samples (39 perirenal and 67 omental) were collected from carcasses of lambs from up to three sheep dairy farms, reared on either ewes milk (EM) or milk replacer (MR). Fatty acid composition of the samples from each fat deposit was first analyzed and, when discriminant-partial least squares regression (PLS) was applied, a perfect discrimination between rearing systems could be established. Additionally, FT-IR spectra of fat samples were obtained and discriminant-PLS and artificial neural network (ANN) based analysis were applied to data sets, the latter using principal component analysis (PCA) or support vector machines (SVM) as processing procedure. Perirenal fat samples were perfectly discriminated from their FT-IR spectra. However, analysis of omental fat showed misclassification rates of 9-13%, with the ANN approach showing a higher discrimination power.

  14. The covariance of the differences between experimental and theoretical chemical shifts as an aid for assigning two-dimensional heteronuclear correlation solid-state NMR spectra

    Czech Academy of Sciences Publication Activity Database

    Czernek, Jiří; Brus, Jiří

    2014-01-01

    Roč. 608, 21 July (2014), s. 334-339 ISSN 0009-2614 R&D Projects: GA ČR(CZ) GA14-03636S Institutional support: RVO:61389013 Keywords : NMR * DFT * covariance Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.897, year: 2014

  15. Comparison of theoretically predicted and observed Solar Maximum Mission X-ray spectra for the 1980 April 13 and May 9 flares

    International Nuclear Information System (INIS)

    Smith, D.F.; Orwig, L.E.

    1982-01-01

    A method for predicting the hard X-ray spectrum in the 10--100 keV range for compact flares during their initial rise is developed on the basis of a thermal model. Observations of the flares of 1980 April 13, 4:05 U.T., and 1980 May 9, 7:12 U.T. are given and their combined spectra from the Hard X-ray Burst Spectrometer and Hard X-ray Imaging Spectrometer on the Solar Maximum Mission are deduced. Constraints on the cross sectional area of the supposed emitting arch are obtained from data from the Hard X-ray Imaging Spectrometer. A power-law spectrum is predicted for the rise of the flare of April 13 for initial arch densities less than 10 10 cm -3 and also for the flare of May 9 for initial arch densities less than 5.4 x 10 10 cm -3 . In both cases power-law spectra are observed. Limitations and implications of these results are discussed

  16. Effects of the voids filling on the lattice vibrations for the CoSb3-based thermoelectric materials-Raman scattering spectra and theoretical study

    International Nuclear Information System (INIS)

    Lu Pengxian; Shen Zigang; Hu Xing

    2010-01-01

    The unfilled CoSb 3 and the voids filled skutterudites (La, Ce and La 0.5 Ce 0.5 ) Fe 3 CoSb 12 powders were synthesized via a hydrothermal route and the effects of the La and Ce filling in the voids on the Raman scattering spectra were investigated. The results suggest that the phonon vibration frequencies of the filled skutterudites in the lower frequency range shift down significantly, while the others in the higher frequency range shift up slightly as compared with the unfilled CoSb 3 . The calculated phonon frequencies for the (La, Ce and La 0.5 Ce 0.5 ) Fe 3 CoSb 12 indicate that all the frequencies shift down, but the frequency shifting down in the lower frequency range is more remarkable than that in the higher frequency range. By comparing the electron density differences of the unfilled CoSb 3 and the voids filled (La, Ce and La 0.5 Ce 0.5 ) Fe 3 CoSb 12 , the frequency shifting phenomena observed in the Raman scattering spectra may be attributed to the complex bonding behaviors between the La or Ce atoms with the parent Co and Sb atoms.

  17. Theoretical studies on the electronic structure, charge distribution and vibrational spectra of diglyme-M +-AsF 6- (M = Li, Na, K)

    Science.gov (United States)

    Pinjari, Rahul V.; Joshi, Kaustubh A.; Gejji, Shridhar P.

    2008-12-01

    Electronic structure and the vibrational spectra of CH 3(OCH 2CH 2) 2OCH 3-M +-AsF 6- (M = Li, Na, K) have been obtained using the density functional theory. Lithium ion exhibits a pentavalent coordination via 3 oxygens from diglyme and two fluorines of AsF 6- whereas Na + and K + exhibit coordinate number 6 with 3 fluorines of the anion binding to alkali metal in these complexes. Analysis of calculated spectra reveal that the CH 2 wag (840-1120 cm -1) vibrations in the complex are sensitive to metal ion coordination. A frequency downshift relative to the free anion has been predicted for the vibrations of AsF 6- anion when the fluorines are directly bonded (denoted by F*) to metal ion. Consequent reorganization of electron density in the complex engenders a frequency shift in the opposite direction for As-F vibrations wherein the fluorine atoms are not coordinating to the alkali metal ion. An approach based on the molecular electron density topography coupled with the difference electron density map explains the direction of the frequency shifts of C-O-C and the As-F stretchings compared to those of free diglyme or AsF 6 anion. A new method, which includes the color-mapping function for the difference molecular electron density (MED), superimposed on the bond critical points in MED topography has been suggested to explain the direction of the frequency shifts in a single attempt.

  18. Theoretical Characterizaiton of Visual Signatures

    Science.gov (United States)

    Kashinski, D. O.; Chase, G. M.; di Nallo, O. E.; Scales, A. N.; Vanderley, D. L.; Byrd, E. F. C.

    2015-05-01

    We are investigating the accuracy of theoretical models used to predict the visible, ultraviolet, and infrared spectra, as well as other properties, of product materials ejected from the muzzle of currently fielded systems. Recent advances in solid propellants has made the management of muzzle signature (flash) a principle issue in weapons development across the calibers. A priori prediction of the electromagnetic spectra of formulations will allow researchers to tailor blends that yield desired signatures and determine spectrographic detection ranges. Quantum chemistry methods at various levels of sophistication have been employed to optimize molecular geometries, compute unscaled vibrational frequencies, and determine the optical spectra of specific gas-phase species. Electronic excitations are being computed using Time Dependent Density Functional Theory (TD-DFT). A full statistical analysis and reliability assessment of computational results is currently underway. A comparison of theoretical results to experimental values found in the literature is used to assess any affects of functional choice and basis set on calculation accuracy. The status of this work will be presented at the conference. Work supported by the ARL, DoD HPCMP, and USMA.

  19. The Rovibronic Spectra of the Cyclopentadienyl Radical

    Science.gov (United States)

    Sharma, Ketan; Miller, Terry A.; Stanton, John F.; Nesbitt, David

    2017-06-01

    Cyclopentadienyl (Cp) radical has been subject to numerous studies for the greater part of half a century. Experimental work has involved photo-electron spectroscopy, laser induced fluorescence excitation and emission, infrared absorption spectroscopy, and recently rotationally resolved spectra in the CH stretch region taken at JILA. Even more theoretical works appear in the literature, but substantial advances in computation have occurred since their completion. Cp's highly symmetric (D_{5h}) structure and doubly degenerate electronic ground (˜{X}^2E_1^{''}), which is subject to linear Jahn-Teller distortion, have been a great motivation for work on it. We have commenced new computational work to obtain a broad understanding of the electronic, vibrational, and rotational, i.e. rovibronic, structure of the Cp radical as revealed by its spectra, with particular emphasis on the new infrared spectra. The goal is to guide experiments and their analyses and reconcile results from spectroscopy and quantum chemistry calculations. T. Ichino, et al. J. Chem. Phys. 129, 084310 (2008) L. Yu, S. C. Foster, J. M. Williamson, M. C. Heaven and T. A. Miller J. Phys. Chem. 92, 4263 (1988) B. E. Applegate, A. J. Bezant and T. A. Miller J. Chem. Phys 114, 4869 (2001) D. Leicht, M. Kaufmann, G. Schwaab, and M. Havenith J. Chem. Phys. 145, 7 (2016), 074304.

  20. Theoretical energy level spectra and transition data for 4p64d, 4p64f and 4p54d2 configurations of W37+ ion

    International Nuclear Information System (INIS)

    Bogdanovich, P.; Kisielius, R.

    2012-01-01

    The ab initio quasirelativistic Hartree–Fock method developed specifically for the calculation of spectral parameters of heavy atoms and highly charged ions was applied to determine atomic data for tungsten ions. The correlation effects were included by adopting the configuration interaction method. The Breit–Pauli approximation for quasirelativistic Hartree–Fock radial orbitals was employed to take into account relativistic effects. The energy level spectra, radiative lifetimes, Lande factors g were calculated for the 4p 6 4d, 4p 6 4f and 4p 5 4d 2 configurations of W 37+ ion. The atomic data, namely, the transition wavelengths, spontaneous emission rates and oscillator strengths for the electric dipole, electric quadrupole and magnetic dipole transitions among and within the levels of these configurations are tabulated.

  1. X-ray absorption spectra and emission spectra of plasmas

    International Nuclear Information System (INIS)

    Peng Yonglun; Yang Li; Wang Minsheng; Li Jiaming

    2002-01-01

    The author reports a theoretical method to calculate the resolved absorption spectra and emission spectra (optically thin) of hot dense plasmas. Due to its fully relativistic treatment incorporated with the quantum defect theory, it calculates the absorption spectra and emission spectra for single element or multi-element plasmas with little computational efforts. The calculated absorption spectra of LTE gold plasmas agree well with the experimental ones. It also calculates the optical thin emission spectra of LTE gold plasmas, which is helpful to diagnose the plasmas of relevant ICF plasmas. It can also provide the relevant parameters such as population density of various ionic stages, precise radiative properties for ICF studies

  2. A comparison of telescopic and Phobos-2 ISM spectra of Mars in the short-wave near-infrared (0.76-1.02 microns)

    Science.gov (United States)

    Bell, James F., III; Mustard, John F.

    1993-01-01

    Recent analyses of near-IR (0.76-3.16 microns) Mars surface reflectance spectra obtained by the Phobos-2 ISM instrument during early 1989 have revealed the presence of substantial variability in surface spectral properties. Strong absorption features seen in the 0.85-1.05 micron region are up to 10-15 percent deep relative to the local continuum and have been interpreted as evidence of Fe(2+) and Fe(3+) bearing minerals (pyroxenes and iron oxides, respectively). Though these observed band depths are comparable to those seen in laboratory reflectance spectra, they are up to three times larger than most previously reported band depths for Mars spectra at these wavelengths. Six regions of variable albedo and geologic setting were identified where ISM and 1988 opposition telescopic coverage either overlapped physically or sampled the same surface geologic unit. The areal sizes and positions of the regions measured telescopically were compiled by Bell et al. ISM pixels falling within these spots were averaged to produce a spatially convolved spectrum that simulates what would have been seen telescopically. To facilitate comparisons of absorption band positions and relative strengths, the convolved ISM data and the 1988 telescopic spectra were scaled to unity at 0.81 microns and are presented. The data have also been convolved to equivalent band pass normalized reflectances in the region of spectral overlap. A scatter diagram of telescopic vs. ISM reflectances is shown. The results from the investigation are discussed.

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

    Science.gov (United States)

    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.

  4. Tunable dual emission in visible and near-infrared spectra using Co(2+)-doped PbSe nanocrystals embedded in a chalcogenide glass matrix.

    Science.gov (United States)

    Lourenço, Sidney A; Silva, Ricardo S; Dantas, Noelio O

    2016-08-17

    Semimagnetic Pb1-xCoxSe nanocrystals were synthesized by a fusion protocol in a glass matrix and characterized by optical absorption (OA), transmission electron microscopy (TEM), and photoluminescence (PL) techniques. OA spectra and TEM images strongly indicated the formation of Pb1-xCoxSe magnetic phases in the glass system and the quantum dot size was manipulated by tuning the annealing time. The OA spectra together with crystal field theory indicate that Co(2+) is located in the tetrahedral site (Td) and the PL of the Pb1-xCoxSe nanocrystals presents characteristic recombination in the visible (∼700 nm) and near-IR (1300-1600 nm) electromagnetic spectral range. With temperature decreasing, the PL spectra, in the visible spectral range, indicate an excited-state crossover yielding PL changes from (4)T1(P) → (4)A2(F) broadband emission to (2)E(G) → (4)A2(F) narrow-line emission. This phenomenon was explained on the basis of a configurational energy model. The OA and PL spectra of PbSe:Co(2+) indicate that the localized energy transition of Co(2+) ((4)A2(F) ↔ (4)T1((4)F)) can be tuned from the band-gap energy to the conduction-band energy of PbSe NCs by changing the NC size by increasing the thermal annealing time. In the near-IR spectral range, the temperature-dependent PL spectra show that the process of thermal activation of localized electrons in Co(2+) states can be transferred to the conduction band of the NCs. This process depends on the energy distance between extended and localized states, which can be controlled by the sample annealing time.

  5. Surface-Enhanced Infrared Spectra of Nicotinic Acid and Pyridoxine on Copper Substrates: What Is the Effect of Temperature and Deposition Conditions?

    Czech Academy of Sciences Publication Activity Database

    Kokaislová, A.; Parchaňský, Václav; Matějka, P.

    2015-01-01

    Roč. 119, č. 47 (2015), s. 26526-26539 ISSN 1932-7447 Institutional support: RVO:61388963 Keywords : absorption spectroscopy SEIRAS * Raman scattering * in situ Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.509, year: 2015

  6. Iminopropadienones RN=C=C=C=O and bisiminopropadienes RN=C=C=C=NR: matrix infrared spectra and anharmonic frequency calculations.

    Science.gov (United States)

    Bégué, Didier; Baraille, Isabelle; Andersen, Heidi Gade; Wentrup, Curt

    2013-10-28

    Methyliminopropadienone MeN=C=C=C=O 1a was generated by flash vacuum thermolysis from four different precursors and isolated in solid argon. The matrix-isolation infrared spectrum is dominated by unusually strong anharmonic effects resulting in complex fine structure of the absorptions due to the NCCCO moiety in the 2200 cm(-1) region. Doubling and tripling of the corresponding absorption bands are observed for phenyliminopropadienone PhN=C=C=C=O 1b and bis(phenylimino)propadiene PhN=C=C=C=NPh 9, respectively. Anharmonic vibrational frequency calculations allow the identification of a number of overtones and combination bands as the cause of the splittings for each molecule. This method constitutes an important tool for the characterization of reactive intermediates and unusual molecules by matrix-isolation infrared spectroscopy.

  7. Behaviour of 29Si NMR and infrared spectra of aqueous sodium and potassium silica solutions as a function of (SiO2/M2+O) ratio

    International Nuclear Information System (INIS)

    Couty, R.; Fernandez, L.

    1996-01-01

    Sodium and potassium solutions of silica with silica concentration of 1,4 mo/kg and R ms = SiO 2 /M + 2 O ratios of 4.56 to 1.6 were obtained by depolymerization of amorphous silica gel in sodium and potassium hydroxide. Solutions have been characterized by 29 Si NMR and infrared spectroscopy. The results indicated that Na + and K + exhibit the same behaviour during the depolymerization of silica. (authors). 11 refs., 4 figs., 2 tabs

  8. 1H NMR spectra of N-methyl-4-tolyl-1-(4-bromonaphthylamine and N-phenyl-1-(4-bromonaphthylamine: a combined experimental and theoretical study

    Directory of Open Access Journals (Sweden)

    Sergiy I. Okovytyy

    2014-03-01

    Full Text Available Theoretical investigations of the conformational properties and 1H NMR chemical shifts for N-methyl-4-tolyl-1-(4-bromonaphthylamine and N-phenyl-1-(4-bromonaphthylamine are reported. The calculations were performed at the DFT level (PBE1PBE functional using magnetically consistent 6-31G## and STO##-3Gmag basis sets. Conformational properties of the amines were studied using potential energy surface scanning. Chemical shifts were calculated using the GIAO and CSGT methods and averaged in proportion to the population of the corresponding conformations. Solvent effects (CDCl3 were accounted via PCM method. The obtained results allowed to assign the 1H NMR signals for the naphthalene moiety, which could not be done based on the experimental data alone.

  9. Atmospheric lifetimes, infrared absorption spectra, radiative forcings and global warming potentials of NF3 and CF3CF2Cl (CFC-115

    Directory of Open Access Journals (Sweden)

    A. Totterdill

    2016-09-01

    Full Text Available Fluorinated compounds such as NF3 and C2F5Cl (CFC-115 are characterised by very large global warming potentials (GWPs, which result from extremely long atmospheric lifetimes and strong infrared absorptions in the atmospheric window. In this study we have experimentally determined the infrared absorption cross sections of NF3 and CFC-115, calculated the radiative forcing and efficiency using two radiative transfer models and identified the effect of clouds and stratospheric adjustment. The infrared cross sections are within 10 % of previous measurements for CFC-115 but are found to be somewhat larger than previous estimates for NF3, leading to a radiative efficiency for NF3 that is 25 % larger than that quoted in the Intergovernmental Panel on Climate Change Fifth Assessment Report. A whole atmosphere chemistry–climate model was used to determine the atmospheric lifetimes of NF3 and CFC-115 to be (509 ± 21 years and (492 ± 22 years, respectively. The GWPs for NF3 are estimated to be 15 600, 19 700 and 19 700 over 20, 100 and 500 years, respectively. Similarly, the GWPs for CFC-115 are 6030, 7570 and 7480 over 20, 100 and 500 years, respectively.

  10. Intelligent evaluation of color sensory quality of black tea by visible-near infrared spectroscopy technology: A comparison of spectra and color data information

    Science.gov (United States)

    Ouyang, Qin; Liu, Yan; Chen, Quansheng; Zhang, Zhengzhu; Zhao, Jiewen; Guo, Zhiming; Gu, Hang

    2017-06-01

    Instrumental test of black tea samples instead of human panel test is attracting massive attention recently. This study focused on an investigation of the feasibility for estimation of the color sensory quality of black tea samples using the VIS-NIR spectroscopy technique, comparing the performances of models based on the spectra and color information. In model calibration, the variables were first selected by genetic algorithm (GA); then the nonlinear back propagation-artificial neural network (BPANN) models were established based on the optimal variables. In comparison with the other models, GA-BPANN models from spectra data information showed the best performance, with the correlation coefficient of 0.8935, and the root mean square error of 0.392 in the prediction set. In addition, models based on the spectra information provided better performance than that based on the color parameters. Therefore, the VIS-NIR spectroscopy technique is a promising tool for rapid and accurate evaluation of the sensory quality of black tea samples.

  11. Novel poly(triphenylamine-alt-fluorene) with asymmetric hexaphenylbenzene and pyrene moieties: synthesis, fluorescence, flexible near-infrared electrochromic devices and theoretical investigation

    KAUST Repository

    Wang, Po-I.

    2016-01-13

    © The Royal Society of Chemistry 2016. In this study, a new triphenylamine-alt-fluorene conjugated copolymer, HPBPYFL6, with hexaphenylbenzene (HPB) and pyrene as asymmetrical pendant groups was synthesized via Suzuki coupling polymerization. The conjugated polymer had a weight-average molecular weight of 5.8 × 104 g mol-1 with a polydispersity index of 2.5 characterized by gel permeation chromatography (GPC). HPBPYFL6 showed good solubility in common organic solvents such as NMP, THF, toluene and dichloromethane at 25°C. In addition, HPBPYFL6 possessed a high glass transition temperature of 260°C and a 10% weight-loss temperature of 503°C in nitrogen. HPBPYFL6 bearing a pyrene moiety had a solvatochromic fluorescence shift from a green to an orange emission as the polarity of the solvent increased. Cyclic voltammetry of HPBPYFL6 films cast onto indium-tin oxide-coated glass (ITO-glass) exhibited two oxidation redox couples at an E1/2 value of 0.82 and 1.17 V versus Ag/Ag+ in an acetonitrile solution. The HPBPYFL6 film on graphene-coated PET had an E1/2 value of 0.24 and 1.12 V. Conjugated polymer films exhibited reversible electrochromic behaviour with a colour change from pale yellow to deep blue upon electrochemical oxidation and high absorbance in the near-infrared (NIR) region. The switching and bleaching times were 5.16 s and 3.12 s for 1231 nm and were 3.30 s and 3.74 s for 1030 nm of HPBPYFL6 on ITO-glass. The strong NIR electrochromic absorbance of HPBPYFL6 was attributed to intervalence charge transfer by the incorporation of the HPB moiety. This phenomenon was confirmed by chemical oxidation as the oxidant contents increased in the solution state. Furthermore, the electrochromic mechanism was interpreted by DFT calculation and the simulated NIR electrochromic spectra of model compound HPBPYFL are in good agreement with the experimental data.

  12. Theoretical, ab initio and DFT, study of the structure and vibrational analysis of Raman, IR and INS spectra of (CH{sub 3}){sub 3}SiNCO

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Liencres, M.P. [Department of Physical and Analytical Chemistry, University of Jaen, 23071 Jaen (Spain)], E-mail: liencres@ujaen.es; Navarro, A. [Department of Physical and Analytical Chemistry, University of Jaen, 23071 Jaen (Spain); Ben Altabef, A. [Instituto de Quimica Fisica, Facultad de Bioquimica, Quimica y Farmacia, Universidad Nacional de Tucuman, San Lorenzo 456, 4000 S.M. de Tucuman (Argentina); Lopez-Gonzalez, J.J. [Department of Physical and Analytical Chemistry, University of Jaen, 23071 Jaen (Spain); Fernandez-Gomez, M. [Department of Physical and Analytical Chemistry, University of Jaen, 23071 Jaen (Spain); Kearley, G.J. [Department of Radiation, Radionuclides and Reactors, Faculty of Applied Sciences, Delft University of Technology, Mekelweg 15, 2629 JB Delft (Netherlands)

    2006-11-08

    The molecular geometry for trimethylsilylisocyanate ((CH{sub 3}){sub 3}SiNCO) has been calculated at MP2 and DFT/B3LYP and DFT/B3PW91 methods, and using the 6-31G*, 6-311G**, 6-311++G**, cc-pVDZ and cc-pVTZ basis sets. The equilibrium structure of the molecule, linear or bent as concerns the -SiNCO moiety, was found to rely on the method employed. The potential energy surface of -SiNC bending has been investigated by quantum mechanical ab initio calculations at MPn (n = 2-4) and QCISD(T) levels of theory with the cc-pVTZ basis set. This large amplitude bending motion (the {upsilon} {sub 24} mode) was determined to be very anharmonic, with a low barrier to linearity of the SiNCO skeleton of {approx}4-25 cm{sup -1}. New vapour and liquid IR, liquid Raman spectra and, for first time, INS spectrum have been recorded, and a complete vibrational assignment has been performed. INS data have allowed to assign two modes at 674 cm{sup -1} and 141 cm{sup -1} which, so far, have been considered as silent, i.e. A{sub 2}, since previous authors have used a frame of C {sub 3v} symmetry for this system. The intermolecular interactions show to have little effect on the torsional region (below 250 cm{sup -1} in INS spectrum) and the isolated-molecule approximation works well in that region. A normal coordinate analysis has been carried out by scaling the force fields calculated at MP2/6-311++G** and B3LYP/cc-pVDZ levels of theory using the scaled quantum mechanical force field (SQMFF) methodology. In order to get the best possible agreement between calculated and observed vibrational wavenumbers, the scale factors were refined by least squares yielding a final r.m.s. of {approx}7 cm{sup -1}.

  13. On the Raman and infrared vibrational spectra of the ɛ and ζ phases of oxygen. Systematic DFT studies with localized basis sets

    Science.gov (United States)

    Ochoa-Calle, A. J.; Zicovich-Wilson, C. M.; Ramírez-Solís, A.

    2015-10-01

    We address the pressure evolution of the Raman and infrared vibrational modes of the ɛ and ζ phases of oxygen. We use DFT with various GGA and hybrid functionals with localized atomic basis sets. The frequency evolution of the OV, MIR, FIR, L1 and L2 modes is in good agreement with experimental data. The better performance of all methods at pressures >30 GPa is related to the decreasing multireference character of the (O2)4 unit cell wavefunction. Hybrid functionals predict the ɛ-ζ phase transition by the appearance of red-shifted L1 and L2 Raman modes in the transition pressure region.

  14. Matrix infrared spectra and density functional calculations of the H2CCN and H2CNC radicals produced from CH3CN.

    Science.gov (United States)

    Cho, Han-Gook; Andrews, Lester

    2011-08-11

    The H(2)CCN and H(2)CNC radicals are observed in matrix IR spectra from acetonitrile exposed to radiation from laser ablation of transition metals, whereas cyc-H(2)CCN, another plausible isomer, is not. Density functional frequency calculations and D and (13)C isotopic substitutions substantiate the vibrational assignments. The cyano methyl radical converts to the 95 kJ/mol higher energy isocyano counterpart on uv photolysis. Computations show that the cyclic isomer is a shallow energy minimum between two transition states. Intrinsic reaction coordinate calculations indicate that conversion between the two products is feasible via the cyclic configuration.

  15. Regional prediction of soil organic carbon content over temperate croplands using visible near-infrared airborne hyperspectral imagery and synchronous field spectra

    Science.gov (United States)

    Vaudour, E.; Gilliot, J. M.; Bel, L.; Lefevre, J.; Chehdi, K.

    2016-07-01

    This study aimed at identifying the potential of Vis-NIR airborne hyperspectral AISA-Eagle data for predicting the topsoil organic carbon (SOC) content of bare cultivated soils over a large peri-urban area (221 km2) with both contrasted soils and SOC contents, located in the western region of Paris, France. Soil types comprised haplic luvisols, calcaric cambisols and colluvic cambisols. Airborne AISA-Eagle data (400-1000 nm, 126 bands) with 1 m-resolution were acquired on 17 April 2013 over 13 tracks. Tracks were atmospherically corrected then mosaicked at a 2 m-resolution using a set of 24 synchronous field spectra of bare soils, black and white targets and impervious surfaces. The land use identification system layer (RPG) of 2012 was used to mask non-agricultural areas, then calculation and thresholding of NDVI from an atmospherically corrected SPOT image acquired the same day enabled to map agricultural fields with bare soil. A total of 101 sites sampled either in 2013 or in the 3 previous years and in 2015 were identified as bare by means of this map. Predictions were made from the mosaic AISA spectra which were related to topsoil SOC contents by means of partial least squares regression (PLSR). Regression robustness was evaluated through a series of 1000 bootstrap data sets of calibration-validation samples, considering 74 sites outside cloud shadows only, and different sampling strategies for selecting calibration samples. Validation root-mean-square errors (RMSE) were comprised between 3.73 and 4.49 g Kg-1 and were ∼4 g Kg-1 in median. The most performing models in terms of coefficient of determination (R2) and Residual Prediction Deviation (RPD) values were the calibration models derived either from Kennard-Stone or conditioned Latin Hypercube sampling on smoothed spectra. The most generalizable model leading to lowest RMSE value of 3.73 g Kg-1 at the regional scale and 1.44 g Kg-1 at the within-field scale and low bias was the cross-validated leave

  16. Infrared and Raman spectra of (η 6-C 6H 6- nX n)Cr(CO) 3 complexes where X = Me ( n = 0-6) or OMe ( n = 0-2). A study of metal—ligand interactions

    Science.gov (United States)

    Armstrong, R. S.; Aroney, M. J.; Barnes, C. M.; Nugent, K. W.

    1994-07-01

    A systematic study is reported of the infrared and Raman spectra of methyl and methoxy substituted benzene chromium tricarbonyl complexes (η 6-C 6H 6- nX n)Cr(CO) 3 where X = Me ( n = 0-6) or OMe ( n = 0-2). Bands have been assigned and intensities calculated for a number of vibrational modes. Trends in the wavenumbers and band intensities of the arenemetal, metalcarbonyl and carbonyl bonds are examined to gain an insight into metal—ligand interactions and intramolecular electron rearrangements with progressive substitution on the arene. The results are discussed with regard σ-, π- and δ-contributions to arenemetal bonding and of σ- and π-components in metal-carbonyl and carbonyl bonding. The intensities are related to the polarities and polarizabilities of individual bonds within the molecules, and variations in these bond electronic properties with arene substitution are examined.

  17. Laser ablation of an indium target: time-resolved Fourier-transform infrared spectra of In I in the 700–7700 cm−1 range

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Kubelík, Petr; Ferus, Martin; Chernov, Vladislav E.; Zanozina, Ekaterina M.; Juha, Libor

    2014-01-01

    Roč. 29, č. 12 (2014), s. 2275-2283 ISSN 0267-9477 R&D Projects: GA MŠk LD14115; GA MŠk(CZ) LG13029 Institutional support: RVO:61388955 ; RVO:68378271 Keywords : time-resolved fluorescence * Fourier transform infra reds * Laser-induced breakdown spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.466, year: 2014

  18. Laser ablation of CsI: time-resolved Fourier-transform infrared spectra of atomic cesium in the 800-8000 cm(-1) range

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Ferus, Martin; Kubelík, Petr; Jelínek, Petr; Chernov, V. E.; Knyazev, M. Yu.

    2012-01-01

    Roč. 29, č. 5 (2012), s. 1112-1118 ISSN 0740-3224 R&D Projects: GA AV ČR IAA400400705 Grant - others:GA MF(CZ) ECPF:049/4V Institutional research plan: CEZ:AV0Z40400503 Keywords : quantum-defect theory * emission spectroscpy * plasma Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.210, year: 2012

  19. Thermoluminescence spectra of amethyst

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Q. [Suzhou Railway Teachers College (China). Dept. of Physics; Yang, B. [Beijing Normal University (China). Dept. of Physics; Wood, R.A.; White, D.R.R.; Townsend, P.D.; Luff, B.J. [Sussex Univ., Brighton (United Kingdom). School of Mathematical and Physical Sciences

    1994-04-01

    Thermoluminescence and cathodoluminescence data from natural and synthetic amethyst and synthetic quartz samples are compared. The spectra include features from the quartz host lattice and from impurity-generated recombination sites. Emission features exist throughout the wavelength range studied, 250-800 nm. The near infrared emission at 740-750 nm appears to be characteristic of the amethyst and is proposed to be due to Fe ion impurity. (Author).

  20. Pseudo-gap and superconducting condensate energies in the infrared spectra of Pr-doped YBa2Cu3O7

    International Nuclear Information System (INIS)

    Lobo, R.P.S.M.; Bontemps, N.; Racah, D.; Dagan, Y.; Deutscher, G.

    2001-01-01

    The (a,b)-plane infrared and visible conductivity (30-30000 cm -1 ) of a 40% praseodymium-substituting yttrium YBa 2 Cu 3 O 7 film displays a loss of spectral weight over two separate energy ranges when lowering the temperature. A first loss of spectral weight is present in the range 300-800 cm -1 from room temperature down to 40 K (T c =35 K). A further distinct spectral weight diminution appears in the superconducting phase at frequencies below 200 cm -1 . This diminution can be observed due to the high signal-to-noise ratio allowed by the large area of the thin film. We propose that the lower energy loss of spectral weight reflects the formation and the properties of the superconducting condensate. (orig.)

  1. Forecast of physicochemical properties and chemical composition of gasoline from infrared spectra, using multivariate calibration; Previsao de propriedades fisico-quimicas e composicao quimica da gasolina a partir de espectros infravermelhos, utilizando calibracao multivariada

    Energy Technology Data Exchange (ETDEWEB)

    Cocco, Lilian Cristina; Yamamoto, Carlos Itsuo [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Lab. de Analise de Combustiveis Automotivos (LACAUTets)

    2008-07-01

    This work describes the attainment of mathematical models, applying multivariate calibration in infrared spectrum with ATR, from 128 gasoline samples with diverse chemical compositions, collected in a period of two and a half years. Infrared spectra had been used to assemble the input matrix for the modeling, whereas the standardized assays and gaseous chromatography had supplied the output matrices. Ninety samples were been used for training and 38 for testing. In order to calibrate chemical composition from chromatography, the techniques of mass spectrometry and chemical ionization were used to identify unknown substances and improve the fitting of the mathematical models. Two hundred and ninety substances were detected and identified, from which 100 were unknown. Six PLS/PCR models were attained to predict some properties as specific mass, Reid vapor pressure, T10, T50, T90 and PFE from distillation curve. Another six PLS/PCR models were attained to predict the amount of aromatics, paraffins, isoparaffins, naphthenes, olefins and oxygenates. In general, mathematical models were attained with good training fit, with correlation coefficients higher than 0,975 (T10) and reaching a maximum of 0,998 (naphthenes) and they are able to forecast an average chemical percentage and properties of interest from gasoline, with acceptable prediction errors. (author)

  2. Quantitative analysis of the effect of zidovudine, efavirenz, and ritonavir on insulin aggregation by multivariate curve resolution alternating least squares of infrared spectra

    International Nuclear Information System (INIS)

    Martí-Aluja, Idoia; Ruisánchez, Itziar; Larrechi, M. Soledad

    2013-01-01

    Highlights: ► The structure of insulin can be changed via interaction with antiretroviral drugs. ► The chemical interaction promotes the formation of aggregates. ► This drug effect was evaluated by MCR-ALS coupled to IR spectroscopy. ► Formation of aggregates was favourable if drugs were able to form hydrogen bonds. ► Higher drug concentrations favoured formation of amorphous aggregates. - Abstract: Quantification of the effect of antiretroviral drugs on the insulin aggregation process is an important area of research due to the serious metabolic diseases observed in AIDS patients after prolonged treatment with these drugs. In this work, multivariate curve resolution alternating least squares (MCR-ALS) was applied to infrared monitoring of the insulin aggregation process in the presence of three antiretroviral drugs to quantify their effect. To evidence concentration dependence in this process, mixtures at two different insulin:drug molar ratios were used. The interaction between insulin and each drug was analysed by 1 H NMR spectroscopy. In all cases, the aggregation process was monitored during 45 min by infrared spectroscopy. The aggregates were further characterised by scanning electron microscopy (SEM). MCR-ALS provided the spectral and concentration profiles of the different insulin–drug conformations that are involved in the process. Their feasible band boundaries were calculated using the MCR-BANDS methodology. The kinetic profiles describe the aggregation pathway and the spectral profiles characterise the conformations involved. The retrieved results show that each of the three drugs modifies insulin conformation in a different way, promoting the formation of aggregates. Ritonavir shows the strongest promotion of aggregation, followed by efavirenz and zidovudine. In the studied concentration range, concentration dependence was only observed for zidovudine, with shorter aggregation time obtained as the amount of zidovudine increased. This factor

  3. Vibrational Spectroscopy of Intramolecular Hydrogen Bonds in the Infrared and Near-Infrared Regions

    DEFF Research Database (Denmark)

    Schrøder, Sidsel Dahl

    and 1,4-diaminobutane). Experimentally, the hydrogen bonds have been studied with vibrational spectroscopy in the infrared and near-infrared regions. The focus is primarily on spectra recorded in the near-infrared regions, which in these studies are dominated by O-H and N-H stretching overtones....... Overtone spectra have been recorded with intracavity laser photoacoustic laser spectroscopy and conventional long path absorption spectroscopy. Theoretically, a combination of electronic structure calculations and local mode models have been employed to guide the assignment of bands in the vibrational......,4-diaminobutane, no sign of intramolecular N-H···N hydrogen bonds were identified in the overtone spectra. However, theoretical analyzes indicate that intramolecular N-H···N hydrogen bonds are present in all three diamines if two hydrogen atoms on one of the methylene groups are substituted with triuoromethyl...

  4. Infrared spectroscopy of different phosphates structures.

    Science.gov (United States)

    Jastrzębski, W; Sitarz, M; Rokita, M; Bułat, K

    2011-08-15

    Infrared (IR) spectroscopic studies of mineral and synthetic phosphates have been presented. The interpretation of the spectra has been preceded by the isolated [PO(4)](3-) tetrahedron spectra analyse. The K(3)PO(4) saturated aqueous solution was measured in the special cell for liquids. The obtained IR results have been compared with the theoretical number of IR-active modes. The number and positions of the bands due to P-O vibrations have been established. The phase composition of the phosphates has been determined using XRD and IR spectroscopy methods. The influence of non-tetrahedral cations on the shape of the spectra and the positions of bands has been analysed and the crystalline field splitting effect has been discussed. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Infrared spectra of BeSo4.4H2O and its deuterated analogue in 4000-1200 cm-1 region

    International Nuclear Information System (INIS)

    Srivastava, B.K.; Khandelwal, D.P.; Bist, H.D.

    1976-01-01

    IR spectra of BeSO 4 .4H 2 O and its deuterated analogue at approximately 300 K and approximately 110 K are reported in the region 4000-1200 cm -1 using thin film and nujol mull techniques. The observed bands have been assigned as the internal modes of the water and the oVertones and combinations of various modes using the recently revised assignments of SO 4 2- and Be(aq) 4 fundamentals in the region 120g-250 cmsub(-) 1 . The splitting of the internal modes of water has been discussed in the light of the effects of deuteration and cooling and it is shown that all the water molecules in a unit cell are asymmetric but crystallographically equivalent. (author)

  6. Theoretical chemistry

    International Nuclear Information System (INIS)

    Anon.

    1975-01-01

    Work in theoretical chemistry was organized under the following topics: scattering theory and dynamics (elastic scattering of the rare gas hydrides, inelastic scattering in Li + H 2 , statistical theory for bimolecular collisions, model study of dissociative scattering, comparative study of elastic scattering computational methods), studies of atmospheric diatomic and triatomic species, structure and spectra of diatomic molecules, the evaluation of van der Waals forces, potential energy surfaces and structure and dynamics, calculation of molecular polarizabilities, and development of theoretical techniques and computing systems. Spectroscopic parameters are tabulated for NO 2 , N 2 O, H 2 O + , VH, and NH. Self-consistent-field wave functions were computed for He 2 in two-center and three-center bases. Rare gas hydride intermolecular potentials are shown. (9 figures, 14 tables) (U.S.)

  7. On the Assessment and Uncertainty of Atmospheric Trace Gas Burden Measurements with High Resolution Infrared Solar Occultation Spectra from Space by the ATMOS Experiment

    Science.gov (United States)

    Abrams, M. C.; Chang, A. Y.; Gunson, M. R.; Abbas, M. M.; Goldman, A.; Irion, F. W.; Michelsen, H. A.; Newchurch, M. J.; Rinsland, C. P.; Stiller, G. P.; hide

    1996-01-01

    The Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument is a high resolution Fourier transform spectrometer that measures atmospheric composition from low Earth orbit with infrared solar occultation sounding in the limb geometry. Following an initial flight in 1985, ATMOS participated in the Atmospheric Laboratory for Applications and Science (ATLAS) 1, 2, and 3 Space Shuttle missions in 1992, 1993, and 1994 yielding a total of 440 occultation measurements over a nine year period. The suite of more than thirty atmospheric trace gases profiled includes CO2, O3, N2O, CH4, H2O, NO, NO2, HNO3, HCl, HF, ClONO2, CCl3F, CCl2F2, CHF2Cl, and N2O5. The analysis method has been revised throughout the mission years culminating in the 'version 2' data set. The spectroscopic error analysis is described in the context of supporting the precision estimates reported with the profiles; in addition, systematic uncertainties assessed from the quality of the spectroscopic database are described and tabulated for comparisons with other experiments.

  8. Optical Properties of β-RDX Thin Films Deposited on Gold and Stainless Steel Substrates Calculated from Reflection-Absorption Infrared Spectra.

    Science.gov (United States)

    Ruiz-Caballero, José L; Aparicio-Bolaño, Joaquín A; Figueroa-Navedo, Amanda M; Pacheco-Londoño, Leonardo C; Hernandez-Rivera, Samuel P

    2017-08-01

    The optical properties for crystalline films of the highly energetic material (HEM) hexahydro-1,3,5-trinitro-s-triazine, which is also known as RDX, deposited on gold (Au) and stainless steel (SS) substrates are presented. RDX has two important stable conformational polymorphs at room temperature: α-RDX and β-RDX. The optical properties obtained in the present work correspond to thin film samples of predominantly β-RDX polymorph. The infrared spectroscopic intensities measured showed significant differences in the β-RDX crystalline films deposited on the two substrates with respect to the calculated real part of refractive index. The β-RDX/Au crystalline films have a high dynamic response, which is characterized by the asymmetric stretching mode of the axial nitro groups, whereas for the β-RDX/SS crystalline films, the dynamic response was mediated by the -N-NO 2 symmetric stretch mode. This result provides an idea of how the electric field vector propagates through the β-RDX crystalline films deposited on the two substrates.

  9. Selecting the optimum number of partial least squares components for the calibration of attenuated total reflectance-mid-infrared spectra of undesigned kerosene samples.

    Science.gov (United States)

    Gómez-Carracedo, M P; Andrade, J M; Rutledge, D N; Faber, N M

    2007-03-07

    Selecting the correct dimensionality is critical for obtaining partial least squares (PLS) regression models with good predictive ability. Although calibration and validation sets are best established using experimental designs, industrial laboratories cannot afford such an approach. Typically, samples are collected in an (formally) undesigned way, spread over time and their measurements are included in routine measurement processes. This makes it hard to evaluate PLS model dimensionality. In this paper, classical criteria (leave-one-out cross-validation and adjusted Wold's criterion) are compared to recently proposed alternatives (smoothed PLS-PoLiSh and a randomization test) to seek out the optimum dimensionality of PLS models. Kerosene (jet fuel) samples were measured by attenuated total reflectance-mid-IR spectrometry and their spectra where used to predict eight important properties determined using reference methods that are time-consuming and prone to analytical errors. The alternative methods were shown to give reliable dimensionality predictions when compared to external validation. By contrast, the simpler methods seemed to be largely affected by the largest changes in the modeling capabilities of the first components.

  10. Infrared Absorption Spectra, Radiative Efficiencies, and Global Warming Potentials of Newly-Detected Halogenated Compounds: CFC-113a, CFC-112 and HCFC-133a

    Directory of Open Access Journals (Sweden)

    Maryam Etminan

    2014-07-01

    Full Text Available CFC-113a (CF3CCl3, CFC-112 (CFCl2CFCl2 and HCFC-133a (CF3CH2Cl are three newly detected molecules in the atmosphere that are almost certainly emitted as a result of human activity. It is important to characterise the possible contribution of these gases to radiative forcing of climate change and also to provide information on the CO2-equivalence of their emissions. We report new laboratory measurements of absorption cross-sections of these three compounds at a resolution of 0.01 cm−1 for two temperatures 250 K and 295 K in the spectral range of 600–1730 cm−1. These spectra are then used to calculate the radiative efficiencies and global warming potentials (GWP. The radiative efficiencies are found to be between 0.15 and 0.3 W∙m−2∙ppbv−1. The GWP for a 100 year time horizon, relative to carbon dioxide, ranges from 340 for the relatively short-lived HCFC-133a to 3840 for the longer-lived CFC-112. At current (2012 concentrations, these gases make a trivial contribution to total radiative forcing; however, the concentrations of CFC-113a and HCFC-133a are continuing to increase. The 2012 CO2-equivalent emissions, using the GWP (100, are estimated to be about 4% of the current global CO2-equivalent emissions of HFC-134a.

  11. Tetrahydrometalate species VH(2)(H(2)), NbH(4), and TaH(4): matrix infrared spectra and quantum chemical calculations.

    Science.gov (United States)

    Wang, Xuefeng; Andrews, Lester

    2011-12-15

    Laser ablated V, Nb, and Ta atoms react with molecular hydrogen in excess neon at 4 K to give vanadium, niobium, and tantalum dihydrides that further react with H(2) to form VH(2)(H(2)), NbH(4), and TaH(4). The reaction products are identified by deuterium and deuterium hydride isotopic substitution. DFT and CCSD theoretical calculations are used to predict energies, geometries, and vibrational frequencies for these novel metal hydrides complex and molecules. The vanadium dihydride hydrogen complex, VH(2)(H(2)), is identified, while the niobium and tantalum tetrahydrides, NbH(4) and TaH(4,) with D(2d) symmetry structures are confirmed. Reactions of group 5 metal atoms with H(2) condensing in solid hydrogen gave VH(2)(H(2)) and the higher tetrahydride-hydrogen complexes NbH(4)(H(2))(4) and TaH(4)(H(2))(4).

  12. Assessment of organic matter resistance to biodegradation in volcanic ash soils assisted by automated interpretation of infrared spectra from humic acid and whole soil samples by using partial least squares

    Science.gov (United States)

    Hernández, Zulimar; Pérez Trujillo, Juan Pedro; Hernández-Hernández, Sergio Alexander; Almendros, Gonzalo; Sanz, Jesús

    2014-05-01

    From a practical viewpoint, the most interesting possibilities of applying infrared (IR) spectroscopy to soil studies lie on processing IR spectra of whole soil (WS) samples [1] in order to forecast functional descriptors at high organizational levels of the soil system, such as soil C resilience. Currently, there is a discussion on whether the resistance to biodegradation of soil organic matter (SOM) depends on its molecular composition or on environmental interactions between SOM and mineral components, such could be the case with physical encapsulation of particulate SOM or organo-mineral derivatives, e.g., those formed with amorphous oxides [2]. A set of about 200 dependent variables from WS and isolated, ash free, humic acids (HA) [3] was obtained in 30 volcanic ash soils from Tenerife Island (Spain). Soil biogeochemical properties such as SOM, allophane (Alo + 1 /2 Feo), total mineralization coefficient (TMC) or aggregate stability were determined in WS. In addition, structural information on SOM was obtained from the isolated HA fractions by visible spectroscopy and analytical pyrolysis (Py-GC/MS). Aiming to explore the potential of partial least squares regression (PLS) in forecasting soil dependent variables, exclusively using the information extracted from WS and HA IR spectral profiles, data were processed by using ParLeS [4] and Unscrambler programs. Data pre-treatments should be carefully chosen: the most significant PLS models from IR spectra of HA were obtained after second derivative pre-treatment, which prevented effects of intrinsically broadband spectral profiles typical in macromolecular heterogeneous material such as HA. Conversely, when using IR spectra of WS, the best forecasting models were obtained using linear baseline correction and maximum normalization pre-treatment. With WS spectra, the most successful prediction models were obtained for SOM, magnetite, allophane, aggregate stability, clay and total aromatic compounds, whereas the PLS

  13. "Long-distance" H/D isotopic self-organization phenomena in scope of the infrared spectra of hydrogen-bonded terephthalic and phthalic acid crystals.

    Science.gov (United States)

    Flakus, Henryk T; Hachuła, Barbara; Hołaj-Krzak, Jakub T; Al-Agel, Faisal A; Rekik, Najeh

    2017-02-15

    This paper deals with the experimental and theoretical studies of abnormal properties of terephthalic acid (TAC) and phthalic acid (PAC) crystals manifested in the H/D isotopic exchange. The widely utilized deuteration routine appeared to be insufficiently effective in the case of the h 6 -TAC isotopomer. In the case of the d 4 -TAC derivative the isotopic exchange process occurred noticeably more effectively. In contrast, both isotopomers of PAC, h 6 and d 4 , appeared much more susceptible for deuteration. A theoretical model was elaborated describing "long-distance" dynamical co-operative interactions involving hydrogen bonds in TAC and PAC crystals. The model assumes extremely strong dynamical co-operative interactions of hydrogen bonds from the adjacent (COOH) 2 cycles. This leads to an additional stabilization of h 6 -TAC molecular chains. The interaction energies affect the chemical equilibrium of the H/D isotopic exchange. The model predicts a differentiated influence of the H and D atoms linked to the aromatic rings on to the process. In this approach the totally-symmetric CH bond stretching vibrations and the proton stretching totally symmetric vibrations couple with the π-electronic motions. It was also shown that identical hydrogen isotope atoms, H or D, in whole TAC molecules, noticeably enlarge the energy of the dynamical co-operative interactions in the crystals, in contrast to the case of different hydrogen isotopes present in the carboxyl groups and linked to the aromatic rings. The "long-distance" dynamical co-operative interactions in PAC crystals were found of a minor importance due to the electronic properties of PAC molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Within-field and regional-scale accuracies of topsoil organic carbon content prediction from an airborne visible near-infrared hyperspectral image combined with synchronous field spectra for temperate croplands

    Science.gov (United States)

    Vaudour, Emmanuelle; Gilliot, Jean-Marc; Bel, Liliane; Lefevre, Josias; Chehdi, Kacem

    2016-04-01

    This study was carried out in the framework of the TOSCA-PLEIADES-CO of the French Space Agency and benefited data from the earlier PROSTOCK-Gessol3 project supported by the French Environment and Energy Management Agency (ADEME). It aimed at identifying the potential of airborne hyperspectral visible near-infrared AISA-Eagle data for predicting the topsoil organic carbon (SOC) content of bare cultivated soils over a large peri-urban area (221 km2) with intensive annual crop cultivation and both contrasted soils and SOC contents, located in the western region of Paris, France. Soils comprise hortic or glossic luvisols, calcaric, rendzic cambisols and colluvic cambisols. Airborne AISA-Eagle images (400-1000 nm, 126 bands) with 1 m-resolution were acquired on 17 April 2013 over 13 tracks. Tracks were atmospherically corrected then mosaicked at a 2 m-resolution using a set of 24 synchronous field spectra of bare soils, black and white targets and impervious surfaces. The land use identification system layer (RPG) of 2012 was used to mask non-agricultural areas, then calculation and thresholding of NDVI from an atmospherically corrected SPOT4 image acquired the same day enabled to map agricultural fields with bare soil. A total of 101 sites, which were sampled either at the regional scale or within one field, were identified as bare by means of this map. Predictions were made from the mosaic AISA spectra which were related to SOC contents by means of partial least squares regression (PLSR). Regression robustness was evaluated through a series of 1000 bootstrap data sets of calibration-validation samples, considering those 75 sites outside cloud shadows only, and different sampling strategies for selecting calibration samples. Validation root-mean-square errors (RMSE) were comprised between 3.73 and 4.49 g. Kg-1 and were ~4 g. Kg-1 in median. The most performing models in terms of coefficient of determination (R²) and Residual Prediction Deviation (RPD) values were the

  15. New investigation of the ν3 C-H stretching region of 12CH4 through the analysis of high temperature infrared emission spectra.

    Science.gov (United States)

    Amyay, Badr; Gardez, Aline; Georges, Robert; Biennier, Ludovic; Vander Auwera, Jean; Richard, Cyril; Boudon, Vincent

    2018-04-07

    The ν 3 C-H stretching region of methane was reinvestigated in this work using high temperature (620-1715 K) emission spectra recorded in Rennes at Doppler limited resolution. This work follows our recent global analysis of the Dyad system Δn = ±1 (1000-1500 cm -1 ), with n being the polyad number [B. Amyay et al., J. Chem. Phys. 144, 24312 (2016)]. Thanks to the high temperature, new assignments of vibration-rotation methane line positions have been achieved successfully in the Pentad system and some associated hot bands (Δn = ±2) observed in the spectral region 2600-3300 cm -1 . In particular, rotational assignments in the cold band [Pentad-ground state (GS)] and in the first related hot band (Octad-Dyad) were extended up to J = 30 and 27, respectively. In addition, 1525 new transitions belonging to the Tetradecad-Pentad hot band system were assigned for the first time, up to J = 20. The effective global model used to deal with the new assignments was developed to the 6th order for the first three polyads (Monad, Dyad, and Pentad), and to the 5th order for both the Octad and the Tetradecad. 1306 effective parameters were fitted with a dimensionless standard deviation σ = 2.64. The root mean square deviations d RMS obtained are 4.18 × 10 -3 cm -1 for the Pentad-GS cold band, 2.48 × 10 -3 cm -1 for the Octad-Dyad, and 1.43 × 10 -3 cm -1 for the Tetradecad-Pentad hot bands.

  16. BETA SPECTRA. I. Negatrons spectra

    International Nuclear Information System (INIS)

    Grau Malonda, A.; Garcia-Torano, E.

    1978-01-01

    Using the Fermi theory of beta decay, the beta spectra for 62 negatrons emitters have been computed introducing a correction factor for unique forbidden transitions. These spectra are plotted vs. energy, once normal i sed, and tabulated with the related Fermi functions. The average and median energies are calculated. (Author)

  17. Comparability of red/near-infrared reflectance and NDVI based on the spectral response function between MODIS and 30 other satellite sensors using rice canopy spectra.

    Science.gov (United States)

    Huang, Weijiao; Huang, Jingfeng; Wang, Xiuzhen; Wang, Fumin; Shi, Jingjing

    2013-11-26

    Long-term monitoring of regional and global environment changes often depends on the combined use of multi-source sensor data. The most widely used vegetation index is the normalized difference vegetation index (NDVI), which is a function of the red and near-infrared (NIR) spectral bands. The reflectance and NDVI data sets derived from different satellite sensor systems will not be directly comparable due to different spectral response functions (SRF), which has been recognized as one of the most important sources of uncertainty in the multi-sensor data analysis. This study quantified the influence of SRFs on the red and NIR reflectances and NDVI derived from 31 Earth observation satellite sensors. For this purpose, spectroradiometric measurements were performed for paddy rice grown under varied nitrogen levels and at different growth stages. The rice canopy reflectances were convoluted with the spectral response functions of various satellite instruments to simulate sensor-specific reflectances in the red and NIR channels. NDVI values were then calculated using the simulated red and NIR reflectances. The results showed that as compared to the Terra MODIS, the mean relative percentage difference (RPD) ranged from -12.67% to 36.30% for the red reflectance, -8.52% to -0.23% for the NIR reflectance, and -9.32% to 3.10% for the NDVI. The mean absolute percentage difference (APD) compared to the Terra MODIS ranged from 1.28% to 36.30% for the red reflectance, 0.84% to 8.71% for the NIR reflectance, and 0.59% to 9.32% for the NDVI. The lowest APD between MODIS and the other 30 satellite sensors was observed for Landsat5 TM for the red reflectance, CBERS02B CCD for the NIR reflectance and Landsat4 TM for the NDVI. In addition, the largest APD between MODIS and the other 30 satellite sensors was observed for IKONOS for the red reflectance, AVHRR1 onboard NOAA8 for the NIR reflectance and IKONOS for the NDVI. The results also indicated that AVHRRs onboard NOAA7-17 showed

  18. Microsolvation of the water cation in neon: Infrared spectra and potential energy surface of the H2O+-Ne open-shell ionic complex

    Science.gov (United States)

    Dopfer, Otto; Roth, Doris; Maier, John P.

    2001-04-01

    The intermolecular potential of the H2O+-Ne open-shell ionic dimer in its doublet electronic ground state has been investigated by infrared spectroscopy in the vicinity of the O-H stretch vibrations (ν1 and ν3) and ab initio calculations at the unrestricted Møller-Plesset second-order (MP2) level with a basis set of aug-cc-pVTZ quality. The rovibrational structure of the photodissociation spectrum is consistent with a proton-bound planar H-O-H-Ne structure and a Ne-H separation of R0=1.815(5) Å. The complexation-induced redshifts are Δν1=-69 cm-1 and Δν3=-6 cm-1, respectively. Tunneling splittings observed in the perpendicular component of the ν3 hybrid band of H2O+-Ne are attributed to hindered internal rotation between the two equivalent proton-bound equilibrium structures. The interpretation of the H2O+-Ne spectrum is supported by the spectrum of the monodeuterated species, for which both the proton-bound and the deuteron-bound isomers are observed (DOH+-Ne, HOD+-Ne). The equilibrium structure of the calculated potential energy surface of H2O+-Ne has a slightly translinear proton bond, which is characterized by a Ne-H separation of Re=1.77 Å, a bond angle of φe=174°, and dissociation energies of De=756 cm-1 and D0=476 cm-1. According to the calculated potential, the exchange tunneling between the two equivalent minima occurs via the planar bridged transition state with C2v symmetry and a barrier of 340 cm-1. In general, the calculated properties of H2O+-Ne show good agreement with the experimental data. Initial steps in the microsolvation of the water cation in neon are discussed by comparing the calculated and experimental properties of H2O+-Nen (n=0-2) with neon matrix isolation data (n→∞).

  19. Infrared Multiple Photon Dissociation Action Spectroscopy and Theoretical Studies of Diethyl Phosphate Complexes: Effects of Protonation and Sodium Cationization on Structure

    NARCIS (Netherlands)

    Fales, B. S.; Fujamade, N. O.; Nei, Y. W.; Oomens, J.; Rodgers, M. T.

    2011-01-01

    The gas-phase structures of deprotonated, protonated, and sodium-cationized complexes of diethyl phosphate (DEP) including [DEP - H](-), [DEP + H](+), [DEP + Na](+), and [DEP - H + 2Na](+) are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy using tunable IR radiation

  20. Raman spectra of lithium compounds

    Science.gov (United States)

    Gorelik, V. S.; Bi, Dongxue; Voinov, Y. P.; Vodchits, A. I.; Gorshunov, B. P.; Yurasov, N. I.; Yurasova, I. I.

    2017-11-01

    The paper is devoted to the results of investigating the spontaneous Raman scattering spectra in the lithium compounds crystals in a wide spectral range by the fibre-optic spectroscopy method. We also present the stimulated Raman scattering spectra in the lithium hydroxide and lithium deuteride crystals obtained with the use of powerful laser source. The symmetry properties of the lithium hydroxide, lithium hydroxide monohydrate and lithium deuteride crystals optical modes were analyzed by means of the irreducible representations of the point symmetry groups. We have established the selection rules in the Raman and infrared absorption spectra of LiOH, LiOH·H2O and LiD crystals.

  1. HARDERSEN IRTF ASTEROID NIR REFLECTANCE SPECTRA V1.0

    Data.gov (United States)

    National Aeronautics and Space Administration — This dataset includes average near-infrared (NIR) reflectance spectra for 68 main-belt asteroids that were observed at the NASA Infrared Telescope Facility (IRTF),...

  2. Infrared spectra of thin films of α-crystalline hexafluoroethane: a manifestation of resonant dipole-dipole interaction in the range of fundamental vibrational modes ν5 and ν10

    Science.gov (United States)

    Golubkova, O. S.; Kataeva, T. S.; Shchepkin, D. N.; Asfin, R. E.

    2017-06-01

    Infrared reflection-absorption spectra of thin films of α-crystalline hexafluoroethane deposited on a gold-plated copper mirror are measured at temperatures of 70 and 80 K. The bands corresponding to strong in the dipole absorption vibrations ν5 and ν10 have complex contours, the shape of which is explained in terms of the resonant dipole-dipole interaction between identical spectrally active molecules of the crystal. Splittings of the complex ν5 and ν10 bands are explained taking into account two effects: the Davydov splitting and the LO-TO splitting of the strong modes. Bands of the asymmetric 13C12CF6 isotopologue in the absorption spectrum of the crystal exhibit an anomalously large isotope shift as compared with the shift in the spectrum of free molecules. This anomaly is explained by intermolecular resonant dipole-dipole interaction of asymmetric 13C12CF6 isotopologue with molecules of the environment, consisting of the most abundant 12C2F6 isotopologue. The correctness of the given interpretation is confirmed calculating these three effects in the model of resonant dipole-dipole interaction.

  3. Classification of specialty seed meals from NIR reflectance spectra

    Science.gov (United States)

    Near infrared reflectance spectroscopy was used to identify alternative seed meals proposed for food and feed formulations. Spectra were collected from cold pressed Camelina (Camelina sativa), Coriander (Coriandrum sativum), and Pennycress (Thlaspi arvense) meals. Additional spectra were collected ...

  4. LARSON FTS SPECTRA V1.0

    Data.gov (United States)

    National Aeronautics and Space Administration — This data set contains 107 asteroid spectra obtained between the years 1975 and 1982 inclusive, with the infrared fourier transform spectrometer (FTS) of H. P....

  5. A high-resolution atlas of the infrared spectrum of the Sun and the Earth atmosphere from space: A compilation of ATMOS spectra of the region from 650 to 4800 cm (2.3 to 16 micron). Volume 1: The Sun

    Science.gov (United States)

    Farmer, Crofton B.; Norton, Robert H.

    1989-01-01

    During the period April 29 through May 2, 1985, the Atmospheric Trace Molecular Spectroscopy experiment was operated as part of the Spacelab-3 payload of the shuttle Challenger. The instrument, a modified Michelson Interferometer covering the frequency range from 600 to 5000/cm, at a spectral resolution of 0.01/cm, recorded infrared spectra of the Sun and of the Earth's atmosphere at times close to entry into and exit from occultation by the Earth's limb as seen from the shuttle orbit of 360 km. Spectra were obtained that are free from absorptions due to constituents of the atmosphere (i.e., solar pure spectra), as well as spectra of the atmosphere itself, covering line-of-sight tangent altitudes that span the range from the lower thermosphere to the bottom of the troposphere. This atlas, believed to be the first record of observations of the continuous high resolution infrared spectrum of the Sun and the Earth's atmosphere from space, provides a compilation of these spectra arranged in a hardcopy format suitable for quick-look reference purposes; the data are also available in digital form.

  6. Structure, spectra and stability of a tetrafluoromethane-water complex.

    Science.gov (United States)

    Mierzwicki, Krzysztof; Mielke, Zofia; Sałdyka, Magdalena; Coussan, Stephane; Roubin, Pascale

    2008-03-07

    The complex formed between water and tetrafluoromethane has been studied by infrared matrix isolation spectroscopy and ab initio calculations. The geometries of the CF4-H2O complexes were optimized in two steps at the MP2/aug-cc-pVTZ level of theory. The structure found at this level was reoptimized on the CP-corrected potential energy surface. The interaction energy was partitioned according to the SAPT scheme and the topological analysis of the electron density was performed. The optimized structure corresponds to the nonhydrogen bonded complex with an oxygen atom of water oriented toward the carbon atom of CF4. The infrared spectra of CF4-H2O /Ne(Ar) matrices demonstrate the presence of a well defined CF4-H2O structure in accord with theoretical prediction. Two complex vibrations were identified in the spectra of neon matrices and four vibrations were observed in the spectra of argon matrices. The available experimental data are in accord with the CP-corrected calculated data.

  7. Iterative maximum a posteriori (IMAP-DOAS for retrieval of strongly absorbing trace gases: Model studies for CH4 and CO2 retrieval from near infrared spectra of SCIAMACHY onboard ENVISAT

    Directory of Open Access Journals (Sweden)

    C. Frankenberg

    2005-01-01

    Full Text Available In the past, differential optical absorption spectroscopy (DOAS has mostly been employed for atmospheric trace gas retrieval in the UV/Vis spectral region. New spectrometers such as SCIAMACHY onboard ENVISAT also provide near infrared channels and thus allow for the detection of greenhouse gases like CH4, CO2, or N2O. However, modifications of the classical DOAS algorithm are necessary to account for the idiosyncrasies of this spectral region, i.e. the temperature and pressure dependence of the high resolution absorption lines. Furthermore, understanding the sensitivity of the measurement of these high resolution, strong absorption lines by means of a non-ideal device, i.e. having finite spectral resolution, is of special importance. This applies not only in the NIR, but can also prove to be an issue for the UV/Vis spectral region. This paper presents a modified iterative maximum a posteriori-DOAS (IMAP-DOAS algorithm based on optimal estimation theory introduced to the remote sensing community by rodgers76. This method directly iterates the vertical column densities of the absorbers of interest until the modeled total optical density fits the measurement. Although the discussion in this paper lays emphasis on satellite retrieval, the basic principles of the algorithm also hold for arbitrary measurement geometries. This new approach is applied to modeled spectra based on a comprehensive set of atmospheric temperature and pressure profiles. This analysis reveals that the sensitivity of measurement strongly depends on the prevailing pressure-height. The IMAP-DOAS algorithm properly accounts for the sensitivity of measurement on pressure due to pressure broadening of the absorption lines. Thus, biases in the retrieved vertical columns that would arise in classical algorithms, are obviated. Here, we analyse and quantify these systematic biases as well as errors due to variations in the temperature and pressure profiles, which is indispensable for

  8. Near infrared and ultraviolet spectra of TLEs

    Czech Academy of Sciences Publication Activity Database

    Gordillo-Vázquez, F.J.; Luque, A.; Šimek, Milan

    2012-01-01

    Roč. 117, č. 5 (2012), s. 1-7 ISSN 0148-0227 Institutional research plan: CEZ:AV0Z20430508 Keywords : sprites * halos * spectroscopy Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 3.174, year: 2012

  9. Infrared spectra of ThH2, ThH4, and the hydride bridging ThH4(H2)x (x = 1-4) complexes in solid neon and hydrogen.

    Science.gov (United States)

    Wang, Xuefeng; Andrews, Lester; Gagliardi, Laura

    2008-02-28

    Laser-ablated Th atoms react with molecular hydrogen to give thorium hydrides and their dihydrogen complexes during condensation in excess neon and hydrogen for characterization by matrix infrared spectroscopy. The ThH2, ThH4, and ThH4(H2)x (x = 1-4) product molecules have been identified through isotopic substitution (HD, D2) and comparison to frequencies calculated by density functional theory and the coupled-cluster, singles, doubles (CCSD) method and those observed previously in solid argon. Theoretical calculations show that the Th-H bond in ThH4 is the most polarized of group 4 and uranium metal tetrahydrides, and as a result, a strong attractive "dihydrogen" interaction was found between the oppositely charged hydride and H2 ligands ThH4(H2)x. This bridge-bonded dihydrogen complex structure is different from that recently computed for tungsten and uranium hydride super dihydrogen complexes but is similar to that recently called the "dihydrogen bond" (Crabtree, R. H. Science 1998, 282, 2000). Natural electron configurations show small charge flow from the Th center to the dihydrogen ligands.

  10. Hydrogen-bridge Si(μ-H)3CeH and inserted H3SiCeH molecules: Matrix infrared spectra and DFT calculations for reaction products of silane with Ce atoms

    Science.gov (United States)

    Xu, Bing; Shi, Peipei; Huang, Tengfei; Wang, Xuefeng

    2017-10-01

    Reactions of laser-ablated cerium atoms with silane were investigated by matrix isolation infrared spectroscopy and theoretical calculations. The reaction products, Si(μ-H)3CeH, H3SiCeH, H2Si(μ-H)CeH and HSi(μ-H)2CeH were identified on the basis of the SiD4 isotopic substitutions and DFT frequency calculations. In the solid argon or krypton matrix, the inserted H3SiCeH molecule was observed as initial product on deposition, which rearranged to hydrogen bridge species Si(μ-H)3CeH on follow-up annealing through H2Si(μ-H)CeH and HSi(μ-H)2CeH species. The Sisbnd Hsbnd Ce hydrogen bridge was investigated by NBO and ELF analysis. Calculation suggested that in Si(μ-H)3CeH molecule Ce atom donated one electron to Si atom, resulting in electron-rich SiH3 subunit, which was confirmed by ESP and AIM analysis. The increased basicity of Sisbnd H bond facilitates the formation of hydrogen bridge bond between Si and Ce. For comparison only insertion H3CCeH structure was obtained from the reaction of Ce atoms with CH4.

  11. Matrix Infrared Spectra of Insertion and Metallacyclopropane Complexes [CH3CH2-MH and (CH2)2-MH2] Prepared in Reactions of Laser-Ablated Group 3 Metal Atoms with Ethane.

    Science.gov (United States)

    Cho, Han-Gook; Andrews, Lester

    2017-11-16

    CH 3 CH 2 -MH and (CH 2 ) 2 -MH 2 were identified in the matrix IR spectra from reactions of laser-ablated group 3 metal atoms with ethane, and they were characterized via theoretical investigations. The observed products are the most stable in the proposed reaction path. Because of the small number of valence electrons, the group 3 metal high oxidation-state complexes are less stable. The C-C insertion product [(CH 3 ) 2 M], which was predicted to be more stable than the observed ones, was not observed probably because of the high energy barrier and a likely slower rate for insertion into one C-C bond than one of six C-H bonds. The C-C bond of the metallacyclopropanes is the shortest among the early transition-metal analogues, and its stretching frequencies are the highest, revealing the weakest interaction between the metal dihydride and ethylidene groups. The undetected ethylidene is not agostic, parallel to the previously examined methylidene.

  12. Espectro Vibracional no Infravermelho Próximo dos Polímeros Poliestireno, Poli(Metacrilato de Metila e Policarbonato Near-Infrared Spectra of Polystyrene, Poly(Methyl Methacrylate and Polycarbonate

    Directory of Open Access Journals (Sweden)

    Sérgio C. de Araújo

    2001-01-01

    Full Text Available Os espectros no infravermelho próximo (NIR dos polímeros amorfos poliestireno (PS, poli(metacrilato de metila (PMMA e policarbonato (PC foram estudados. A tentativa de atribuição das bandas harmônicas e de combinação dos modos vibracionais do PS, PMMA e PC foi realizada baseando-se na teoria de modos locais e pelo uso do método matemático de ajuste de curvas. A correção de anarmonicidade e freqüência mecânica foi determinada em um gráfico de Birge-Sponer. Uma correção de anarmonicidade de 57 e 58 cm-1 foi obtida para os modos de estiramento dos grupos CH2 e CH do PS; 59 e 9 cm-1 para os modos de estiramento dos grupos CH3 e CO do PMMA e 53, 59 e 10 cm-1 para os modos de estiramento dos grupos CH, CH3 e CO do PC, respectivamente.The near-infrared (NIR spectra of the amorphous polymers polystyrene (PS, poly(methyl methacrylate (PMMA, and polycarbonate (PC have been studied. The tentative assignment of the overtone and combination frequencies is made using the curve fitting calculations and the local mode theory. Anharmonicity correction and mechanical frequency were determined from a Birge-Sponer plot. A tentative assignment of stretch overtone frequency of CH2 and CH functional groups of PS; CH3 and CO functional groups of PMMA and CH, CH3 and CO functional groups of PC has been made. An anharmonicity correction of 57 and 58 cm-1 was obtained for CH2 and CH stretch modes of PS; 59 and 9 cm-1 for CH3 and CO stretch modes of PMMA and 53, 59 and 10 cm-1 for CH, CH3 and CO stretch modes of PC, respectively.

  13. Theoretical and experimental drying of a cylindrical sample by applying hot air and infrared radiation in an inert medium fluidized bed

    Directory of Open Access Journals (Sweden)

    B. Honarvar

    2012-06-01

    Full Text Available Drying of a cylindrical sample in a fluidized bed dryer containing inert particles was studied. For this purpose, a pilot-scaled fluidized bed dryer was constructed in which two different heat sources, hot air and infrared radiation were applied, and pieces of carrot were chosen as test samples. The heat transfer coefficient for cylindrical objects in a fluidized bed was also measured. The heat absorption coefficient for carrot was studied. The absorption coefficient can be computed by dividing the absorbed heat by the carrot to the heat absorbed for the water and black ink. In this regard, absorbed heat values by the carrot, water and black ink were used A mathematical model was proposed based on the mass and heat transfer phenomena within the drying sample. The results obtained by the proposed model were in favorable agreement with the experimental data.

  14. Adsorption and co-adsorption of isotopic molecular hydrogen species H2, HD and D2 in NaA. Thermogravimetry, infrared spectrometry and theoretical interpretation

    International Nuclear Information System (INIS)

    Victoire-Stephanie, F.

    1997-12-01

    The study of isotopic hydrogen species adsorbed in NaA zeolite shows the adsorbate mass influence on adsorption and co-adsorption phenomenons. As these molecules have the same electronic composition and size, they interact with the zeolite in the same way. The adsorbed molecule amount (adsorption isotherms) is more important for the heaviest molecules. This observation has been explained by the same co-volume variation with the molecular mass. From the isotherms modeling, thermodynamic quantities such as adsorption heat and entropy have been determined. The heats are the same for the different species. As a matter of fact, the interaction is similar for isotopes. The entropy differs by the symmetry and the ortho-para form of the molecules. From the entropies, external and frequencies have been calculated. The vibrational frequencies correspond to the same rotation barrier height for the different molecules; that confirms again that the adsorbent-adsorbate interaction is the same. The three isotopic species have an induced infrared spectrum by the electric field due to the crystal ions. The spectral analysis of the pure isotopic molecules highlights the mass effect on the frequency shifts and the band-shape evolution. For all the species, the band-shape evolution with respect to the adsorbed amount (from 1 to 6 molecules per cavity) shows three main components which can be related to different energetic adsorption sites in the cavity. In the co-adsorption study by infrared spectrometry, the separation factor evolution of H 2 -HD, HD-D 2 , and H 2 -D 2 mixtures with regards to the temperature and the molecular mass is discussed by taking into account: i)the quantum effect at low temperature, ii)a possible ortho-para conversion of H 2 or/and D 2 in the zeolite. (author)

  15. Growth, Properties, and Theoretical Analysis of M2LiVO4 (M = Rb, Cs) Crystals: Two Potential Mid-Infrared Nonlinear Optical Materials.

    Science.gov (United States)

    Han, Guopeng; Wang, Ying; Su, Xin; Yang, Zhihua; Pan, Shilie

    2017-05-15

    Mid-Infrared nonlinear optical (Mid-IR NLO) crystals with excellent performances play a particularly important role for applications in areas such as telecommunications, laser guidance, and explosives detection. However, the design and growth of high performance Mid-IR NLO crystals with large NLO efficiency and high laser-damage threshold (LDT) still face numerous fundamental challenge. In this study, two potential Mid-IR NLO materials, Rb 2 LiVO 4 (RLVO) and Cs 2 LiVO 4 (CLVO) with noncentrosymmetric structures (Orthorhombic, Cmc2 1 ) were synthesized by high-temperature solution method. Thermal analysis and powder X-ray diffraction demonstrate that RLVO and CLVO melt congruently. Centimeter sized crystals of CLVO have been grown by the top-seeded solution growth method. RLVO and CLVO exhibit strong second harmonic generation (SHG) effects (about 4 and 5 times that of KH 2 PO 4 , respectively) with a phase-matching behavior at 1.064 μm, and a wide transparency range (0.33-6.0 μm for CLVO). More importantly, RLVO and CLVO possess a high LDT value (~28 × AgGaS 2 ). In addition, the density functional theory (DFT) and dipole moments studies indicate that the VO 4 anionic groups have a dominant contribution to the SHG effects in RLVO and CLVO. These results suggest that the title compounds are promising NLO candidate crystals applied in the Mid-IR region.

  16. Infrared cryoscopy

    International Nuclear Information System (INIS)

    Korolik, E.V.

    1989-01-01

    The use of cryospectroscopy for investigating the structure of compounds with a developed system of inter- and intramolecular hydrogen bonds is discussed. The changes in the H-bond energy observed on cooling, which are due to the conformation ordering of hydroxyl groups, make IR cryospectroscopy an effective method for studying the structure carbohydrates. In the present work, using an example of carbohydrates, the main directions of cryospectroscopy are analyzed: experimental procedure, peculiarities and interpretation of spectra, structural-analytical application. To this end, vibrational spectra of a number of mono-, di- and polysaccharides have been obtained and interpreted at liquid-helium temperature. Comparative analysis of the experimental data and theoretical calculations allowed a number of important problems to be solved involving the detailed interpretation of spectra of these complex compounds, among them those of the formation of intra- and intermolecular H-bonds. Correlation have been established between the structure of the carbohydrates studied and their spectral characteristics at liquid-helium temperatures. IR cryospectroscopy is shown to open up unique possibilities of revealing defects of carbohydrate crystalline structures. (author)

  17. Mid-infrared upconversion spectroscopy

    DEFF Research Database (Denmark)

    Tidemand-Lichtenberg, Peter; Dam, Jeppe Seidelin; Andersen, H. V.

    2016-01-01

    Mid-infrared (MIR) spectroscopy is emerging as an attractive alternative to near-infrared or visible spectroscopy. MIR spectroscopy offers a unique possibility to probe the fundamental absorption bands of a large number of gases as well as the vibrational spectra of complex molecules. In this paper...

  18. PCA: Principal Component Analysis for spectra modeling

    Science.gov (United States)

    Hurley, Peter D.; Oliver, Seb; Farrah, Duncan; Wang, Lingyu; Efstathiou, Andreas

    2012-07-01

    The mid-infrared spectra of ultraluminous infrared galaxies (ULIRGs) contain a variety of spectral features that can be used as diagnostics to characterize the spectra. However, such diagnostics are biased by our prior prejudices on the origin of the features. Moreover, by using only part of the spectrum they do not utilize the full information content of the spectra. Blind statistical techniques such as principal component analysis (PCA) consider the whole spectrum, find correlated features and separate them out into distinct components. This code, written in IDL, classifies principal components of IRS spectra to define a new classification scheme using 5D Gaussian mixtures modelling. The five PCs and average spectra for the four classifications to classify objects are made available with the code.

  19. Theoretical Characterizaiton of Visual Signatures (Muzzle Flash)

    Science.gov (United States)

    Kashinski, D. O.; Scales, A. N.; Vanderley, D. L.; Chase, G. M.; di Nallo, O. E.; Byrd, E. F. C.

    2014-05-01

    We are investigating the accuracy of theoretical models used to predict the visible, ultraviolet and infrared spectra of product materials ejected from the muzzle of currently fielded systems. Recent advances in solid propellants has made the management of muzzle signature (flash) a principle issue in weapons development across the calibers. A priori prediction of the electromagnetic spectra of formulations will allow researchers to tailor blends that yield desired signatures and determine spectrographic detection ranges. We are currently employing quantum chemistry methods at various levels of sophistication to optimize molecular geometries, compute vibrational frequencies, and determine the optical spectra of specific gas-phase molecules and radicals of interest. Electronic excitations are being computed using Time Dependent Density Functional Theory (TD-DFT). A comparison of computational results to experimental values found in the literature is used to assess the affect of basis set and functional choice on calculation accuracy. The current status of this work will be presented at the conference. Work supported by the ARL, and USMA.

  20. DFT and experimental studies of the structure and vibrational spectra of 2-(tert-buroxycarbonyl (Boc) - amino)-5-bromopyridine

    Science.gov (United States)

    Premkumar, S.; Jawahar, A.; Umadevi, M.; Sathe, V. G.; Asath, R. Mohamed; Franklin Benial, A. Milton

    2014-04-01

    The vibrational frequencies and frontier molecular orbitals of 2-(tert-buroxycarbonyl (Boc) -amino)-5-bromopyridine (BABP) were theoretically calculated by the DFT/B3LYP method with cc-pVTZ basis set using Gaussian 09 program. The vibrational spectra were experimentally recorded by Fourier transform-infrared (FT-IR) and Raman spectrometer. The computed vibrational frequencies were scaled by scale factors to yield a good agreement with observed vibrational frequencies. Theoretically calculated and experimentally observed vibrational frequencies were compared and assigned. The molecular interaction, stability and intermolecular charge transfer of BABP were studied using frontier molecular orbitals (FMO) analysis.