The two photocycles of photoactive yellow protein from Rhodobacter sphaeroides.

PubMed

Haker, Andrea; Hendriks, Johnny; van Stokkum, Ivo H M; Heberle, Joachim; Hellingwerf, Klaas J; Crielaard, Wim; Gensch, Thomas

2003-03-07

The absorption spectrum of the photoactive yellow protein from Rhodobacter sphaeroides (R-PYP) shows two maxima, absorbing at 360 nm (R-PYP(360)) and 446 nm (R-PYP(446)), respectively. Both forms are photoactive and part of a temperature- and pH-dependent equilibrium (Haker, A., Hendriks, J., Gensch, T., Hellingwerf, K. J., and Crielaard, W. (2000) FEBS Lett. 486, 52-56). At 20 degrees C, for PYP characteristic, the 446-nm absorbance band displays a photocycle, in which the depletion of the 446-nm ground state absorption occurs in at least three phases, with time constants of <30 ns, 0.5 micros, and 17 micros. Intermediates with both blue- and red-shifted absorption maxima are transiently formed, before a blue-shifted intermediate (pB(360), lambda(max) = 360 nm) is established. The photocycle is completed with a monophasic recovery of the ground state with a time constant of 2.5 ms. At 7 degrees C these photocycle transitions are slowed down 2- to 3-fold. Upon excitation of R-PYP(360) with a UV-flash (330 +/- 50 nm) a species with a difference absorption maximum at approximately 435 nm is observed that returns to R-PYP(360) on a minute time scale. Recovery can be accelerated by a blue light flash (450 nm). R-PYP(360) and R-PYP(446) differ in their overall protein conformation, as well as in the isomerization and protonation state of the chromophore, as determined with the fluorescent polarity probe Nile Red and Fourier Transform Infrared spectroscopy, respectively.

[Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

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

Eyring, E.M.

1992-01-01

The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd[sup 3+] + L(ligand), [RuL[sub 5]H[sub 2]O][sup 2+], laser flash photolysis of Mo(CO)[sub 6] + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd[sup 3+] ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO)[sub 6]-2,2'-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

[Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

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

Eyring, E.M.

1992-10-01

The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd{sup 3+} + L(ligand), [RuL{sub 5}H{sub 2}O]{sup 2+}, laser flash photolysis of Mo(CO){sub 6} + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd{sup 3+} ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO){sub 6}-2,2`-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

Iminopropadienones RN=C=C=C=O and bisiminopropadienes RN=C=C=C=NR: Matrix infrared spectra and anharmonic frequency calculations

NASA Astrophysics Data System (ADS)

Bégué, Didier; Baraille, Isabelle; Andersen, Heidi Gade; Wentrup, Curt

2013-10-01

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.

Triplet excited state spectra and dynamics of carotenoids from the thermophilic purple photosynthetic bacterium Thermochromatium tepidum

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

Niedzwiedzki, Dariusz; Kobayashi, Masayuki; Blankenship, R. E.

Light-harvesting complex 2 from the anoxygenic phototrophic purple bacterium Thermochromatium tepidum was purified and studied by steady-state absorption, fluorescence and flash photolysis spectroscopy. Steady-state absorption and fluorescence measurements show that carotenoids play a negligible role as supportive energy donors and transfer excitation to bacteriochlorophyll-a with low energy transfer efficiency of ~30%. HPLC analysis determined that the dominant carotenoids in the complex are rhodopin and spirilloxanthin. Carotenoid excited triplet state formation upon direct (carotenoid) or indirect (bacteriochlorophyll-a Q{sub x} band) excitation shows that carotenoid triplets are mostly localized on spirilloxanthin. In addition, no triplet excitation transfer between carotenoids was observed. Suchmore » specific carotenoid composition and spectroscopic results strongly suggest that this organism optimized carotenoid composition in the light-harvesting complex 2 in order to maximize photoprotective capabilities of carotenoids but subsequently drastically suppressed their supporting role in light-harvesting process.« less

Tunable bandgap energy of fluorinated nanocrystals for flash memory applications produced by low-damage plasma treatment.

PubMed

Huang, Chi-Hsien; Lin, Chih-Ting; Wang, Jer-Chyi; Chou, Chien; Ye, Yu-Ren; Cheng, Bing-Ming; Lai, Chao-Sung

2012-11-30

A plasma system with a complementary filter to shield samples from damage during tetrafluoromethane (CF(4)) plasma treatment was proposed in order to incorporate fluorine atoms into gadolinium oxide nanocrystals (Gd(2)O(3)-NCs) for flash memory applications. X-ray photoelectron spectroscopy confirmed that fluorine atoms were successfully introduced into the Gd(2)O(3)-NCs despite the use of a filter in the plasma-enhanced chemical vapour deposition system to shield against several potentially damaging species. The number of incorporated fluorine atoms can be controlled by varying the treatment time. The optimized memory window of the resulting flash memory devices was twice that of devices treated by a filterless system because more fluorine atoms were incorporated into the Gd(2)O(3)-NCs film with very little damage. This enlarged the bandgap energy from 5.48 to 6.83 eV, as observed by ultraviolet absorption measurements. This bandgap expansion can provide a large built-in electric field that allows more charges to be stored in the Gd(2)O(3)-NCs. The maximum improvement in the retention characteristic was >60%. Because plasma damage during treatment is minimal, maximum fluorination can be achieved. The concept of simply adding a filter to a plasma system to prevent plasma damage exhibits great promise for functionalization or modification of nanomaterials for advanced nanoelectronics while introducing minimal defects.

Nanostructure of tetrafunctional epoxy resins and composites: Correlation to moisture absorption properties

NASA Astrophysics Data System (ADS)

Bolan, Brett Andrew

The effect that changes in network topology, while maintaining a constant network polarity (i.e. thermodynamic driving force was kept constant), had upon the moisture absorption properties of an aerospace grade tetrafunctional epoxy (TGMDA) cured with multifunctional amines were investigated. Utilizing Positron Annihilation Lifetime Spectroscopy (PALS) to characterize the nanoscale structure of these epoxies, it was found that as the "static" hole volume (a measurement of packing defects at 0K) increased so did the equilibrium uptake. PALS studies of one of these resins cured to varying extents, found that this static amount increased with degree of cure indicating that the network becomes more open as a direct consequence of crosslinking. Polar groups, which are the attractive force for diffusion, are in the vicinity of these crosslinks, therefore it is believed that the increase in static hole volume results in exposing more polar groups for absorption. The diffusion coefficient, which is representative of the kinetic aspect of diffusion, was also investigated. It was discovered that the amount of nanohole volume in the polymer; whether the total, the static, or dynamic (i.e. thermally activated) does not correlate to the diffusion coefficient in anyway. Furthermore, at an isotherm the diffusion coefficients for all these materials were relatively constant. From this it is hypothesized that it is the similar sub-Tsb{g} motions of these resins which is the rate limiting step in diffusion. This was bolstered by the fact that the activation energy for diffusion and for the sub-Tsb{g} motions for these epoxies are of the same order of magnitude. The nanostructure of fiber reinforced epoxy composites (i.e. a boron/epoxy and a graphite/epoxy) were probed with the bulk PALS technique as well. It was observed that for the graphite/epoxy composite and its flash (i.e. no fibers present) cured under identical conditions, that the nanoholes in the composite were larger than those present in the flash at temperatures below the epoxy's Tsb{g}. Curiously the boron/epoxy composite and its flash showed an opposite trend. Several potential explanations were examined. The only viable explanation for the observed nanostructural differences between the flash and the resin in these composites utilizes a micromechanics approach involving the CTE mismatch between the fibers and the matrix material. In this approach it is proposed that the fibers in the composite act as a constraint, preventing the nanohole from freely contracting (upon cooling through Tsb{g}) in the axial direction, while Poisson's ratio forces the holes to contract more in the transverse direction than the unrestrained hole in the flash. Therefore the resultant nanoholes in the composite maybe elongated in the fiber direction and shortened in the transverse direction when below the curing temperature. When the PALS technique probed these elongated holes it averaged their dimensions (but weighted the shortest dimension more heavily), thereby yielding the observed results. Despite slightly smaller static holes in the boron/epoxy composite than its flash, no difference in equilibrium uptake was noticed. The diffusion coefficient for the epoxy resin in this composite was found to be an order of magnitude higher than its flash. Nanostructure is not believed to be the cause of this but rather the glass fiber scrim cloth utilized in the processing of the prepreg.

Direct detection of the triphenylpyrylium-derived short-lived intermediates in the photocatalyzed degradation of acetaminophen, acetamiprid, caffeine and carbamazepine.

PubMed

Martinez-Haya, R; Gomis, J; Arques, A; Amat, A M; Miranda, M A; Marin, M L

2017-09-09

Advanced oxidation processes are useful methodologies to accomplish abatement of contaminants; however, elucidation of the reaction mechanisms is hampered by the difficult detection of the short-lived primary key species involved in the photocatalytic processes. Nevertheless, herein the combined use of an organic photocatalyst such as triphenylpyrylium (TPP + ) and photophysical techniques based on emission and absorption spectroscopy allowed monitoring the photocatalyst-derived short-lived intermediates. This methodology has been applied to the photocatalyzed degradation of different pollutants, such as acetaminophen, acetamiprid, caffeine and carbamazepine. First, photocatalytic degradation of a mixture of the pollutants showed that acetaminophen was the most easily photodegraded, followed by carbamazepine and caffeine, being the abatement of acetamiprid almost negligible. This process was accompanied by mineralization, as demonstrated by trapping of carbon dioxide using barium hydroxide. Then, emission spectroscopy measurements (steady-state and time-resolved fluorescence) allowed demonstrating quenching of the singlet excited state of TPP + . Laser flash photolysis experiments with absorption detection showed that oxidation of contaminants is accompanied by TPP + reduction, with formation of a pyranyl radical (TPP), that constituted a fingerprint of the redox nature of the occurring process. The relative amounts of TPP detected was also correlated with the efficiency of the photodegradation process. Copyright © 2017 Elsevier B.V. All rights reserved.

Direct detection of the triphenylpyrylium-derived short-lived intermediates in the photocatalyzed degradation of acetaminophen, acetamiprid, caffeine and carbamazepine.

PubMed

Martinez-Haya, R; Gomis, J; Arques, A; Amat, A M; Miranda, M A; Marin, M L

2018-08-15

Advanced oxidation processes are useful methodologies to accomplish abatement of contaminants; however, elucidation of the reaction mechanisms is hampered by the difficult detection of the short-lived primary key species involved in the photocatalytic processes. Nevertheless, herein the combined use of an organic photocatalyst such as triphenylpyrylium (TPP + ) and photophysical techniques based on emission and absorption spectroscopy allowed monitoring the photocatalyst-derived short-lived intermediates. This methodology has been applied to the photocatalyzed degradation of different pollutants, such as acetaminophen, acetamiprid, caffeine and carbamazepine. First, photocatalytic degradation of a mixture of the pollutants showed that acetaminophen was the most easily photodegraded, followed by carbamazepine and caffeine, being the abatement of acetamiprid almost negligible. This process was accompanied by mineralization, as demonstrated by trapping of carbon dioxide using barium hydroxide. Then, emission spectroscopy measurements (steady-state and time-resolved fluorescence) allowed demonstrating quenching of the singlet excited state of TPP + . Laser flash photolysis experiments with absorption detection showed that oxidation of contaminants is accompanied by TPP + reduction, with formation of a pyranyl radical (TPP), that constituted a fingerprint of the redox nature of the occurring process. The relative amounts of TPP detected was also correlated with the efficiency of the photodegradation process. Copyright © 2018. Published by Elsevier B.V.

Studies on the nature of the primary reactions of photosystem II in photosynthesis. I. The electrochromic 515 nm absorption change as an appropriate indicator for the functional state of the photochemical active centers of system II in DCMY poisoned chloroplasts.

PubMed

Renger, G; Wolff, C

1975-01-01

The field indicating electrochromic 515 nm absorption change has been measured under different excitation conditions in DCMU poisoned chloroplasts in the presence of benzylviologen as electron acceptor. It has been found: 1. The amplitude of the 515 nm absorption change is nearly completely suppressed under repetitive single turnover flash excitation conditions which kinetically block the back reaction around system II (P. Bennoun, Biochim. Biophys. Acta 216, 357 [1970]). 2. The amplitude of the 515 nm absorption change measured under repetitive single turnover flash excitation conditions which allow the completion of the back reaction during the dark time between the flashes (measuring light beam switched off) amounts in the presence of 2 mum DCMU nearly 50% of the electrochromic 515 nm amplitude obtained in the absence of DCMU. In DCMU poisoned chloroplasts this amplitude is significantly decreased by hydroxylaminhydrochloride, but nearly doubled in the presence of CDIP+ascorbate. 3. The dependence of the 515 nm amplitude on the time td between the flashes kinetically resembles the back reaction around system ?II. The time course of the back reaction can be fairly described either by a second order reaction or by a two phase exponential kinetics. 4. 1,3-dinitrobenzene (DNE) or alpha-bromo-alpha-benzylmalodinitril (BBMD) reduce the 515 nm amplitude in DCMU poisoned chloroplasts, but seem to influecne only slightly the kinetics of the back reaction. 5. The dependence of the 515 nm amplitude on the flash light intensity (the amplitude normalized to 1 at 100% flash light intensity) is not changed by DNB. Based on these experimental data it has been concluded that in DCMU poisoned chloroplasts the amplitude of the 515 nm absorption change reflects the functional state of photosystem II centers (designated as photoelectric dipole generators II) under suitable excitation conditions. Furthermore, it is inferred that in DCMU poisoned chlorplasts the photoelectric dipole generators II either cooperate (probably as twin-pairs) or exist in two functionally different forms. With respect to BBMD and DNB it is assumed that these agents transform the phtooelectric dipole generators II into powerful nonphotochemical quenchers, which significantly reduce the variable fluorescence in DCMU-poisoned chloroplasts.

The examination of berberine excited state by laser flash photolysis

NASA Astrophysics Data System (ADS)

Cheng, Lingli; Wang, Mei; Zhao, Ping; Zhu, Hui; Zhu, Rongrong; Sun, Xiaoyu; Yao, Side; Wang, Shilong

2009-07-01

The property of the excited triplet state of berberine (BBR) was investigated by using time-resolved laser flash photolysis of 355 nm in acetonitrile. The transient absorption spectra of the excited triplet BBR were obtained in acetonitrile, which have an absorption maximum at 420 nm. And the ratio of excitation to ionization of BBR in acetonitrile solvent was calculated. The self-decay and self-quenching rate constants, and the absorption coefficient of 3BBR* were investigated and the excited state quantum yield was determined. Furthermore utilizing the benzophenone (BEN) as a triplet sensitizer, and the β-carotene (Car) as an excited energy transfer acceptor, the assignment of 3BBR* was further confirmed and the related energy transfer rate constants were also determined.

Electrical wire explosion process of copper/silver hybrid nano-particle ink and its sintering via flash white light to achieve high electrical conductivity.

PubMed

Chung, Wan-Ho; Hwang, Yeon-Taek; Lee, Seung-Hyun; Kim, Hak-Sung

2016-05-20

In this work, combined silver/copper nanoparticles were fabricated by the electrical explosion of a metal wire. In this method, a high electrical current passes through the metal wire with a high voltage. Consequently, the metal wire evaporates and metal nanoparticles are formed. The diameters of the silver and copper nanoparticles were controlled by changing the voltage conditions. The fabricated silver and copper nano-inks were printed on a flexible polyimide (PI) substrate and sintered at room temperature via a flash light process, using a xenon lamp and varying the light energy. The microstructures of the sintered silver and copper films were observed using a scanning electron microscope (SEM) and a transmission electron microscope (TEM). To investigate the crystal phases of the flash-light-sintered silver and copper films, x-ray diffraction (XRD) was performed. The absorption wavelengths of the silver and copper nano-inks were measured using ultraviolet-visible spectroscopy (UV-vis). Furthermore, the resistivity of the sintered silver and copper films was measured using the four-point probe method and an alpha step. As a result, the fabricated Cu/Ag film shows a high electrical conductivity (4.06 μΩcm), which is comparable to the resistivity of bulk copper (1.68 μΩcm). In addition, the fabricated Cu/Ag nanoparticle film shows superior oxidation stability compared to the Cu nanoparticle film.

Development of novel two-photon absorbing chromophores

NASA Astrophysics Data System (ADS)

Rogers, Joy E.; Slagle, Jonathan E.; McLean, Daniel G.; Sutherland, Richard L.; Krein, Douglas M.; Cooper, Thomas M.; Brant, Mark; Heinrichs, James; Kannan, Ramamurthi; Tan, Loon-Seng; Urbas, Augustine M.; Fleitz, Paul A.

2006-08-01

There has been much interest in the development of two-photon absorbing materials and many efforts to understand the nonlinear absorption properties of these dyes but this area is still not well understood. A computational model has been developed in our lab to understand the nanosecond nonlinear absorption properties that incorporate all of the measured one-photon photophysical parameters of a class of materials called AFX. We have investigated the nonlinear and photophysical properties of the AFX chromophores including the two-photon absorption cross-section, the excited state cross-section, the intersystem crossing quantum yield, and the singlet and triplet excited state lifetimes using a variety of experimental techniques that include UV-visible, fluorescence and phosphorescence spectroscopy, time correlated single photon counting, ultrafast transient absorption, and nanosecond laser flash photolysis. The model accurately predicts the nanosecond nonlinear transmittance data using experimentally measured parameters. Much of the strong nonlinear absorption has been shown to be due to excited state absorption from both the singlet and triplet excited states. Based on this understanding of the nonlinear absorption and the importance of singlet and triplet excited states we have begun to develop new two-photon absorbing molecules within the AFX class as well as linked to other classes of nonlinear absorbing molecules. This opens up the possibilities of new materials with unique and interesting properties. Specifically we have been working on a new class of two-photon absorbing molecules linked to platinum poly-ynes. In the platinum poly-yne chromophores the photophysics are more complicated and we have just started to understand what drives both the linear and non-linear photophysical properties.

From the tunneling dimer to the onset of microsolvation: Infrared spectroscopy of allyl radical water aggregates in helium nanodroplets

NASA Astrophysics Data System (ADS)

Leicht, Daniel; Kaufmann, Matin; Pal, Nitish; Schwaab, Gerhard; Havenith, Martina

2017-03-01

The infrared spectrum of allyl:water clusters embedded in helium nanodroplets was recorded. Allyl radicals were produced by flash vacuum pyrolysis and trapped in helium droplets. Deuterated water was added to the doped droplets, and the infrared spectrum of the radical water aggregates was recorded in the frequency range 2570-2820 cm-1. Several absorption bands are observed and assigned to 1:1 and 1:2 allyl:D2O clusters, based on pressure dependent measurements and accompanying quantum chemical calculations. The analysis of the 1:1 cluster spectrum revealed a tunneling splitting as well as a combination band. For the 1:2 cluster, we observe a water dimer-like motif that is bound by one π-hydrogen bond to the allyl radical.

Metrology of fused silica

NASA Astrophysics Data System (ADS)

Nürnberg, F.; Kühn, B.; Rollmann, K.

2016-12-01

In over 100 years of quartz glass fabrication, the applications and the optical requirements for this type of optical material have significantly changed. Applications like spectroscopy, UV flash lamps, the Apollo missions as well as the growth in UV and IR applications have directed quartz glass development towards new products, technologies or methods of measurement. The boundaries of the original measurement methods have been achieved and more sensitive measurements with precise resolution for transmission, purity, radiation resistance, absorption, thermal and mechanical stability as well as optical properties like homogeneity, stress birefringence, striae and bubbles/inclusions had to be found. This article will provide an overview of the development of measuring methods of quartz glass, discuss their limits and accuracy and point out the parameters which are of high relevance for today's laser applications.

Generalizing the flash technique in the front-face configuration to measure the thermal diffusivity of semitransparent solids

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

Pech-May, Nelson Wilbur; Department of Applied Physics, CINVESTAV Unidad Mérida, carretera Antigua a Progreso km6, A.P. 73 Cordemex, Mérida Yucatán 97310, México; Mendioroz, Arantza

2014-10-15

In this work, we have extended the front-face flash method to retrieve simultaneously the thermal diffusivity and the optical absorption coefficient of semitransparent plates. A complete theoretical model that allows calculating the front surface temperature rise of the sample has been developed. It takes into consideration additional effects, such as multiple reflections of the heating light beam inside the sample, heat losses by convection and radiation, transparency of the sample to infrared wavelengths, and heating pulse duration. Measurements performed on calibrated solids, covering a wide range of absorption coefficients (from transparent to opaque) and thermal diffusivities, validate the proposed method.

Fourier transform spectrometer observations of solar carbon monoxide. III - Time-resolved spectroscopy of the Delta V = 1 bands

NASA Astrophysics Data System (ADS)

Ayres, Thomas R.; Brault, James W.

1990-11-01

Time series of the 2100/cm Delta v = 1 absorption bands of CO at the center of the solar disk and at the extreme limb have been recorded by Fourier transform spectrometer. The photospheric 5-min oscillation appears prominently at sun center. The peak-to-peak brightness temperature amplitude is roughly 300 K, and the peak-to-peak Doppler shift is roughly 1100 m/s. The 70 deg phase lag of maximum core intensity with respect to maximum redshift for the strongest Delta v = 1 absorptions is less than the 90 deg expected in the adiabatic limit. No dominant four-minute signal in the line intensity like that reported by Deming et al. (1984, 1986, and 1987) is found, nor is evidence for extreme fluctuations on short time scales like those proposed by Kalkofen et al. (1984). The strong Delta v = 1 lines exhibit systematic Doppler shifts of less than about 1 km/s, contrary to the predictions of transonic redshifts if the CO 'clouds' are associated with a dynamic cooling phase of the Ca II 'cell flashes.'

Comparison of TiO₂ and ZnO solar cells sensitized with an indoline dye: time-resolved laser spectroscopy studies of partial charge separation processes.

PubMed

Sobuś, Jan; Burdziński, Gotard; Karolczak, Jerzy; Idígoras, Jesús; Anta, Juan A; Ziółek, Marcin

2014-03-11

Time-resolved laser spectroscopy techniques in the time range from femtoseconds to seconds were applied to investigate the charge separation processes in complete dye-sensitized solar cells (DSC) made with iodide/iodine liquid electrolyte and indoline dye D149 interacting with TiO2 or ZnO nanoparticles. The aim of the studies was to explain the differences in the photocurrents of the cells (3-4 times higher for TiO2 than for ZnO ones). Electrochemical impedance spectroscopy and nanosecond flash photolysis studies revealed that the better performance of TiO2 samples is not due to the charge collection and dye regeneration processes. Femtosecond transient absorption results indicated that after first 100 ps the number of photoinduced electrons in the semiconductor is 3 times higher for TiO2 than for ZnO solar cells. Picosecond emission studies showed that the lifetime of the D149 excited state is about 3 times longer for ZnO than for TiO2 samples. Therefore, the results indicate that lower performance of ZnO solar cells is likely due to slower electron injection. The studies show how to correlate the laser spectroscopy methodology with global parameters of the solar cells and should help in better understanding of the behavior of alternative materials for porous electrodes for DSC and related devices.

Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

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

Liang, Wenchuan

X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S 2 state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S 2 state with the g~4 electron paramagnetic resonance (EPR) signal (S 2-g4 state) was compared with that in the S 2 state with multiline signal (S 2-MLS state) and the S 1 state. The S 2-g4 statemore » has a higher XAS inflection point energy than that of the S 1 state, indicating the oxidation of Mn in the advance from the S 1 to the S 2-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S 2-g4 state is different from that in the S 2-MLS or the S 1 state. In the S 2-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S 1 or S 2-MLS states. The third shell of the S 2-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S 2-MLS or the S 1 state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S 1 → S 2 transition.« less

Fourier transform infrared difference and time-resolved infrared detection of the electron and proton transfer dynamics in photosynthetic water oxidation.

PubMed

Noguchi, Takumi

2015-01-01

Photosynthetic water oxidation, which provides the electrons necessary for CO₂ reduction and releases O₂ and protons, is performed at the Mn₄CaO₅ cluster in photosystem II (PSII). In this review, studies that assessed the mechanism of water oxidation using infrared spectroscopy are summarized focusing on electron and proton transfer dynamics. Structural changes in proteins and water molecules between intermediates known as Si states (i=0-3) were detected using flash-induced Fourier transform infrared (FTIR) difference spectroscopy. Electron flow in PSII and proton release from substrate water were monitored using the infrared changes in ferricyanide as an exogenous electron acceptor and Mes buffer as a proton acceptor. Time-resolved infrared (TRIR) spectroscopy provided information on the dynamics of proton-coupled electron transfer during the S-state transitions. In particular, a drastic proton movement during the lag phase (~200μs) before electron transfer in the S3→S0 transition was detected directly by monitoring the infrared absorption of a polarizable proton in a hydrogen bond network. Furthermore, the proton release pathways in the PSII proteins were analyzed by FTIR difference measurements in combination with site-directed mutagenesis, isotopic substitutions, and quantum chemical calculations. Therefore, infrared spectroscopy is a powerful tool for understanding the molecular mechanism of photosynthetic water oxidation. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Terrestrial solar spectral modeling. [SOLTRAN, BRITE, and FLASH codes

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

Bird, R.E.

The utility of accurate computer codes for calculating the solar spectral irradiance under various atmospheric conditions was recognized. New absorption and extraterrestrial spectral data are introduced. Progress is made in radiative transfer modeling outside of the solar community, especially for space and military applications. Three rigorous radiative transfer codes SOLTRAN, BRITE, and FLASH are employed. The SOLTRAN and BRITE codes are described and results from their use are presented.

A two-column flash chromatography approach to pyoverdin production from Pseudomonas putida GB1.

PubMed

Duckworth, Owen W; Markarian, Dawn S; Parker, Dorothy L; Harrington, James M

2017-04-01

Our knowledge of the biological and environmental reactivity of siderophores is limited by the difficulty and cost of obtaining reasonable quantities by purification or synthesis. In this note, we describe a modified procedure for the low-cost, mg-scale purification of pyoverdin-type siderophores using a dual-flash chromatography (reverse-phase absorption and size exclusion) approach. Copyright © 2017 Elsevier B.V. All rights reserved.

Spectroscopic temperature measurements in interior ballistic environments

NASA Astrophysics Data System (ADS)

Klingenberg, G.; Mach, H.

1984-11-01

Spectroscopic temperature measurements during the interior ballistic cycle of a 20 mm test fixture gun and inside the muzzle flash of a 7.62 mm rifle are described. The investigation yields information on temperature distribution in the burning propellant charge of the 20 mm test fixture and on radial temperature profiles in the 7.62 mm muzzle flash region. A technique to obtain temperature during the ignition and combustion within the 20 mm propellant charge is presented. Additional in-bore measurements by quartz windows mounted into bores along the barrel and emission-absorption measurements inside the muzzle flash of the 20 mm test fixture yield a complete temperature profile for the gun system. Spectroscopic infrared measurements inside the muzzle flash of a 7.62 mm rifle complete the investigation.

Deep Space Detection of Oriented Ice Crystals

NASA Astrophysics Data System (ADS)

Marshak, A.; Varnai, T.; Kostinski, A. B.

2017-12-01

The deep space climate observatory (DSCOVR) spacecraft resides at the first Lagrangian point about one million miles from Earth. A polychromatic imaging camera onboard delivers nearly hourly observations of the entire sun-lit face of the Earth. Many images contain unexpected bright flashes of light over both ocean and land. We constructed a yearlong time series of flash latitudes, scattering angles and oxygen absorption to demonstrate conclusively that the flashes over land are specular reflections off tiny ice crystals floating in the air nearly horizontally. Such deep space detection of tropospheric ice can be used to constrain the likelihood of oriented crystals and their contribution to Earth albedo.

Magnetic field effect corroborated with docking study to explore photoinduced electron transfer in drug-protein interaction.

PubMed

Chakraborty, Brotati; Roy, Atanu Singha; Dasgupta, Swagata; Basu, Samita

2010-12-30

Conventional spectroscopic tools such as absorption, fluorescence, and circular dichroism spectroscopy used in the study of photoinduced drug-protein interactions can yield useful information about ground-state and excited-state phenomena. However, photoinduced electron transfer (PET) may be a possible phenomenon in the drug-protein interaction, which may go unnoticed if only conventional spectroscopic observations are taken into account. Laser flash photolysis coupled with an external magnetic field can be utilized to confirm the occurrence of PET and authenticate the spin states of the radicals/radical ions formed. In the study of interaction of the model protein human serum albumin (HSA) with acridine derivatives, acridine yellow (AY) and proflavin (PF(+)), conventional spectroscopic tools along with docking study have been used to decipher the binding mechanism, and laser flash photolysis technique with an associated magnetic field (MF) has been used to explore PET. The results of fluorescence study indicate that fluorescence resonance energy transfer takes place from the protein to the acridine-based drugs. Docking study unveils the crucial role of Ser 232 residue of HSA in explaining the differential behavior of the two drugs towards the model protein. Laser flash photolysis experiments help to identify the radicals/radical ions formed in the due course of PET (PF(•), AY(•-), TrpH(•+), Trp(•)), and the application of an external MF has been used to characterize their initial spin-state. Owing to its distance dependence, MF effect gives an idea about the proximity of the radicals/radical ions during interaction in the system and also helps to elucidate the reaction mechanisms. A prominent MF effect is observed in homogeneous buffer medium owing to the pseudoconfinement of the radicals/radical ions provided by the complex structure of the protein.

The flash-quench technique in protein-DNA electron transfer: reduction of the guanine radical by ferrocytochrome c.

PubMed

Stemp, E D; Barton, J K

2000-08-21

Electron transfer from a protein to oxidatively damaged DNA, specifically from ferrocytochrome c to the guanine radical, was examined using the flash-quench technique. Ru(phen)2dppz2+ (dppz = dipyridophenazine) was employed as the photosensitive intercalator, and ferricytochrome c (Fe3+ cyt c), as the oxidative quencher. Using transient absorption and time-resolved luminescence spectroscopies, we examined the electron-transfer reactions following photoexcitation of the ruthenium complex in the presence of poly(dA-dT) or poly(dG-dC). The luminescence-quenching titrations of excited Ru(phen)2dppz2+ by Fe3+ cyt c are nearly identical for the two DNA polymers. However, the spectral characteristics of the long-lived transient produced by the quenching depend strongly upon the DNA. For poly(dA-dT), the transient has a spectrum consistent with formation of a [Ru(phen)2dppz3+, Fe2+ cyt c] intermediate, indicating that the system regenerates itself via electron transfer from the protein to the Ru(III) metallointercalator for this polymer. For poly(dG-dC), however, the transient has the characteristics expected for an intermediate of Fe2+ cyt c and the neutral guanine radical. The characteristics of the transient formed with the GC polymer are consistent with rapid oxidation of guanine by the Ru(III) complex, followed by slow electron transfer from Fe2+ cyt c to the guanine radical. These experiments show that electron holes on DNA can be repaired by protein and demonstrate how the flash-quench technique can be used generally in studying electron transfer from proteins to guanine radicals in duplex DNA.

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

Wang, Ya; Su, Yingna; Hong, Zhenxiang

In this paper, we report our first-step results of high resolution He i 10830 Å narrow-band imaging (bandpass: 0.5 Å) of an M1.8 class two-ribbon flare on 2012 July 5. The flare was observed with the 1.6 m aperture New Solar Telescope at Big Bear Solar Observatory. For this unique data set, sunspot dynamics during flaring were analyzed for the first time. By directly imaging the upper chromosphere, running penumbral waves are clearly seen as an outward extension of umbral flashes; both take the form of absorption in the 10830 Å narrow-band images. From a space–time image made of amore » slit cutting across a flare ribbon and the sunspot, we find that the dark lanes for umbral flashes and penumbral waves are obviously broadened after the flare. The most prominent feature is the sudden appearance of an oscillating absorption strip inside the ribbon when it sweeps into the sunspot’s penumbral and umbral regions. During each oscillation, outwardly propagating umbral flashes and subsequent penumbral waves rush out into the inwardly sweeping ribbon, followed by a return of the absorption strip with similar speed. We tentatively explain the phenomena as the result of a sudden increase in the density of ortho-helium atoms in the area of the sunspot being excited by the flare’s extreme ultraviolet illumination. This explanation is based on the observation that 10830 Å absorption around the sunspot area gets enhanced during the flare. Nevertheless, questions are still open and we need further well-devised observations to investigate the behavior of sunspot dynamics during flares.« less

High resolution He I 10830 angstrom narrow-band imaging of an M-class flare.I-analysis of sunspot dynamics during flaring

NASA Astrophysics Data System (ADS)

Wang, Ya; Su, Yingna; Hong, Zhenxiang; Zeng, Zhicheng; Ji, Kaifan; Goode, Philip R.; Cao, Wenda; Ji, Haisheng

2016-10-01

We report our first-step results of high resolution He I 1083 nm narrow-band imaging of an M 1.8 class two-ribbon flare on July 5,2012. The flare was observed with the 1.6 meter aperture New Solar Telescope at Big Bear Solar Observatory. For this unique data set, sunspot dynamics during flaring were analyzed for the first time. By directly imaging the upper chromosphere, running penumbral waves are clearly seen as an outward extention of umbral flashes, both take the form of absorption in our 1083 nm narrow-band images. From a space-time image made of a slit cutting across the ribbon and the sunspot, we find that dark lanes for umbral flashes and penumbral waves are obviously broadened after the flare. The most prominent feature is the sudden appearance of an oscillating absorption strip inside one ribbon of the flare when it sweeps into sunspot's penumbral and umbral regions. During each oscillation, outwardly propagating umbral flashes and subsequent penumbral waves rush out into the inwardly sweeping ribbon, followed by a returning of the absorption strip with similar speed. We tentatively explain the phenomenon as the result of a sudden increase in the density of ortho-Helium atoms in the area of the sunspot area being excited by the flare's EUV illumination. This explanation is based on the obsevation that 1083 nm absorption in the sunspot area gets enhanced during the flare. Nevertheless, questions are still open and we need further well-devised observations to investigate the behavior of sunspot dynamics during flares.

Studies of ClO and BrO reactions important in the polar stratosphere: Kinetics and mechanism of the ClO+BrO and ClO+ClO reactions

NASA Technical Reports Server (NTRS)

Friedl, Randall R.; Sander, Stanley P.

1988-01-01

The reactions, BrO + ClO yields Br + ClOO (1a) yields Br + OClO (1b) yields BrCl + O2 (1c) and ClO + ClO yields Cl + CiOO (2a) yields Cl + OClO (2b) yields Cl2 + O2 (2c) yields (ClO)2 (2d) have assumed new importance in explaining the unusual springtime depletion of ozone observed in the Antarctic stratosphere. The mechanisms of these reactions involve the formation of metastable intermediates which subsequently decompose through several energetically allowed products providing the motivation to study these reactions using both the discharge flow-mass spectrometric and flash photolysis - ultraviolet absorption techniques. These methods have also been used to explore aspects of the kinetics and spectroscopy of the ClO dimer.

Formation of silicon nanocrystals in silicon carbide using flash lamp annealing

NASA Astrophysics Data System (ADS)

Weiss, Charlotte; Schnabel, Manuel; Prucnal, Slawomir; Hofmann, Johannes; Reichert, Andreas; Fehrenbach, Tobias; Skorupa, Wolfgang; Janz, Stefan

2016-09-01

During the formation of Si nanocrystals (Si NC) in SixC1-x layers via solid-phase crystallization, the unintended formation of nanocrystalline SiC reduces the minority carrier lifetime and therefore the performance of SixC1-x as an absorber layer in solar cells. A significant reduction in the annealing time may suppress the crystallization of the SiC matrix while maintaining the formation of Si NC. In this study, we investigated the crystallization of stoichiometric SiC and Si-rich SiC using conventional rapid thermal annealing (RTA) and nonequilibrium millisecond range flash lamp annealing (FLA). The investigated SixC1-x films were prepared by plasma-enhanced chemical vapor deposition and annealed at temperatures from 700 °C to 1100 °C for RTA and at flash energies between 34 J/cm2 and 62 J/cm2 for FLA. Grazing incidence X-ray diffraction and Fourier transformed infrared spectroscopy were conducted to investigate hydrogen effusion, Si and SiC NC growth, and SiC crystallinity. Both the Si content and the choice of the annealing process affect the crystallization behavior. It is shown that under certain conditions, FLA can be successfully utilized for the formation of Si NC in a SiC matrix, which closely resembles Si NC in a SiC matrix achieved by RTA. The samples must have excess Si, and the flash energy should not exceed 40 J/cm2 and 47 J/cm2 for Si0.63C0.37 and Si0.77C0.23 samples, respectively. Under these conditions, FLA succeeds in producing Si NC of a given size in less crystalline SiC than RTA does. This result is discussed in terms of nucleation and crystal growth using classical crystallization theory. For FLA and RTA samples, an opposite relationship between NC size and Si content was observed and attributed either to the dependence of H effusion on Si content or to the optical absorption properties of the materials, which also depend on the Si content.

Role of the PufX protein in photosynthetic growth of Rhodobacter sphaeroides. 2. PufX is required for efficient ubiquinone/ubiquinol exchange between the reaction center QB site and the cytochrome bc1 complex.

PubMed

Barz, W P; Verméglio, A; Francia, F; Venturoli, G; Melandri, B A; Oesterhelt, D

1995-11-21

The PufX membrane protein is essential for photosynthetic growth of Rhodobacter sphaeroides because it is required for multiple-turnover electron transfer under anaerobic conditions [see accompanying article; Barz, W. P., Francia, F., Venturoli, G., Melandri, B. A., Verméglio, A., & Oesterhelt, D. (1995) Biochemistry 34, 15235-15247]. In order to understand the molecular role of PufX, light-induced absorption spectroscopy was performed using a pufX- mutant, a pufX+ strain, and two suppressor mutants. We show that the reaction center (RC) requires PufX for its functionality under different redox conditions than the cytochrome bc1 complex: When the kinetics of flash-induced reduction of cytochrome b561 were monitored in chromatophores, we observed a requirement of PufX for turnover of the cytochrome bc1 complex only at high redox potential (Eh > 140 mV), suggesting a function of PufX in lateral ubiquinol transfer from the RC. In contrast, PufX is required for multiple turnover of the RC only under reducing conditions: When the Q pool was partially oxidized in vivo using oxygen or electron acceptors like dimethyl sulfoxide or trimethylamine N-oxide, the deletion of PufX had no effect on light-driven electron flow through the RC. Flash train experiments under anaerobic in vivo conditions revealed that RC photochemistry does not depend on PufX for the first two flash excitations. Following the third and subsequent flashes, however, efficient charge separation requires PufX, indicating an important role of PufX for fast Q/QH2 exchange at the QB site of the RC. We show that the Q/QH2 exchange rate is reduced approximately 500-fold by the deletion of PufX when the Q pool is nearly completely reduced, demonstrating an essential role of PufX for the access of ubiquinone to the QB site. The fast ubiquinone/ubiquinol exchange is partially restored by suppressor mutations altering the macromolecular antenna structure. These results suggest an indirect role of PufX in structurally organizing a functional photosynthetic apparatus.

Taking Snapshots of Photosynthetic Water Oxidation Using Femtosecond X-ray Diffraction and Spectroscopy

PubMed Central

Kern, Jan; Tran, Rosalie; Alonso-Mori, Roberto; Koroidov, Sergey; Echols, Nathaniel; Hattne, Johan; Ibrahim, Mohamed; Gul, Sheraz; Laksmono, Hartawan; Sierra, Raymond G.; Gildea, Richard J.; Han, Guangye; Hellmich, Julia; Lassalle-Kaiser, Benedikt; Chatterjee, Ruchira; Brewster, Aaron S.; Stan, Claudiu A.; Glöckner, Carina; Lampe, Alyssa; DiFiore, Dörte; Milathianaki, Despina; Fry, Alan R.; Seibert, M. Marvin; Koglin, Jason E.; Gallo, Erik; Uhlig, Jens; Sokaras, Dimosthenis; Weng, Tsu-Chien; Zwart, Petrus H.; Skinner, David E.; Bogan, Michael J.; Messerschmidt, Marc; Glatzel, Pieter; Williams, Garth J.; Boutet, Sébastien; Adams, Paul D.; Zouni, Athina; Messinger, Johannes; Sauter, Nicholas K.; Bergmann, Uwe; Yano, Junko; Yachandra, Vittal K.

2014-01-01

The dioxygen we breathe is formed from water by its light-induced oxidation in photosystem II. O2 formation takes place at a catalytic manganese cluster within milliseconds after the photosystem II reaction center is excited by three single-turnover flashes. Here we present combined X-ray emission spectra and diffraction data of 2 flash (2F) and 3 flash (3F) photosystem II samples, and of a transient 3F′ state (250 μs after the third flash), collected under functional conditions using an X-ray free electron laser. The spectra show that the initial O-O bond formation, coupled to Mn-reduction, does not yet occur within 250 μs after the third flash. Diffraction data of all states studied exhibit an anomalous scattering signal from Mn but show no significant structural changes at the present resolution of 4.5 Å. This study represents the initial frames in a molecular movie of the structural changes during the catalytic reaction in photosystem II. PMID:25006873

Taking snapshots of photosynthetic water oxidation using femtosecond X-ray diffraction and spectroscopy

NASA Astrophysics Data System (ADS)

Kern, Jan; Tran, Rosalie; Alonso-Mori, Roberto; Koroidov, Sergey; Echols, Nathaniel; Hattne, Johan; Ibrahim, Mohamed; Gul, Sheraz; Laksmono, Hartawan; Sierra, Raymond G.; Gildea, Richard J.; Han, Guangye; Hellmich, Julia; Lassalle-Kaiser, Benedikt; Chatterjee, Ruchira; Brewster, Aaron S.; Stan, Claudiu A.; Glöckner, Carina; Lampe, Alyssa; Difiore, Dörte; Milathianaki, Despina; Fry, Alan R.; Seibert, M. Marvin; Koglin, Jason E.; Gallo, Erik; Uhlig, Jens; Sokaras, Dimosthenis; Weng, Tsu-Chien; Zwart, Petrus H.; Skinner, David E.; Bogan, Michael J.; Messerschmidt, Marc; Glatzel, Pieter; Williams, Garth J.; Boutet, Sébastien; Adams, Paul D.; Zouni, Athina; Messinger, Johannes; Sauter, Nicholas K.; Bergmann, Uwe; Yano, Junko; Yachandra, Vittal K.

2014-07-01

The dioxygen we breathe is formed by light-induced oxidation of water in photosystem II. O2 formation takes place at a catalytic manganese cluster within milliseconds after the photosystem II reaction centre is excited by three single-turnover flashes. Here we present combined X-ray emission spectra and diffraction data of 2-flash (2F) and 3-flash (3F) photosystem II samples, and of a transient 3F’ state (250 μs after the third flash), collected under functional conditions using an X-ray free electron laser. The spectra show that the initial O-O bond formation, coupled to Mn reduction, does not yet occur within 250 μs after the third flash. Diffraction data of all states studied exhibit an anomalous scattering signal from Mn but show no significant structural changes at the present resolution of 4.5 Å. This study represents the initial frames in a molecular movie of the structural changes during the catalytic reaction in photosystem II.

Laser photolysis studies of ω-bond dissociation in aromatic carbonyls with a C-C triple bond stimulated by triplet sensitization.

PubMed

Yamaji, Minoru; Horimoto, Ami; Marciniak, Bronislaw

2017-07-14

We have prepared three types of carbonyl compounds, benzoylethynylmethyl phenyl sulfide (2@SPh), (p-benzoyl)phenylethynylmethyl phenyl sulfide (3@SPh) and p-(benzoylethynyl)benzyl phenyl sulfide (4@SPh) with benzoyl and phenylthiylmethyl groups, which are interconnected with a C-C triple bond and a phenyl ring. Laser flash photolysis of 3@SPh and 4@SPh in acetonitrile provided the transient absorption spectra of the corresponding triplet states where no chemical reactions were recognized. Upon laser flash photolysis of 2@SPh, the absorption band due to the phenylthiyl radical (PTR) was obtained, indicating that the C-S bond cleaved in the excited state. Triplet sensitization of these carbonyl compounds using acetone and xanthone was conducted using laser photolysis techniques. The formation of triplet 3@SPh was seen in the transient absorption, whereas the PTR formation was observed for 2@SPh and 4@SPh, indicating that the triplet states were reactive for the C-S bond dissociation. The C-S bond dissociation mechanism for 4@SPh upon triplet sensitization is discussed in comparison with those for 2@SPh and 3@SPh.

Primary photochemical processes for Pt(iv) diazido complexes prospective in photodynamic therapy of tumors.

PubMed

Shushakov, Anton A; Pozdnyakov, Ivan P; Grivin, Vjacheslav P; Plyusnin, Victor F; Vasilchenko, Danila B; Zadesenets, Andrei V; Melnikov, Alexei A; Chekalin, Sergey V; Glebov, Evgeni M

2017-07-25

Diazide diamino complexes of Pt(iv) are considered as prospective prodrugs in oxygen-free photodynamic therapy (PDT). Primary photophysical and photochemical processes for cis,trans,cis-[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] and trans,trans,trans-[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] complexes were studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The process of photolysis is multistage. The first stage is the photosubstitution of an azide ligand to a water molecule. This process was shown to be a chain reaction involving redox stages. Pt(iv) and Pt(iii) intermediates responsible for the chain propagation were recorded using ultrafast kinetic spectroscopy and nanosecond laser flash photolysis. The mechanism of photosubstitution is proposed.

All-photonic drying and sintering process via flash white light combined with deep-UV and near-infrared irradiation for highly conductive copper nano-ink

PubMed Central

Hwang, Hyun-Jun; Oh, Kyung-Hwan; Kim, Hak-Sung

2016-01-01

We developed an ultra-high speed photonic sintering method involving flash white light (FWL) combined with near infrared (NIR) and deep UV light irradiation to produce highly conductive copper nano-ink film. Flash white light irradiation energy and the power of NIR/deep UV were optimized to obtain high conductivity Cu films. Several microscopic and spectroscopic characterization techniques such as scanning electron microscopy (SEM), a x-ray diffraction (XRD), and Fourier-transform infrared (FT-IR) spectroscopy were employed to characterize the Cu nano-films. Optimally sintered Cu nano-ink films produced using a deep UV-assisted flash white light sintering technique had the lowest resistivity (7.62 μΩ·cm), which was only 4.5-fold higher than that of bulk Cu film (1.68 μΩ•cm). PMID:26806215

All-photonic drying and sintering process via flash white light combined with deep-UV and near-infrared irradiation for highly conductive copper nano-ink.

PubMed

Hwang, Hyun-Jun; Oh, Kyung-Hwan; Kim, Hak-Sung

2016-01-25

We developed an ultra-high speed photonic sintering method involving flash white light (FWL) combined with near infrared (NIR) and deep UV light irradiation to produce highly conductive copper nano-ink film. Flash white light irradiation energy and the power of NIR/deep UV were optimized to obtain high conductivity Cu films. Several microscopic and spectroscopic characterization techniques such as scanning electron microscopy (SEM), a x-ray diffraction (XRD), and Fourier-transform infrared (FT-IR) spectroscopy were employed to characterize the Cu nano-films. Optimally sintered Cu nano-ink films produced using a deep UV-assisted flash white light sintering technique had the lowest resistivity (7.62 μΩ·cm), which was only 4.5-fold higher than that of bulk Cu film (1.68 μΩ•cm).

Terrestrial glint seen from deep space: Oriented ice crystals detected from the Lagrangian point

NASA Astrophysics Data System (ADS)

Marshak, Alexander; Várnai, Tamás.; Kostinski, Alexander

2017-05-01

The Deep Space Climate Observatory (DSCOVR) spacecraft resides at the first Lagrangian point about one million miles from Earth. A polychromatic imaging camera onboard delivers nearly hourly observations of the entire sunlit face of the Earth. Many images contain unexpected bright flashes of light over both ocean and land. We construct a yearlong time series of flash latitudes, scattering angles, and oxygen absorption to demonstrate conclusively that the flashes over land are specular reflections off tiny ice platelets floating in the air nearly horizontally. Such deep space detection of tropospheric ice can be used to constrain the likelihood of oriented crystals and their contribution to Earth albedo. These glint observations also support proposals for detecting starlight glints off faint companions in our search for habitable exoplanets.

Applications of absorption spectroscopy using quantum cascade lasers.

PubMed

Zhang, Lizhu; Tian, Guang; Li, Jingsong; Yu, Benli

2014-01-01

Infrared laser absorption spectroscopy (LAS) is a promising modern technique for sensing trace gases with high sensitivity, selectivity, and high time resolution. Mid-infrared quantum cascade lasers, operating in a pulsed or continuous wave mode, have potential as spectroscopic sources because of their narrow linewidths, single mode operation, tunability, high output power, reliability, low power consumption, and compactness. This paper reviews some important developments in modern laser absorption spectroscopy based on the use of quantum cascade laser (QCL) sources. Among the various laser spectroscopic methods, this review is focused on selected absorption spectroscopy applications of QCLs, with particular emphasis on molecular spectroscopy, industrial process control, combustion diagnostics, and medical breath analysis.

Shock compression and flash-heating of molecular adsorbates on the picosecond time scale

NASA Astrophysics Data System (ADS)

Berg, Christopher Michael

An ultrafast nonlinear coherent laser spectroscopy termed broadband multiplex vibrational sum-frequency generation (SFG) with nonresonant suppression was employed to monitor vibrational transitions of molecular adsorbates on metallic substrates during laser-driven shock compression and flash-heating. Adsorbates were in the form of well-ordered self-assembled monolayers (SAMs) and included molecular explosive simulants, such as nitroaromatics, and long chain-length alkanethiols. Based on reflectance measurements of the metallic substrates, femtosecond flash-heating pulses were capable of producing large-amplitude temperature jumps with DeltaT = 500 K. Laser-driven shock compression of SAMs produced pressures up to 2 GPa, where 1 GPa ≈ 1 x 104 atm. Shock pressures were estimated via comparison with frequency shifts observed in the monolayer vibrational transitions during hydrostatic pressure measurements in a SiC anvil cell. Molecular dynamics during flash-heating and shock loading were probed with vibrational SFG spectroscopy with picosecond temporal resolution and sub-nanometer spatial resolution. Flash-heating studies of 4-nitrobenzenethiolate (NBT) on Au provided insight into effects from hot-electron excitation of the molecular adsorbates at early pump-probe delay times. At longer delay times, effects from the excitation of SAM lattice modes and lower-energy NBT vibrations were shown. In addition, flash-heating studies of alkanethiolates demonstrated chain disordering behaviors as well as interface thermal conductances across the Au-SAM junction, which was of specific interest within the context of molecular electronics. Shock compression studies of molecular explosive simulants, such as 4-nitrobenzoate (NBA), demonstrated the proficiency of this technique to observe shock-induced molecular dynamics, in this case orientational dynamics, on the picosecond time scale. Results validated the utilization of these refined shock loading techniques to probe the shock initiation or first bond-breaking reactions in molecular explosives such as delta-HMX: a necessary study for the development of safer and more effective energetic materials.

Picosecond flash spectroscopic studies on ultraviolet stabilizers and stabilized polymers

NASA Technical Reports Server (NTRS)

Scott, G. W.

1982-01-01

Spectroscopic and excited state decay kinetics are reported for monomeric and polymeric forms of ultraviolet stabilizers in the 2-(2'-hydroxyphenyl)-benzotriazole and 2-hydroxybenzophenone classes. For some of these molecules in various solvents at room temperature, (1) ground state absorption spectra, (2) emission spectra, (3) picosecond time-resolved transient absorption spectra, (4) ground state absorption recovery kinetics, (5) emission kinetics, and (6) transient absorption kinetics are reported. In the solid state at low temperatures, emission spectra and their temperature dependent kinetics up to approximately 200K as well as, in one case, the 12K excitation spectra of the observed dual emission are also reported.

Laboratory studies of stratospheric bromine chemistry: Kinetics of the reactions of bromine monoxide with nitrogen dioxide and atomic oxygen

NASA Astrophysics Data System (ADS)

Thorn, Robert Peyton

A laser flash photolysis - long path absorption - technique has been employed to study the kinetics of the reaction BrO+NO2+M(k(sub 16)) yields products as a function of temperature (248-346 K), pressure (16-800 Torr), and buffer gas identity (N2, CF4). 351 nm photolysis of NO2/Br2/N2 mixtures generated BrO. The BrO decay in the presence of excess NO2 was followed by UV absorption at 338.3 nm. The reaction is in the falloff regime between third and second order over the entire range of conditions investigated. This is the first study where temperature dependent measurements of k(sub 16)(P,T) have been reported at pressures greater than 12 Torr; hence, these results help constrain choices of k(sub 16)(P,T) for use in modeling stratospheric BrO(x) chemistry. The kinetics of the important stratospheric reaction BrO+O(P-3)(k(sub 14)) yields Br+O2 in N2 buffer gas have been studied as a function of temperature (233-328 K) and pressure (25-150 Torr) using a novel dual laser flash photolysis/long path absorption/resonance fluorescence technique. 248 nm pulsed laser photolysis of Br2/O3/N2 mixtures produces O atoms in excess over Br2. After a delay sufficient for BrO to be generated, a 532 nm laser pulse photolysis a small fraction of the O3 to generate O(P-3). The decay of O(P-3) in the presence of an excess, known concentration of BrO, as determined by UV absorption at 338.3 nm and by numerical simulation, is then followed by time-resoved atomic resonance fluorescence spectroscopy. The experimental results have shown the reaction kinetics to be independent of pressure, to increase with decreasing temperature, and to be faster than suggested by the only previous (indirect) measurement. The resulting Anhenius expression for k(sub 14)(T) is k(sub 14)(T) = 1.64 x 10(exp -11) exp(263/T) cm(exp 3) molecule(exp-1)s(exp -1). The absolute accuracy of k(sub 14)(T) at any temperature within the range studied is estimated to be +/- 25%. Possible kinetic interferences from production of vibrationally or electronically excited O2 are discussed. The effect of the faster reaction rate coefficients that are reported for the BrO + NO2 + M and BrO + O(P-3) reactions upon bromine partitioning and ozone depletion in the stratosphere is discussed.

Laboratory Studies of Stratospheric Bromine Chemistry: Kinetics of the Reactions of Bromine Monoxide with Nitrogen Dioxide and Atomic Oxygen.

NASA Astrophysics Data System (ADS)

Thorn, Robert Peyton, Jr.

A laser flash photolysis - long path absorption technique has been employed to study the kinetics of the reaction rm BrO + NO_2 + M{k _{16}atopto} products as a function of temperature (248-346 K), pressure (16 -800 Torr), and buffer gas identity (rm N _2,CF_4). 351 nm photolysis of rm NO_2/Br_2/N_2 mixtures generated BrO. The BrO decay in the presence of excess NO_2 was followed by UV absorption at 338.3 nm. The reaction is in the falloff regime between third and second order over the entire range of conditions investigated. This is the first study where temperature dependent measurements of k_{16} (P,T) have been reported at pressures greater than 12 Torr; hence, these results help constrain choices of k_{16}(P,T) for use in modeling stratospheric BrO_{rm x} chemistry. The kinetics of the important stratospheric reaction rm BrO+O(^3P)_sp{to }{k_{14}}Br+O_2 in N_2 buffer gas have been studied as a function of temperature (233-328 K) and pressure (25 -150 Torr) using a novel dual laser flash photolysis/long path absorption/resonance fluorescence technique. 248 nm pulsed laser photolysis of rm Br_2/O _3/N_2 mixtures produces O atoms in excess over Br_2. After a delay sufficient for BrO to be generated, a 532 nm laser pulse photolyses a small fraction of the O_3 to generate O(^3P). The decay of O(^3P) in the presence of an excess, known concentration of BrO, as determined by UV absorption at 338.3 nm and by numerical simulation, is then followed by time-resolved atomic resonance fluorescence spectroscopy. The experimental results have shown the reaction kinetics to be independent of pressure, to increase with decreasing temperature, and to be faster than suggested by the only previous (indirect) measurement. The resulting Anhenius expression for k_{14}(T) is given below.rm k_{14 }(T) = 1.64times 10^{-11} exp (263/T) cm^3 molecule ^{-1} s^{-1} The absolute accuracy of k_{14 }(T) at any temperature within the range studied is estimated to be +/-25%. Possible kinetic interferences from production of vibrationally or electronically excited O_2 are discussed. The effect of the faster reaction rate coefficients that are reported for the rm BrO + NO_2 + M and BrO + O(^3P) reactions upon bromine partitioning and ozone depletion in the stratosphere is discussed.

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

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

Use of side-chain incompatibility for tailoring long-range p/n heterojunctions: photoconductive nanofibers formed by self-assembly of an amphiphilic donor-acceptor dyad consisting of oligothiophene and perylenediimide.

PubMed

Li, Wei-Shi; Saeki, Akinori; Yamamoto, Yohei; Fukushima, Takanori; Seki, Shu; Ishii, Noriyuki; Kato, Kenichi; Takata, Masaki; Aida, Takuzo

2010-07-05

To tailor organic p/n heterojunctions with molecular-level precision, a rational design strategy using side-chain incompatibility of a covalently connected donor-acceptor (D-A) dyad has been successfully carried out. An oligothiophene-perylenediimide dyad, when modified with triethylene glycol side chains at one terminus and dodecyl side chains at the other (2(Amphi)), self-assembles into nanofibers with a long-range D/A heterojunction. In contrast, when the dyad is modified with dodecyl side chains at both termini (2(Lipo)), ill-defined microfibers result. In steady-state measurements using microgap electrodes, a cast film of the nanofiber of 2(Amphi) displays far better photoconducting properties than that of the microfiber of 2(Lipo). Flash-photolysis time-resolved microwave conductivity measurements, in conjunction with transient absorption spectroscopy, clearly indicate that the nanofiber of 2(Amphi) intrinsically allows for better carrier generation and transport properties than the microfibrous assembly of 2(Lipo).

Determination of Calcium in Cereal with Flame Atomic Absorption Spectroscopy: An Experiment for a Quantitative Methods of Analysis Course

ERIC Educational Resources Information Center

Bazzi, Ali; Kreuz, Bette; Fischer, Jeffrey

2004-01-01

An experiment for determination of calcium in cereal using two-increment standard addition method in conjunction with flame atomic absorption spectroscopy (FAAS) is demonstrated. The experiment is intended to introduce students to the principles of atomic absorption spectroscopy giving them hands on experience using quantitative methods of…

Optoelectronic properties of dicyanofluorene-based n-type polymers.

PubMed

Vijayakumar, Chakkooth; Saeki, Akinori; Seki, Shu

2012-08-01

Three new donor-acceptor-type copolymers (P1-P3) consisting of dicyanofluorene as acceptor and various donor moieties were designed and synthesized. Optoelectronic properties were studied in detail by means of UV-visible absorption and fluorescence spectroscopy, cyclic voltammetry, space-charge-limited current (SCLC), flash-photolysis time-resolved microwave conductivity (FP-TRMC), and density functional theory (DFT). All polymers showed strong absorption in the UV-visible region and the absorption maximum undergoes redshift with an increasing number of thiophene units in the polymer backbone. SCLC analysis showed that the electron mobilities of the polymers in the bulk state were 1 to 2 orders higher than that of the corresponding hole mobilities, which indicated the n-type nature of the materials. By using FP-TRMC, the intrapolymer charge-carrier mobility was assessed and compared with the interpolymer mobility obtained by SCLC. The polymers exhibited good electron-accepting properties sufficiently high enough to oxidize the excited states of regioregular poly(3-hexylthiophene) (P3HT (donor)), as evident from the FP-TRMC analysis. The P3 polymer exhibited the highest FP-TRMC transients in the pristine form as well as when blended with P3HT. Use of these polymers as n-type materials in all-polymer organic solar cells was also explored in combination with P3HT. In accordance with the TRMC results, P3 exhibited superior electron-transport and photovoltaic properties to the other two polymers, which is explained by the distribution of the energy levels of the polymers by using DFT calculations. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR Appendix G to Part 50 - Reference Method for the Determination of Lead in Suspended Particulate Matter Collected From...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Absorption Spectroscopy.” Published by Interscience Company, New York, NY (1968). 5. Kirkbright, G. F., and Sargent, M., “Atomic Absorption and Fluorescence Spectroscopy.” Published by Academic Press, New York, NY... County, IL, by Atomic Absorption Spectroscopy.” Envir. Sci. and Tech., 3, 472-475 (1969). 7. “Proposed...

Fermi GBM Observations of Terrestrial Gamma Flashes

NASA Technical Reports Server (NTRS)

Wilson-Hodge, Colleen A.; Briggs, M. S.; Connaughton, V.; Fishman, G. J.; Bhat, P. N.; Paciesas, W. S.; Preece, R. D.; Kippen, R. M.; vonKienlin, A.; Dwyer, J. R.;

Investigation of the evolution of nitrogen defects in flash-lamp-annealed InGaZnO films and their effects on transistor characteristics

NASA Astrophysics Data System (ADS)

Eom, Tae-Yil; Ahn, Chee-Hong; Kang, Jun-Gu; Saad Salman, Muhammad; Lee, Sun-Young; Kim, Yong-Hoon; Lee, Hoo-Jeong; Kang, Chan-Mo; Kang, Chiwon

2018-06-01

In this study, we show the evolution of nitrogen defects during a sol–gel reaction in flash-lamp-annealed InGaZnO (IGZO) films and their effects on the device characteristics of their thin-film transistors (TFTs). The flash lamp annealing (FLA) of the IGZO TFT for 16 s helps achieve a mobility of approximately 7 cm2 V‑1 s‑1. However, further extension of the annealing time results only in drastic increases in carrier concentration and off-current. The X-ray photoelectron spectroscopy (XPS) analysis of the N 1s peak unravels the presence of oxygen-vacancy-associated nitrogen defects and their evolution with annealing time, which is possibly responsible for the increase in carrier concentration.

Hyperspectral photoacoustic spectroscopy of highly-absorbing samples for diagnostic ocular imaging applications

NASA Astrophysics Data System (ADS)

Lim, Hoong-Ta; Murukeshan, Vadakke Matham

2017-01-01

Photoacoustic spectroscopy has been used to measure optical absorption coefficient and the application of tens of wavelength bands in photoacoustic spectroscopy was reported. Using optical methods, absorption-related information is, generally, derived from reflectance or transmittance values. Hence measurement accuracy is limited for highly absorbing samples where the reflectance or transmittance is too low to give reasonable signal-to-noise ratio. In this context, this paper proposes and illustrates a hyperspectral photoacoustic spectroscopy system to measure the absorption-related properties of highly absorbing samples directly. The normalized optical absorption coefficient spectrum of the highly absorbing iris is acquired using an optical absorption coefficient standard. The proposed concepts and the feasibility of the developed diagnostic medical imaging system are demonstrated using fluorescent microsphere suspensions and porcine eyes as test samples.

Direct stimulation of the retina by the method of virtual-quanta for heavy cosmic-ray nuclei

NASA Technical Reports Server (NTRS)

Mcnulty, P. J.; Madey, R.

1972-01-01

The contribution to the frequency of visual sensations induced in the dark-adapted eye by the virtual photon field was calculated, this field is associated with the heavy nuclei that exist in space beyond the geomagnetic field. In order to determine the probability that the virtual photon field induces a light flash, only the portion of the virtual photon spectrum that corresponds to the known frequency dependence of the sensitivity of human rods to visible light was utilized. The results can be expressed as a curve of the mean frequency of light flashes induced by the absorption of at least R virtual photons versus the threshold number R. The contribution to the light flash frequency from the virtual photon field of heavy cosmic ray nuclei is smaller than that from Cerenkov photons. The flux and energy spectra of galactic cosmic ray nuclei helium to iron were used.

Pressure and temperature dependence kinetics study of the NO + BrO yielding NO2 + Br reaction - Implications for stratospheric bromine photochemistry

NASA Technical Reports Server (NTRS)

Watson, R. T.; Sander, S. P.; Yung, Y. L.

1979-01-01

The reactivity of NO with BrO radicals over a wide range of pressure (100-700 torr) and temperature (224-398 K) is investigated using the flash photolysis-ultraviolet absorption technique. The flash photolysis system consists of a high-pressure xenon arc light source, a reaction cell/gas filter/flash lamp combination, and a 216.5 half-meter monochromator/polychromator/spectrography for wavelength selectivity. The details of the reaction and its corresponding Arrhenius expression are identified. The results are compared with previous measurements, and atmospheric implications of the reaction are discussed. The NO + BrO yielding NO2 + Br reaction is shown to be important in controlling the concentration ratios of BrO/Br and BrO/HBr in the stratosphere, but this reaction does not affect the catalytic efficiency of BrOx in ozone destruction.

p/n-Polarity of thiophene oligomers in photovoltaic cells: role of molecular vs. supramolecular properties.

PubMed

Ghosh, Tanwistha; Gopal, Anesh; Saeki, Akinori; Seki, Shu; Nair, Vijayakumar C

2015-04-28

Molecular and supramolecular properties play key roles in the optoelectronic properties and photovoltaic performances of organic materials. In the present work, we show how small changes in the molecular structure affect such properties, which in turn control the intrinsic and fundamental properties such as the p/n-polarity of organic semiconductors in bulk-heterojunction solar cells. Herein, we designed and synthesized two acceptor-donor-acceptor type semiconducting thiophene oligomers end-functionalized with oxazolone/isoxazolone derivatives (OT1 and OT2 respectively). The HOMO-LUMO energy levels of both derivatives were found to be positioned in such a way that they can act as electron acceptors to P3HT and electron donors to PCBM. However, OT1 functions as a donor (with PCBM) and OT2 as an acceptor (with P3HT) in BHJ photovoltaic cells, and their reverse roles results in either no or poor performance of the cells. Detailed studies using UV-vis absorption and fluorescence spectroscopy, time-correlated single photon counting, UV-photoelectron spectroscopy, density functional theory calculations, X-ray diffraction, and thermal gravimetric analysis proved that both molecular and supramolecular properties contributed equally but in a contrasting manner to the abovementioned observation. The obtained results were further validated by flash-photolysis time-resolved microwave conductivity studies which showed an excellent correlation between the structure, property, and device performances of the materials.

The photocurrent, noise and spectral sensitivity of rods of the monkey Macaca fascicularis.

PubMed Central

Baylor, D A; Nunn, B J; Schnapf, J L

1984-01-01

Visual transduction in rods of the cynomolgus monkey, Macaca fascicularis, was studied by recording membrane current from single outer segments projecting from small pieces of retina. Light flashes evoked transient outward-going photocurrents with saturating amplitudes of up to 34 pA. A flash causing twenty to fifty photoisomerizations gave a response of half the saturating amplitude. The response-stimulus relation was of the form 1-e-x where x is flash strength. The response to a dim flash usually had a time to peak of 150-250 ms and resembled the impulse response of a series of six low-pass filters. From the average spectral sensitivity of ten rods the rhodopsin was estimated to have a peak absorption near 491 nm. The spectral sensitivity of the rods was in good agreement with the average human scotopic visibility curve determined by Crawford (1949), when the human curve was corrected for lens absorption and self-screening of rhodopsin. Fluctuations in the photocurrent evoked by dim lights were consistent with a quantal event about 0.7 pA in peak amplitude. A steady light causing about 100 photoisomerizations s-1 reduced the flash sensitivity to half the dark-adapted value. At higher background levels the rod rapidly saturated. These results support the idea that dim background light desensitizes human scotopic vision by a mechanism central to the rod outer segments while scotopic saturation may occur within the outer segments. Recovery of the photocurrent after bright flashes was marked by quantized step-like events. The events had the properties expected if bleached rhodopsin in the disks occasionally caused an abrupt blockage of the dark current over about one-twentieth of the length of the outer segment. It is suggested that superposition of these events after bleaching may contribute to the threshold elevation measured psychophysically. The current in darkness showed random fluctuations which disappeared in bright light. The continuous component of the noise had a variance of about 0.03 pA2 and a power spectrum that fell to half near 3 Hz. A second component, consisting of discrete events resembling single-photon responses, was estimated to occur at a rate of 0.006 s-1. It is suggested that the continuous component of the noise may be removed from scotopic vision by a thresholding operation near the rod output. PMID:6512705

The photocurrent, noise and spectral sensitivity of rods of the monkey Macaca fascicularis.

PubMed

Baylor, D A; Nunn, B J; Schnapf, J L

1984-12-01

Visual transduction in rods of the cynomolgus monkey, Macaca fascicularis, was studied by recording membrane current from single outer segments projecting from small pieces of retina. Light flashes evoked transient outward-going photocurrents with saturating amplitudes of up to 34 pA. A flash causing twenty to fifty photoisomerizations gave a response of half the saturating amplitude. The response-stimulus relation was of the form 1-e-x where x is flash strength. The response to a dim flash usually had a time to peak of 150-250 ms and resembled the impulse response of a series of six low-pass filters. From the average spectral sensitivity of ten rods the rhodopsin was estimated to have a peak absorption near 491 nm. The spectral sensitivity of the rods was in good agreement with the average human scotopic visibility curve determined by Crawford (1949), when the human curve was corrected for lens absorption and self-screening of rhodopsin. Fluctuations in the photocurrent evoked by dim lights were consistent with a quantal event about 0.7 pA in peak amplitude. A steady light causing about 100 photoisomerizations s-1 reduced the flash sensitivity to half the dark-adapted value. At higher background levels the rod rapidly saturated. These results support the idea that dim background light desensitizes human scotopic vision by a mechanism central to the rod outer segments while scotopic saturation may occur within the outer segments. Recovery of the photocurrent after bright flashes was marked by quantized step-like events. The events had the properties expected if bleached rhodopsin in the disks occasionally caused an abrupt blockage of the dark current over about one-twentieth of the length of the outer segment. It is suggested that superposition of these events after bleaching may contribute to the threshold elevation measured psychophysically. The current in darkness showed random fluctuations which disappeared in bright light. The continuous component of the noise had a variance of about 0.03 pA2 and a power spectrum that fell to half near 3 Hz. A second component, consisting of discrete events resembling single-photon responses, was estimated to occur at a rate of 0.006 s-1. It is suggested that the continuous component of the noise may be removed from scotopic vision by a thresholding operation near the rod output.

Temperature dependence of the NO3 absorption spectrum

NASA Technical Reports Server (NTRS)

Sander, Stanley P.

1986-01-01

The absorption spectrum of the gas-phase NO3 radical has been studied between 220 and 700 nm by using both flash photolysis and discharge flow reactors for the production of NO3. In the flash photolysis method, cross sections at the peak of the (0,0) band at 661.9 nm were measured relative to the cross section of ClONO2 at several different wavelengths. From the best current measurements of the ClONO2 spectrum, the NO3 cross section at 661.9 nm was determined to be (2.28 + or 0.34) x 10 to the -17th sq cm/molecule at 298 K. Measurements at 230 K indicated that the cross section increases by a factor of 1.18 at the peak of the (0,0) band. The discharge flow method was used both to obtain absolute cross sections at 661.9 nm and to obtain relative absorption spectra between 300 and 700 nm at 298 and 230 K. A value of (1.83 + or - 0.27) x 10 to the -17th sq cm/molecule was obtained for sigma NO3 at 661.9 nm at 298 K. Upper limits to the NO3 cross sections were also measured between 220 and 260 nm with the discharge flow method.

Excitonic Transitions and Off-resonant Optical Limiting in CdS Quantum Dots Stabilized in a Synthetic Glue Matrix

PubMed Central

2007-01-01

Stable films containing CdS quantum dots of mean size 3.4 nm embedded in a solid host matrix are prepared using a room temperature chemical route of synthesis. CdS/synthetic glue nanocomposites are characterized using high resolution transmission electron microscopy, infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis. Significant blue shift from the bulk absorption edge is observed in optical absorption as well as photoacoustic spectra indicating strong quantum confinement. The exciton transitions are better resolved in photoacoustic spectroscopy compared to optical absorption spectroscopy. We assign the first four bands observed in photoacoustic spectroscopy to 1se–1sh, 1pe–1ph, 1de–1dhand 2pe–2phtransitions using a non interacting particle model. Nonlinear absorption studies are done using z-scan technique with nanosecond pulses in the off resonant regime. The origin of optical limiting is predominantly two photon absorption mechanism.

Force-detected nanoscale absorption spectroscopy in water at room temperature using an optical trap

NASA Astrophysics Data System (ADS)

Parobek, Alexander; Black, Jacob W.; Kamenetska, Maria; Ganim, Ziad

2018-04-01

Measuring absorption spectra of single molecules presents a fundamental challenge for standard transmission-based instruments because of the inherently low signal relative to the large background of the excitation source. Here we demonstrate a new approach for performing absorption spectroscopy in solution using a force measurement to read out optical excitation at the nanoscale. The photoinduced force between model chromophores and an optically trapped gold nanoshell has been measured in water at room temperature. This photoinduced force is characterized as a function of wavelength to yield the force spectrum, which is shown to be correlated to the absorption spectrum for four model systems. The instrument constructed for these measurements combines an optical tweezer with frequency domain absorption spectroscopy over the 400-800 nm range. These measurements provide proof-of-principle experiments for force-detected nanoscale spectroscopies that operate under ambient chemical conditions.

Energy transfer dynamics in strongly inhomogeneous hot-dense-matter systems

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

Stillman, C. R.; Nilson, P. M.; Sefkow, A. B.

Direct measurements of energy transfer across steep density and temperature gradients in a hot-dense-matter system are presented. Hot dense plasma conditions were generated by high-intensity laser irradiation of a thin-foil target containing a buried metal layer. Energy transfer to the layer was measured using picosecond time-resolved x-ray emission spectroscopy. Here, the data show two x-ray flashes in time. Fully explicit, coupled particle-in-cell and collisional-radiative atomic kinetics model predictions reproduce these observations, connecting the two x-ray flashes with staged radial energy transfer within the target.

Energy transfer dynamics in strongly inhomogeneous hot-dense-matter systems

DOE PAGES

Stillman, C. R.; Nilson, P. M.; Sefkow, A. B.; ...

2018-06-25

Direct measurements of energy transfer across steep density and temperature gradients in a hot-dense-matter system are presented. Hot dense plasma conditions were generated by high-intensity laser irradiation of a thin-foil target containing a buried metal layer. Energy transfer to the layer was measured using picosecond time-resolved x-ray emission spectroscopy. Here, the data show two x-ray flashes in time. Fully explicit, coupled particle-in-cell and collisional-radiative atomic kinetics model predictions reproduce these observations, connecting the two x-ray flashes with staged radial energy transfer within the target.

A transmission-grating-modulated pump-probe absorption spectroscopy and demonstration of diffusion dynamics of photoexcited carriers in bulk intrinsic GaAs film.

PubMed

Chen, Ke; Wang, Wenfang; Chen, Jianming; Wen, Jinhui; Lai, Tianshu

2012-02-13

A transmission-grating-modulated time-resolved pump-probe absorption spectroscopy is developed and formularized. The spectroscopy combines normal time-resolved pump-probe absorption spectroscopy with a binary transmission grating, is sensitive to the spatiotemporal evolution of photoinjected carriers, and has extensive applicability in the study of diffusion transport dynamics of photoinjected carriers. This spectroscopy has many advantages over reported optical methods to measure diffusion dynamics, such as simple experimental setup and operation, and high detection sensitivity. The measurement of diffusion dynamics is demonstrated on bulk intrinsic GaAs films. A carrier density dependence of carrier diffusion coefficient is obtained and agrees well with reported results.

UV-VIS absorption spectroscopy: Lambert-Beer reloaded

NASA Astrophysics Data System (ADS)

Mäntele, Werner; Deniz, Erhan

2017-02-01

UV-VIS absorption spectroscopy is used in almost every spectroscopy laboratory for routine analysis or research. All spectroscopists rely on the Lambert-Beer Law but many of them are less aware of its limitations. This tutorial discusses typical problems in routine spectroscopy that come along with technical limitations or careless selection of experimental parameters. Simple rules are provided to avoid these problems.

Non-destructive inspections of illicit drugs in envelope using terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Li, Ning; Shen, Jingling; Lu, Meihong; Jia, Yan; Sun, Jinhai; Liang, Laishun; Shi, Yanning; Xu, Xiaoyu; Zhang, Cunlin

2006-09-01

The absorption spectra of two illicit drugs, methylenedioxyamphetarnine (MDA) and methamphetamine (MA), within and without two conventional envelopes are studied using terahertz time-domain spectroscopy technique. The characteristic absorption spectra of MDA and MA are obtained in the range of 0.2 THz to 2.5 THz. MDA has an obvious absorption peak at 1.41 THz while MA has obvious absorption peaks at 1.23 THz, 1.67 THz, 1.84 THz and 2.43 THz. We find that the absorption peaks of MDA and MA within the envelopes are almost the same as those without the envelopes respectively although the two envelopes have some different absorption in THz waveband. This result indicates that the type of illicit drugs in envelopes can be determined by identifying their characteristic absorption peaks, and THz time-domain spectroscopy is one of the most powerful candidates for illicit drugs inspection.

Extended X-ray Absorption Fine Structure Study of Bond Constraints in Ge-Sb-Te Alloys

DTIC Science & Technology

2011-02-07

Ray Absorption Spectroscopy, or EXAFS. Using the spectroscopic capabilities provided by the MCAT line at the Advanced Photon Source at Argonne...Absorption Spectroscopy, or EXAFS. Using the spectroscopic capabilities provided by the MCAT line at the Advanced Photon Source at Argonne National

Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

Rose bengal in poly(2-hydroxyethyl methacrylate) thin films: self-quenching by photoactive energy traps

NASA Astrophysics Data System (ADS)

Ezquerra Riega, Sergio D.; Rodríguez, Hernán B.; San Román, Enrique

2017-03-01

The effect of dye concentration on the fluorescence,ΦF, and singlet molecular oxygen,ΦΔ, quantum yields of rose bengal loaded poly(2-hydroxyethyl methacrylate) thin films (∼200 nm thick) was investigated, with the aim of understanding the effect of molecular interactions on the photophysical properties of dyes in crowded constrained environments. Films were characterized by absorption and fluorescence spectroscopy, singlet molecular oxygen (1O2) production was quantified using a chemical monitor, and the triplet decay was determined by laser flash-photolysis. For the monomeric dilute dye, ΦF = 0.05 ± 0.01 and ΦΔ = 0.76 ± 0.14. The effect of humidity and the photostability of the dye were also investigated. Spectral changes in absorption and fluorescence in excess of 0.05 M and concentration self-quenching after 0.01 M are interpreted in the context of a quenching radius model. Calculations of energy migration and trapping rates were performed assuming random distribution of the dye. Best fits of fluorescence quantum yields with concentration are obtained in the whole concentration range with a quenching radius r Q = 1.5 nm, in the order of molecular dimensions. Agreement is obtained only if dimeric traps are considered photoactive, with an observed fluorescence quantum yield ratio ΦF,trap/ΦF,monomer ≈ 0.35. Fluorescent traps are capable of yielding triplet states and 1O2. Results show that the excited state generation efficiency, calculated as the product between the absorption factor and the fluorescence quantum yield, is maximized at around 0.15 M, a very high concentration for random dye distributions. Relevant information for the design of photoactive dyed coatings is provided.

Using high spectral resolution spectrophotometry to study broad mineral absorption features on Mars

NASA Technical Reports Server (NTRS)

Blaney, D. L.; Crisp, D.

1993-01-01

Traditionally telescopic measurements of mineralogic absorption features have been made using relatively low to moderate (R=30-300) spectral resolution. Mineralogic absorption features tend to be broad so high resolution spectroscopy (R greater than 10,000) does not provide significant additional compositional information. Low to moderate resolution spectroscopy allows an observer to obtain data over a wide wavelength range (hundreds to thousands of wavenumbers) compared to the several wavenumber intervals that are collected using high resolution spectrometers. However, spectrophotometry at high resolution has major advantages over lower resolution spectroscopy in situations that are applicable to studies of the Martian surface, i.e., at wavelengths where relatively weak surface absorption features and atmospheric gas absorption features both occur.

Pilot plant test of the advanced flash stripper for CO2 capture.

PubMed

Lin, Yu-Jeng; Chen, Eric; Rochelle, Gary T

2016-10-20

Alternative stripping processes have been proposed to reduce energy use for CO 2 capture, but only a few have been applied to pilot-scale experiments. This paper presents the first pilot plant test results of one of the most promising stripper configurations, the advanced flash stripper with cold and warm rich solvent bypass. The campaign using aqueous piperazine was carried out at UT Austin in 2015. The advanced flash stripper improves the heat duty by over 25% compared to previous campaigns using the two-stage flash, achieving 2.1 GJ per tonne CO 2 of heat duty and 32 kJ mol -1 CO 2 of total equivalent work. The bypass control strategy proposed minimized the heat duty. The test successfully demonstrated the remarkable energy performance and the operability of this advanced system. An Aspen Plus® model was validated using the pilot plant data and used to explore optimum operating and design conditions. The irreversibility analysis showed that the pilot plant performance has attained 50% thermodynamic efficiency and further energy improvement should focus on the absorber and the cross exchanger by increasing absorption rate and solvent capacity.

Flash x-ray radiography of argon jets in ambient air

NASA Astrophysics Data System (ADS)

Geiswiller, J.; Robert, E.; Huré, L.; Cachoncinlle, C.; Viladrosa, R.; Pouvesle, J. M.

1998-09-01

This paper describes the development and application of a soft x-ray flash radiography technique. A very compact soft x-ray flash source has been specially designed for these studies. The table-top x-ray source developed in this work emits strong doses, up to one roentgen at the output window, of x-ray photons, with most of them in the characteristic lines of the anode material (photon energy in the energy range 5-10 keV), in pulse of 20 ns FWHM with an x-ray emission zone smaller than 0957-0233/9/9/024/img1. All these characteristics make this source attractive for the x-ray radiography of high-speed phenomena, down to ten nanoseconds duration and/or for the media presenting weak absorption for the harder x-ray photons emitted by more conventional flash x-ray systems. Argon streams in ambient air were chosen as a typical case to enlighten the potentialities of this method. Single-shot radiographs of such an argon jet through rectangular nozzles were obtained. No attempt of quantitative measurement of local density in the argon stream has yet been performed, only the qualitative structure of the jet has been investigated. Nevertheless, these preliminary results enable us to state that the diagnostics of gaseous or plasma media, even at rather low pressures, can proceed using soft x-ray flash radiography.

Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene/Guanine Interface - A Proposal for High Mobility, Organic Graphene Field Effect Transistors

DTIC Science & Technology

2015-07-01

AFRL-AFOSR-UK-TR-2015-0034 Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine...Interface – A Proposal for High Mobility, Organic Graphene Field Effect Transistors Eva Campo BANGOR UNIVERSITY COLLEGE ROAD BANGOR...April 2015 4. TITLE AND SUBTITLE Studies by Near Edge X-ray Absorption Spectroscopies of Bonding Dynamics at the Graphene /Guanine Interface - A

Multiplexed absorption tomography with calibration-free wavelength modulation spectroscopy

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

Cai, Weiwei; Kaminski, Clemens F., E-mail: cfk23@cam.ac.uk

2014-04-14

We propose a multiplexed absorption tomography technique, which uses calibration-free wavelength modulation spectroscopy with tunable semiconductor lasers for the simultaneous imaging of temperature and species concentration in harsh combustion environments. Compared with the commonly used direct absorption spectroscopy (DAS) counterpart, the present variant enjoys better signal-to-noise ratios and requires no baseline fitting, a particularly desirable feature for high-pressure applications, where adjacent absorption features overlap and interfere severely. We present proof-of-concept numerical demonstrations of the technique using realistic phantom models of harsh combustion environments and prove that the proposed techniques outperform currently available tomography techniques based on DAS.

[The study of CO2 cavity enhanced absorption and highly sensitive absorption spectroscopy].

PubMed

Pei, Shi-Xin; Gao, Xiao-Ming; Cui, Fen-Ping; Huang, Wei; Shao, Jie; Fan, Hong; Zhang, Wei-Jun

2005-12-01

Cavity enhanced absorption spectroscopy (CEAS) is a new spectral technology that is based on the cavity ring down absorption spectroscopy. In the present paper, a DFB encapsulation narrow line width tunable diode laser (TDL) was used as the light source. At the center output, the TDL radiation wavelength was 1.573 microm, and an optical cavity, which consisted of two high reflectivity mirrors (near 1.573 microm, the mirror reflectivity was about 0.994%), was used as a sample cell. A wavemeter was used to record the accurate frequency of the laser radiation. In the experiment, the method of scanning the optical cavity to change the cavity mode was used, when the laser frequency was coincident with one of the cavity mode; the laser radiation was coupled into the optical cavity and the detector could receive the light signals that escaped the optical cavity. As a result, the absorption spectrum of carbon dioxide weak absorption at low pressure was obtained with an absorption intensity of 1.816 x 10(-23) cm(-1) x (molecule x cm(-2)(-1) in a sample cell with a length of only 33.5 cm. An absorption sensitivity of about 3.62 x 10(-7) cm(-1) has been achieved. The experiment result indicated that the cavity enhanced absorption spectroscopy has the advantage of high sensivity, simple experimental setup, and easy operation.

Absorption and quasiguided mode analysis of organic solar cells with photonic crystal photoactive layers.

PubMed

Tumbleston, John R; Ko, Doo-Hyun; Samulski, Edward T; Lopez, Rene

2009-04-27

We analyze optical absorption enhancements and quasiguided mode properties of organic solar cells with highly ordered nanostructured photoactive layers comprised of the bulk heterojunction blend, poly-3-hexylthiophene/[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) and a low index of refraction conducting material (LICM). This photonic crystal geometry is capable of enhancing spectral absorption by approximately 17% in part due to the excitation of quasiguided modes near the band edge of P3HT:PCBM. A nanostructure thickness between 200 nm and 300 nm is determined to be optimal, while the LICM must have an index of refraction approximately 0.3 lower than P3HT:PCBM to produce absorption enhancements. Quasiguided modes that differ in lifetime by an order of magnitude are also identified and yield absorption that is concentrated in the P3HT:PCBM flash layer.

Kinetic and thermochemical studies of the ClO + ClO + M ↔ Cl2O2 + M reaction

NASA Astrophysics Data System (ADS)

Ferracci, V.; Rowley, D. M.

2009-12-01

Chlorine monoxide (ClO) radicals play a crucial role in polar ozone destruction events and the ClO dimer cycle has been identified as one of the most effective ozone-depleting catalytic cycles operating in the polar winter. A recent paper by von Hobe et al.1 highlighted significant inconsistencies between laboratory results, theoretical calculations and field observations concerning the ClO dimer ozone destruction cycle. This work has investigated the temperature dependence of the equilibrium constant of one of the key reactions in this cycle, ClO + ClO + M ↔ Cl2O2 + M (1, -1), by means of laser flash photolysis coupled with time-resolved UV absorption spectroscopy. ClO radicals were generated via laser flash photolysis of Cl2/Cl2O mixtures in synthetic air. The concentration of radicals was monitored via UV absorption spectroscopy: the use of a Charge Coupled Device (CCD) detector allowed time resolution over a broad range of wavelengths. The equilibrium constant Keq was determined as the ratio of the rate constants of the forward and reverse reaction (1, -1) over the T range 256 - 312 K. Second Law and Third Law analytical methods were employed to determine the standard enthalpy and entropy changes of reaction 1, ΔrH° and ΔrS°, from the measured equilibrium constants. The values obtained from the Second Law analysis (ΔrH° = - 80.8 ± 2.2 kJ mol-1; ΔrS° = - 168.4 ± 7.9 J K-1 mol-1) are in good agreement with previous work 2 but greater in magnitude than current NASA recommendations 3. It was also found that, under typical laboratory conditions employed in this work, [ClO] decay exhibits pure second order kinetics at T ≤ 250 K. A higher rate constant for the ClO recombination reaction (1) was also observed in this work (compared to the NASA evaluation 3), implying a higher Keq and a different partitioning between ClO and Cl2O2, shifting towards the dimer. 1. M. Von Hobe, R. J. Salawitch, T. Canty, H. Keller-Rudek, G. K. Moortgat, J.-U. Grooss, R. Müller, F. Stroh, Atmospheric Chemistry and Physics, 2007, 7, 3055 2. S. L. Nickolaisen, R. R. Friedl, S. P. Sander, Journal of Physical Chemistry, 1994, 98, 155 3. S. P. Sander, R. R. Friedl, D. M. Golden, M. J. Kurylo, R. E. Huie, V. L. Orkin, G. K. Moortgat, A. R. Ravishankara, C. E. Kolb, M. J. Molina, B. J. Finlayson-Pitts, Chemical Kinetics and Photochemical Data for use in Atmospheric Studies, Evaluation No. 14, JPL Publication 02-25, NASA Jet Propulsion Laboratory, Pasadena CA, 2003

Alternative stripper configurations for CO{sub 2} capture by aqueous amines

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

Oyenekan, B.A.; Rochelle, G.T.

2007-12-15

Aqueous absorption/stripping is a promising technology for the capture of CO{sub 2} from existing or new coal-fired power plants. Four new stripper configurations (matrix, internal exchange, flashing feed, and multipressure with split feed) have been evaluated with seven model solvents that approximate the thermodynamic and rate properties of 7m (30 wt %) monoethanolamine (MEA), potassium carbonate promoted bypiperazine (PZ), promoted MEA, methyldiethanolamine (MDEA) promoted by PZ, and hindered amines. The results show that solvents with high heats of absorption (MEA, MEA/PZ) favor operation at normal pressure. The relative performance of the alternative configurations is matrix > internal exchange > multipressuremore » with split feed > flashing feed. MEA/PZ and MDEA/PZ are attractive alternatives to 7m MEA. The best solvent and process configuration, matrix with MDEA/PZ, offers 22 and 15% energy savings over the baseline and improved baseline, respectively,with stripping and compression to 10 MPa. The energy requirement for stripping and compression to 10 MPa is about 20% of the power output from a 500 MW power plant with 90% CO{sub 2} removal.« less

Incipient fire detection system

DOEpatents

Brooks, Jr., William K.

1999-01-01

A method and apparatus for an incipient fire detection system that receives gaseous samples and measures the light absorption spectrum of the mixture of gases evolving from heated combustibles includes a detector for receiving gaseous samples and subjecting the samples to spectroscopy and determining wavelengths of absorption of the gaseous samples. The wavelengths of absorption of the gaseous samples are compared to predetermined absorption wavelengths. A warning signal is generated whenever the wavelengths of absorption of the gaseous samples correspond to the predetermined absorption wavelengths. The method includes receiving gaseous samples, subjecting the samples to light spectroscopy, determining wavelengths of absorption of the gaseous samples, comparing the wavelengths of absorption of the gaseous samples to predetermined absorption wavelengths and generating a warning signal whenever the wavelengths of absorption of the gaseous samples correspond to the predetermined absorption wavelengths. In an alternate embodiment, the apparatus includes a series of channels fluidically connected to a plurality of remote locations. A pump is connected to the channels for drawing gaseous samples into the channels. A detector is connected to the channels for receiving the drawn gaseous samples and subjecting the samples to spectroscopy. The wavelengths of absorption are determined and compared to predetermined absorption wavelengths is provided. A warning signal is generated whenever the wavelengths correspond.

Trace gas absorption spectroscopy using laser difference-frequency spectrometer for environmental application

NASA Technical Reports Server (NTRS)

Chen, W.; Cazier, F.; Boucher, D.; Tittel, F. K.; Davies, P. B.

2001-01-01

A widely tunable infrared spectrometer based on difference frequency generation (DFG) has been developed for organic trace gas detection by laser absorption spectroscopy. On-line measurements of concentration of various hydrocarbons, such as acetylene, benzene, and ethylene, were investigated using high-resolution DFG trace gas spectroscopy for highly sensitive detection.

UV-VIS absorption spectroscopy: Lambert-Beer reloaded.

PubMed

Mäntele, Werner; Deniz, Erhan

2017-02-15

UV-VIS absorption spectroscopy is used in almost every spectroscopy laboratory for routine analysis or research. All spectroscopists rely on the Lambert-Beer Law but many of them are less aware of its limitations. This tutorial discusses typical problems in routine spectroscopy that come along with technical limitations or careless selection of experimental parameters. Simple rules are provided to avoid these problems. Copyright © 2016 Elsevier B.V. All rights reserved.

Absorption spectroscopy at the ultimate quantum limit from single-photon states

NASA Astrophysics Data System (ADS)

Whittaker, R.; Erven, C.; Neville, A.; Berry, M.; O'Brien, J. L.; Cable, H.; Matthews, J. C. F.

2017-02-01

Absorption spectroscopy is routinely used to characterise chemical and biological samples. For the state-of-the-art in laser absorption spectroscopy, precision is theoretically limited by shot-noise due to the fundamental Poisson-distribution of photon number in laser radiation. In practice, the shot-noise limit can only be achieved when all other sources of noise are eliminated. Here, we use wavelength-correlated and tuneable photon pairs to demonstrate how absorption spectroscopy can be performed with precision beyond the shot-noise limit and near the ultimate quantum limit by using the optimal probe for absorption measurement—single photons. We present a practically realisable scheme, which we characterise both the precision and accuracy of by measuring the response of a control feature. We demonstrate that the technique can successfully probe liquid samples and using two spectrally similar types of haemoglobin we show that obtaining a given precision in resolution requires fewer heralded single probe photons compared to using an idealised laser.

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

DOE PAGES

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.; ...

2017-02-20

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

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

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

[The Research for Trace Ammonia Escape Monitoring System Based on Tunable Diode Laser Absorption Spectroscopy].

PubMed

Zhang, Li-fang; Wang, Fei; Yu, Li-bin; Yan, Jian-hua; Cen, Ke-fa

2015-06-01

In order to on-line measure the trace ammonia slip of the commercial power plant in the future, this research seeks to measure the trace ammonia by using tunable diode laser absorption spectroscopy under ambient temperature and pressure, and at different temperatures, and the measuring temperature is about 650 K in the power plant. In recent years lasers have become commercially available in the near-infrared where the transitions are much stronger, and ammonia's spectroscopy is pretty complicated and the overlapping lines are difficult to resolve. A group of ammonia transitions near 4 433.5 cm(-1) in the v2 +v3 combination band have been thoroughly selected for detecting lower concentration by analyzing its absorption characteristic and considering other absorption interference in combustion gases where H2O and CO2 mole fraction are very large. To illustrate the potential for NH3 concentration measurements, predictions for NH3, H2O and CO2 are simultaneously simulated, NH3 absorption lines near 4 433.5 cm(-1) wavelength meet weaker H2O absorption than the commercial NH3 lines, and there is almost no CO2 absorption, all the parameters are based on the HITRAN database, and an improved detection limit was obtained for interference-free NH3 monitoring, this 2.25 μm band has line strengths several times larger than absorption lines in the 1.53 μm band which was often used by NH3 sensors for emission monitoring and analyzing. The measurement system was developed with a new Herriott cell and a heated gas cell realizing fast absorption measurements of high resolution, and combined with direct absorption and wavelenguh modulation based on tunable diode laser absorption spectroscopy at different temperatures. The lorentzian line shape is dominant at ambient temperature and pressure, and the estimated detectivity is approximately 0.225 x 10(-6) (SNR = 1) for the directed absorption spectroscopy, assuming a noise-equivalent absorbance of 1 x 10(-4). The heated cell experiments with controlled the temperature were performed to validate the sensing strategy. Here the Wavelength Modulation Spectroscopy (WMS) strategy was usually used to measure lower gas concentration for high noise immunity to the non-absorption transmission losses. The great agreement 2f signal with the calibrated concentration is within the uncertainty at different temperatures by using simple digital signal processing such as multiple averages, wavelet analysis and so on. The denoise processing has a great advantage in application and implementation over other noise suppression techniques. The result provided a good basis for trace ammonia escape detection based on tunable diode laser absorption spectroscopy.

Surface plasmon resonance near-infrared spectroscopy.

PubMed

Ikehata, Akifumi; Itoh, Tamitake; Ozaki, Yukihiro

2004-11-01

Near-infrared (NIR) spectroscopy is ill-suited to microanalysis because of its low absorptivity. We have developed a highly sensitive detection method for NIR spectroscopy based on absorption-sensitive surface plasmon resonance (SPR). The newly named SPR-NIR spectroscopy, which may open the way for NIR spectroscopy in microanalysis and surface science, is realized by an attachment of the Kretschmann configuration equipped with a mechanism for fine angular adjustment of incident light. The angular sweep of incident light enables us to make a tuning of a SPR peak for an absorption band of sample medium. From the dependences of wavelength, incident angle, and thickness of a gold film on the intensity of the SPR peak, it has been found that the absorbance can be enhanced by approximately 100 times compared with the absorbance obtained without the gold film under optimum conditions. This article reports the details of the experimental setup and the characteristics of absorption-sensitive SPR in the NIR region, together with some experimental results obtained by using it.

Simultaneous optimization method for absorption spectroscopy postprocessing.

PubMed

Simms, Jean M; An, Xinliang; Brittelle, Mack S; Ramesh, Varun; Ghandhi, Jaal B; Sanders, Scott T

2015-05-10

A simultaneous optimization method is proposed for absorption spectroscopy postprocessing. This method is particularly useful for thermometry measurements based on congested spectra, as commonly encountered in combustion applications of H2O absorption spectroscopy. A comparison test demonstrated that the simultaneous optimization method had greater accuracy, greater precision, and was more user-independent than the common step-wise postprocessing method previously used by the authors. The simultaneous optimization method was also used to process experimental data from an environmental chamber and a constant volume combustion chamber, producing results with errors on the order of only 1%.

OH absorption spectroscopy in a flame using spatial heterodyne spectroscopy

NASA Astrophysics Data System (ADS)

Bartula, Renata J.; Ghandhi, Jaal B.; Sanders, Scott T.; Mierkiewicz, Edwin J.; Roesler, Fred L.; Harlander, John M.

2007-12-01

We demonstrate measurements of OH absorption spectra in the post-flame zone of a McKenna burner using spatial heterodyne spectroscopy (SHS). SHS permits high-resolution, high-throughput measurements. In this case the spectra span ~308-310 nm with a resolution of 0.03 nm, even though an extended source (extent of ~2×10-7 m2 rad2) was used. The high spectral resolution is important for interpreting spectra when multiple absorbers are present for inferring accurate gas temperatures from measured spectra and for monitoring weak absorbers. The present measurement paves the way for absorption spectroscopy by SHS in practical combustion devices, such as reciprocating and gas-turbine engines.

Fourier Transform Infrared Absorption Spectroscopy of Gas-Phase and Surface Reaction Products during Si Etching in Inductively Coupled Cl2 Plasmas

NASA Astrophysics Data System (ADS)

Miyata, Hiroki; Tsuda, Hirotaka; Fukushima, Daisuke; Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

2011-10-01

A better understanding of plasma-surface interactions is indispensable during etching, including the behavior of reaction or etch products, because the products on surfaces and in the plasma are important in passivation layer formation through their redeposition on surfaces. In practice, the nanometer-scale control of plasma etching would still rely largely on such passivation layer formation as well as ion-enhanced etching on feature surfaces. This paper presents in situ Fourier transform infrared (FTIR) absorption spectroscopy of gas-phase and surface reaction products during inductively coupled plasma (ICP) etching of Si in Cl2. The observation was made in the gas phase by transmission absorption spectroscopy (TAS), and also on the substrate surface by reflection absorption spectroscopy (RAS). The quantum chemical calculation was also made of the vibrational frequency of silicon chloride molecules. The deconvolution of the TAS spectrum revealed absorption features of Si2Cl6 and SiClx (x = 1-3) as well as SiCl4, while that of the RAS spectrum revealed relatively increased absorption features of unsaturated silicon chlorides. A different behavior was also observed in bias power dependence between the TAS and RAS spectra.

Fluorescence Lyman-Alpha Stratospheric Hygrometer (FLASH): application on meteorological balloons, long duration balloons and unmanned aerial vehicles.

NASA Astrophysics Data System (ADS)

Lykov, Alexey; Khaykin, Sergey; Yushkov, Vladimir; Efremov, Denis; Formanyuk, Ivan; Astakhov, Valeriy

The FLASH instrument is based on the fluorescent method, which uses H2O molecules photodissociation at a wavelength lambda=121.6 nm (Lalpha - hydrogen emission) followed by the measurement of the fluorescence of excited OH radicals. The source of Lyman-alpha radiation is a hydrogen discharge lamp while the detector of OH fluorescence at 308 -316 nm is a photomultiplier run in photon counting mode. The intensity of the fluorescent light as well as the instrument readings is directly proportional to the water vapor mixing ratio under stratospheric conditions with negligible oxygen absorption. Initially designed for rocket-borne application, FLASH has evolved into a light-weight balloon sonde (FLASH-B) for measurements in the upper troposphere and stratosphere on board meteorological and small plastic balloons. This configuration has been used in over 100 soundings at numerous tropical mid-latitude and polar locations within various international field campaigns. An airborne version of FLASH instrument is successfully utilized onboard stratospheric M55-Geophysica aircraft and tropospheric airborne laboratory YAK42-Roshydromet. The hygrometer was modified for application onboard stratospheric long-duration balloons (FLASH-LDB version). This version was successfully used onboard CNES super-pressure balloon launched from SSC Esrange in March 2007 and flown during 10 days. Special design for polar long duration balloon PoGOLite was created for testing work during polar day in June 2013. Installation and measurement peculiarities as well as observational results are presented. Observations of water vapour using FLASH-B instrument, being of high quality are rather costly as the payload recovery is often complicated and most of the time impossible. Following the goal to find a cost-efficient solution, FLASH was adapted for use onboard Unmanned Aerial Vehicles (UAV). This solution was only possible thanks to compactness and light-weight (0.5 kg) of FLASH instrument. The hygrometer was installed at the nose of a small GPS-controlled glider, which was lifted by a meteorological balloon into the stratosphere and released by a remote command. GPS-based flight control guides and lands the UAV at the launch point thereby allowing multiple usage of its payload. Another sounding platform allowing for multiple usage of the FLASH instrument is a GPS-guided paraglide. The results of measurements acquired in the test flights using different types of balloon-lifted UAVs are presented.

Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor

NASA Astrophysics Data System (ADS)

Porterfield, Jessica P.; Nguyen, Thanh Lam; Baraban, Joshua H.; Buckingham, Grant; Troy, Tyler; Kostko, Oleg; Ahmed, Musahid; Stanton, John F.; Daily, John W.; Ellison, Barney

2016-06-01

he thermal decomposition of cyclohexanone (C_6H10=O) has been studied in a set of flash-pyrolysis micro-reactors. Samples of C_6H10=O were first observed to decompose at 1200 K. Short residence times of 100 μsec and dilution of samples (<0.1%) isolate unimolecular decomposition. Products were identified by tunable VUV photoionization mass spectroscopy, photoionization appearance thresholds, and complementary matrix infrared absorption spectroscopy. Thermal cracking of cyclohexanone appeared to result from a variety of competing pathways pictured to the right. Isomerization of cyclohexanone to the enol, cyclohexen-1-ol (C_6H_9OH), is followed by retro-Diels-Alder cleavage to CH_2=CH_2 and CH_2=C(OH)-CH=CH_2. Further isomerization of CH_2=C(OH)CH=CH_2 to methyl vinyl ketone (CH_3COCH=CH_2, MVK) was also observed. Photoionization spectra identified both enols, C_6H_9OH and CH=C(OH)CH=CH_2, and the ionization threshold of C_6H_9OH was measured to be 8.2 ± 0.1 eV. At 1200 K, the products of cyclohexanone pyrolysis were found to be: C_6H_9OH, CH_2=C(OH)CH=CH_2, MVK, CH_2CHCH_2, CO, CH_2=C=O, CH_3, CH_2=C=CH_2, CH_2=CH-CH=CH_2, CH_2=CHCH_2CH_3, CH_2=CH_2, and HCCH.

New Observational Evidence of Flash Mixing on the White Dwarf Cooling Curve

NASA Technical Reports Server (NTRS)

Brown, T. M.; Lanz, T.; Sweigart, A. V.; Cracraft, Misty; Hubeny, Ivan; Landsman, W. B.

2011-01-01

Blue hook stars are a class of subluminous extreme horizontal branch stars that were discovered in UV images of the massive globular clusters w Cen and NGC 2808. These stars occupy a region of the HR diagram that is unexplained by canonical stellar evolution theory. Using new theoretical evolutionary and atmospheric models, we have shown that the blue hook stars are very likely the progeny of stars that undergo extensive internal mixing during a late helium-core flash on the white dwarf cooling curve. This "flash mixing" produces hotter-than-normal EHB stars with atmospheres significantly enhanced in helium and carbon. The larger bolometric correction, combined with the decrease in hydrogen opacity, makes these stars appear sub luminous in the optical and UV. Flash mixing is more likely to occur in stars born with a high helium abundance, due to their lower mass at the main sequence turnoff. For this reason, the phenomenon is more common in those massive globular clusters that show evidence for secondary populations enhanced in helium. However, a high helium abundance does not, by itself, explain the presence of blue hook stars in massive globular clusters. Here, we present new observational evidence for flash mixing, using recent HST observations. These include UV color-magnitude diagrams of six massive globular clusters and far-UV spectroscopy of hot subdwarfs in one of these clusters (NGC 2808).

Structural, microstructural and magnetic evolution in cryo milled carbon doped MnAl.

PubMed

Fang, Hailiang; Cedervall, Johan; Hedlund, Daniel; Shafeie, Samrand; Deledda, Stefano; Olsson, Fredrik; von Fieandt, Linus; Bednarcik, Jozef; Svedlindh, Peter; Gunnarsson, Klas; Sahlberg, Martin

2018-02-06

The low cost, rare earth free τ-phase of MnAl has high potential to partially replace bonded Nd 2 Fe 14 B rare earth permanent magnets. However, the τ-phase is metastable and it is experimentally difficult to obtain powders suitable for the permanent magnet alignment process, which requires the fine powders to have an appropriate microstructure and high τ-phase purity. In this work, a new method to make high purity τ-phase fine powders is presented. A high purity τ-phase Mn 0.55 Al 0.45 C 0.02 alloy was synthesized by the drop synthesis method. The drop synthesized material was subjected to cryo milling and  followed by a flash heating process. The crystal structure and microstructure of the drop synthesized, cryo milled and flash heated samples were studied by X-ray in situ powder diffraction, scanning electron microscopy, X-ray energy dispersive spectroscopy and electron backscatter diffraction. Magnetic properties and magnetic structure of the drop synthesized, cryo milled, flash heated  samples were characterized by magnetometry and neutron powder diffraction, respectively. The results reveal that the 2 and 4 hours cryo milled and flash heated samples both exhibit high τ-phase purity and micron-sized round particle shapes. Moreover, the flash heated samples display high saturation magnetization as well as increased coercivity.

The DTIC Review: Volume 2, Number 4, Surviving Chemical and Biological Warfare

DTIC Science & Technology

1996-12-01

CHROMATOGRAPHIC ANALYSIS, NUCLEAR MAGNETIC RESONANCE, INFRARED SPECTROSCOPY , ARMY RESEARCH, DEGRADATION, VERIFICATION, MASS SPECTROSCOPY , LIQUID... mycotoxins . Such materials are not attractive as weapons of mass destruction however, as large amounts are required to produce lethal effects. In...VERIFICATION, ATOMIC ABSORPTION SPECTROSCOPY , ATOMIC ABSORPTION. AL The DTIC Review Defense Technical Information Center AD-A285 242 AD-A283 754 EDGEWOOO

Hollow waveguide cavity ringdown spectroscopy

NASA Technical Reports Server (NTRS)

Dreyer, Chris (Inventor); Mungas, Greg S. (Inventor)

2012-01-01

Laser light is confined in a hollow waveguide between two highly reflective mirrors. This waveguide cavity is used to conduct Cavity Ringdown Absorption Spectroscopy of loss mechanisms in the cavity including absorption or scattering by gases, liquid, solids, and/or optical elements.

Flameless Atomic Absorption Spectroscopy: Effects of Nitrates and Sulfates.

DTIC Science & Technology

1980-05-01

ATTACHED DDJ~P 1413 EDITION 01 INO, 6 5 IabSoLEr J UjN!LbAa~ A- i SELU 0 IONOF I tG 651 J Flameless Atomic Absorption Spectroscopy: Effects of Nitrates...analytical techniques, flameless atomic absorption is subject to matrix or interference effects. Upon heating, nitrate and sulfate salts decompose to...Eklund and J.E. Smith, Anal Chem, 51, 1205 (1979) R.H. Eklund and J.A. Holcombe, Anal Chim. Acta, 109, 97 (1979) FLAMELESS ATOMIC ABSORPTION

Infrared heterodyne spectroscopy of atmospheric ozone

NASA Technical Reports Server (NTRS)

Frerking, M. A.; Muehlner, D. J.

1977-01-01

The absorption spectrum of atmospheric ozone is measured within a 1/cm region at 1100/cm, using an IR heterodyne detector (spectrometer with CO2 local oscillator) developed for astronomical work. Absorption spectra obtained by passing radiation from the tunable diode laser through an absorption cell, heterodyne spectra of atmospheric ozone, and a predicted atmospheric spectrum are compared. Water vapor absorbing in the region of interest (1100/cm) is also considered. Preliminary results encourage the use of diode laser local oscillators in tunable heterodyne detector systems for spectroscopy of atmospheric ozone and remote high-resolution spectroscopy of atmospheric constituents and pollutants.

Optical remote measurement of toxic gases

NASA Technical Reports Server (NTRS)

Grant, W. B.; Kagann, R. H.; McClenny, W. A.

1992-01-01

Enactment of the Clean Air Act Amendments (CAAA) of 1990 has resulted in increased ambient air monitoring needs for industry, some of which may be met efficiently using open-path optical remote sensing techniques. These techniques include Fourier transform spectroscopy, differential optical absorption spectroscopy, laser long-path absorption, differential absorption lidar, and gas cell correlation spectroscopy. With this regulatory impetus, it is an opportune time to consider applying these technologies to the remote and/or path-averaged measurement and monitoring of toxic gases covered by the CAAA. This article reviews the optical remote sensing technology and literature for that application.

Improving Optical Absorption Models for Harsh Planetary Atmospheres: Laboratory Spectroscopy at Venus Surface Conditions

NASA Astrophysics Data System (ADS)

Cole, Ryan Kenneth; Schroeder, Paul James; Diego Draper, Anthony; Rieker, Gregory Brian

2018-06-01

Modelling absorption spectra in high pressure, high temperature environments is complicated by the increased relevance of higher order collisional phenomena (e.g. line mixing, collision-induced absorption, finite duration of collisions) that alter the spectral lineshape. Accurate reference spectroscopy in these conditions is of interest for mineralogy and radiative transfer studies of Venus as well as other dense planetary atmospheres. We present a new, high pressure, high temperature absorption spectroscopy facility at the University of Colorado Boulder. This facility employs a dual frequency comb absorption spectrometer to record broadband (500nm), high resolution (~0.002nm) spectra in conditions comparable to the Venus surface (730K, 90bar). Measurements of the near-infrared spectrum of carbon dioxide at high pressure and temperature will be compared to modeled spectra extrapolated from the HITRAN 2016 database as well as other published models that include additional collisional physics. This comparison gives insight into the effectiveness of existing absorption databases for modeling the lower Venus atmosphere as well as the need to expand absorption models to suit these conditions.

A best-case probe, light source, and database for H2O absorption thermometry to 2100 K and 50 bar

NASA Astrophysics Data System (ADS)

Brittelle, Mack S.

This work aspired to improve the ability of forthcoming researchers to utilize near IR H2O absorption spectroscopy for thermometry with development of three best-case techniques: the design of novel high temperature sapphire optical access probes, the construction of a fixed-wavelength H 2O absorption spectroscopy system enhanced by an on-board external-cavity diode laser, and the creation of an architecture for a high-temperature and -pressure H2O absorption cross-section database. Each area's main goal was to realize the best-case for direct absorption spectroscopy H2O vapor thermometry at combustion conditions. Optical access to combustion devices is explored through the design and implementation of two versions of novel high-temperature (2000 K) sapphire immersion probes (HTSIPs) for use in ambient flames and gas turbine combustors. The development and evaluation of a fixed wavelength H2O absorption spectroscopy (FWAS) system that is demonstrates how the ECDL allows the system to operate in multiple modes that enhance FWAS measurement accuracy by improving wavelength position monitoring, and reducing non-absorption based contamination in spectral scans. The architecture of a high temperature (21000 K) and pressure (50 bar) database (HTPD) is developed that can enhance absorption spectroscopy based thermometry. The HTPD formation is developed by the evaluation of two approaches, a line-by-line (LBL) approach, where transition lineshape parameters are extracted from spectra and used along with a physics based model to allow the simulation of spectra over a wide range of temperatures and pressures, or an absorption cross-section (sigmaabs) approach, where spectra generated from a high temperature and pressure furnace are catalog spectra at various conditions forming a database of absorption cross-sections that is then interpolated to provide a simulated absorbance spectra based on measured reference grade spectra. Utilizing near future reference grade H2O absorption spectra, generated by the Sanders Group by means of an ECDL and a high temperature and pressure furnace, a unique opportunity is taken to provide the research community with a database that can be utilized for optical thermometry.

Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry.

PubMed

Wentrup, Curt

2018-05-29

There has been significant progress in the direct observation of carbenes, nitrenes, and many other reactive intermediates in recent years due to the application of matrix photolysis and flash vacuum pyrolysis linked with matrix isolation at cryogenic temperatures. Our understanding of singlet and triplet states has improved through the interplay of spectroscopy and computations. Bistable carbenes and nitrenes as well as many examples of tunneling have been discovered. Numerous rearrangements and fragmentations have been documented. This minireview aims to give an overview of some of these developments but will not generally cover laser flash photolysis and chemical reactions in liquid solution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water types and their relaxation behavior in partially rehydrated CaFe-mixed binary oxide obtained from CaFe-layered double hydroxide in the 155-298 K temperature range.

PubMed

Bugris, Valéria; Haspel, Henrik; Kukovecz, Ákos; Kónya, Zoltán; Sipiczki, Mónika; Sipos, Pál; Pálinkó, István

2013-10-29

Heat-treated CaFe-layered double hydroxide samples were equilibrated under conditions of various relative humidities (11%, 43% and 75%). Measurements by FT-IR and dielectric relaxation spectroscopies revealed that partial to full reconstruction of the layered structure took place. Water types taking part in the reconstruction process were identified via dielectric relaxation measurements either at 298 K or on the flash-cooled (to 155 K) samples. The dynamics of water molecules at the various positions was also studied by this method, allowing the flash-cooled samples to warm up to 298 K.

In2Ga2ZnO7 oxide semiconductor based charge trap device for NAND flash memory.

PubMed

Hwang, Eun Suk; Kim, Jun Shik; Jeon, Seok Min; Lee, Seung Jun; Jang, Younjin; Cho, Deok-Yong; Hwang, Cheol Seong

2018-04-01

The programming characteristics of charge trap flash memory device adopting amorphous In 2 Ga 2 ZnO 7 (a-IGZO) oxide semiconductors as channel layer were evaluated. Metal-organic chemical vapor deposition (MOCVD) and RF-sputtering processes were used to grow a 45 nm thick a-IGZO layer on a 20 nm thick SiO 2 (blocking oxide)/p ++ -Si (control gate) substrate, where 3 nm thick atomic layer deposited Al 2 O 3 (tunneling oxide) and 5 nm thick low-pressure CVD Si 3 N 4 (charge trap) layers were intervened between the a-IGZO and substrate. Despite the identical stoichiometry and other physicochemical properties of the MOCVD and sputtered a-IGZO, a much faster programming speed of MOCVD a-IGZO was observed. A comparable amount of oxygen vacancies was found in both MOCVD and sputtered a-IGZO, confirmed by x-ray photoelectron spectroscopy and bias-illumination-instability test measurements. Ultraviolet photoelectron spectroscopy analysis revealed a higher Fermi level (E F ) of the MOCVD a-IGZO (∼0.3 eV) film than that of the sputtered a-IGZO, which could be ascribed to the higher hydrogen concentration in the MOCVD a-IGZO film. Since the programming in a flash memory device is governed by the tunneling of electrons from the channel to charge trapping layer, the faster programming performance could be the result of a higher E F of MOCVD a-IGZO.

In2Ga2ZnO7 oxide semiconductor based charge trap device for NAND flash memory

NASA Astrophysics Data System (ADS)

Hwang, Eun Suk; Kim, Jun Shik; Jeon, Seok Min; Lee, Seung Jun; Jang, Younjin; Cho, Deok-Yong; Hwang, Cheol Seong

2018-04-01

The programming characteristics of charge trap flash memory device adopting amorphous In2Ga2ZnO7 (a-IGZO) oxide semiconductors as channel layer were evaluated. Metal-organic chemical vapor deposition (MOCVD) and RF-sputtering processes were used to grow a 45 nm thick a-IGZO layer on a 20 nm thick SiO2 (blocking oxide)/p++-Si (control gate) substrate, where 3 nm thick atomic layer deposited Al2O3 (tunneling oxide) and 5 nm thick low-pressure CVD Si3N4 (charge trap) layers were intervened between the a-IGZO and substrate. Despite the identical stoichiometry and other physicochemical properties of the MOCVD and sputtered a-IGZO, a much faster programming speed of MOCVD a-IGZO was observed. A comparable amount of oxygen vacancies was found in both MOCVD and sputtered a-IGZO, confirmed by x-ray photoelectron spectroscopy and bias-illumination-instability test measurements. Ultraviolet photoelectron spectroscopy analysis revealed a higher Fermi level (E F) of the MOCVD a-IGZO (∼0.3 eV) film than that of the sputtered a-IGZO, which could be ascribed to the higher hydrogen concentration in the MOCVD a-IGZO film. Since the programming in a flash memory device is governed by the tunneling of electrons from the channel to charge trapping layer, the faster programming performance could be the result of a higher E F of MOCVD a-IGZO.

Synthesis of zirconium oxynitride in air under DC electric fields

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

Morisaki, Nobuhiro; Tokunaga, Tomoharu; Sasaki, Katsuhiro

We synthesized zirconium oxynitride from yttria-stabilized zirconia (YSZ) in air by applying DC electric fields that produced a controlled electric current in the specimen. When YSZ was heated under an applied DC electric field, the electric current of the specimen steeply increased at a critical temperature, called a flash event, during flash sintering. By keeping the electric current of the specimen constant during the flash event and then holding the specimen at the critical temperature, YSZ was transformed into zirconium oxynitride under the optimal conditions of 50 V/cm, 500 mA, and 1000 °C. We confirmed that zirconium oxynitride formed using high-resolution transmission electronmore » microscopy, electron energy-loss spectroscopy, and energy-dispersive spectrometry. To convert oxides to nitrides, reducing conditions are necessary to form excess oxygen vacancies. Our technique produced the strong reducing conditions necessary to form nitrides from the oxides by delivering a controlled electric current to the specimen.« less

XANES, EXAFS and Kbeta spectroscopic studies of the oxygen-evolving complex in Photosystem II

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

Robblee, John Henry

A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S 3 → [S 4] → S 0 transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kβ X-ray emission spectroscopy (Kb XES) to this problem for the first time. The Kβ XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electronmore » paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S 2 → S 3 transition, in contrast to the S 0 → S 1 and S 1 → S 2 transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese μ-oxo bridge radical formation during the S 2 → S 3 transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S 0 state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-μ-oxo-bridged Mn-Mn moieties increases from 2.7 Å in the S 1} state to 2.85 Å in the S 0 state. Furthermore, evidence is presented that shows three di-μ-oxo binuclear Mn 2 clusters may be present in the OEC, which is contrary to the widely held theory that two such clusters are present in the OEC. The EPR properties of the S 0 state have been investigated and a characteristic ''multiline'' signal in the S 0 state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S 0 state is paramagnetic. In addition, this signal was simulated using parameters derived from three possible oxidation states of Mn in the S 0 state. The dichroic nature of X-rays from synchrotron radiation and single-crystal Mn complexes have been exploited to selectively probe Mn-ligand bonds using XANES and EXAFS spectroscopy. The results from single-crystal Mn complexes show that dramatic dichroism exists in these complexes, and are suggestive of a promising future for single-crystal studies of PS II.« less

Femtosecond transient absorption, Raman, and electrochemistry studies of tetrasulfonated copper phthalocyanine in water solutions.

PubMed

Abramczyk, H; Brozek-Płuska, B; Kurczewski, K; Kurczewska, M; Szymczyk, I; Krzyczmonik, P; Błaszczyk, T; Scholl, H; Czajkowski, W

2006-07-20

Ultrafast time-resolved electronic spectra of the primary events induced in the copper tetrasulfonated phthalocyanine Cu(tsPc)4-) in aqueous solution has been measured by femtosecond pump-probe transient absorption spectroscopy. The primary events initiated by the absorption of a photon occurring within the femtosecond time scale are discussed on the basis of the electron transfer mechanism between the adjacent phthalocyanine rings proposed recently in our laboratory. The femtosecond transient absorption results are compared with the low temperature emission spectra obtained with Raman spectroscopy and the voltammetric curves.

X-Ray Absorption near Edge Structure Spectroscopy of Nanodiamonds from the Allende Meteorite

NASA Technical Reports Server (NTRS)

Flynn, G. J.; Keller, L. P.; Hill, H.; Jacobsen, C.; Wirick, S.

2000-01-01

Carbon X-ray Absorption Near Edge Structure Spectroscopy shows Allende DM nanodiamonds have two pre-edge peaks, consistent with other small diamonds, but fail to show a diamond exciton which is seen in 3.6 nm diamond thin films.

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

Wojciech, Blachucki

This work treats of the high energy resolution off-resonant X-ray spectroscopy (HEROS) method of determining the density of unoccupied electronic states in the vicinity of the absorption edge. HEROS is an alternative to the existing X-ray absorption spectroscopy (XAS) methods and opens the way for new studies not achievable before.

DETERMINING BERYLLIUM IN DRINKING WATER BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROSCOPY

EPA Science Inventory

A direct graphite furnace atomic absorption spectroscopy method for the analysis of beryllium in drinking water has been derived from a method for determining beryllium in urine. Ammonium phosphomolybdate and ascorbic acid were employed as matrix modifiers. The matrix modifiers s...

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

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

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

Environmentally Controlled Infrared Spectroscopy System for Fundamental Studies of Polymer Electrolyte Membranes

DTIC Science & Technology

2015-10-15

to state-of- hydration . Polarization modulated infrared reflection- absorption spectroscopy experiments are enabled by the use of a spin-coater to coat...NAME(S) AND ADDRESS (ES) U.S. Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 SPEEK, Nafion, Ionomers, state-of- hydration ...enabled correlation of the exchange site structure to state-of- hydration . Polarization modulated infrared reflection-absorption spectroscopy experiments

Single-tone and two-tone AM-FM spectral calculations for tunable diode laser absorption spectroscopy

NASA Technical Reports Server (NTRS)

Chou, Nee-Yin; Sachse, Glen W.

1987-01-01

A generalized theory for optical heterodyne spectroscopy with phase modulated laser radiation is used which allows the calculation of signal line shapes for frequency modulation spectroscopy of Lorentzian gas absorption lines. In particular, synthetic spectral line shapes for both single-tone and two-tone modulation of lead-salt diode lasers are presented in which the contributions from both amplitude and frequency modulations are included.

Flash Vacuum Pyrolysis: Techniques and Reactions.

PubMed

Wentrup, Curt

2017-11-20

Flash vacuum pyrolysis (FVP) had its beginnings in the 1940s and 1950s, mainly through mass spectrometric detection of pyrolytically formed free radicals. In the 1960s many organic chemists started performing FVP experiments with the purpose of isolating new and interesting compounds and understanding pyrolysis processes. Meanwhile, many different types of apparatus and techniques have been developed, and it is the purpose of this review to present the most important methods as well as a survey of typical reactions and observations that can be achieved with the various techniques. This includes preparative FVP, chemical trapping reactions, matrix isolation, and low temperature spectroscopy of reactive intermediates and unstable molecules, the use of online mass, photoelectron, microwave, and millimeterwave spectroscopies, gas-phase laser pyrolysis, pulsed pyrolysis with supersonic jet expansion, very low pressure pyrolysis for kinetic investigations, solution-spray and falling-solid FVP for involatile compounds, and pyrolysis over solid supports and reagents. Moreover, the combination of FVP with matrix isolation and photochemistry is a powerful tool for investigations of reaction mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interaction of photosystem I from Phaeodactylum tricornutum with plastocyanins as compared with its native cytochrome c6: Reunion with a lost donor.

PubMed

Bernal-Bayard, Pilar; Pallara, Chiara; Carmen Castell, M; Molina-Heredia, Fernando P; Fernández-Recio, Juan; Hervás, Manuel; Navarro, José A

2015-12-01

In the Phaeodactylum tricornutum alga, as in most diatoms, cytochrome c6 is the only electron donor to photosystem I, and thus they lack plastocyanin as an alternative electron carrier. We have investigated, by using laser-flash absorption spectroscopy, the electron transfer to Phaeodactylum photosystem I from plastocyanins from cyanobacteria, green algae and plants, as compared with its own cytochrome c6. Diatom photosystem I is able to effectively react with eukaryotic acidic plastocyanins, although with less efficiency than with Phaeodactylum cytochrome c6. This efficiency, however, increases in some green alga plastocyanin mutants mimicking the electrostatics of the interaction site on the diatom cytochrome. In addition, the structure of the transient electron transfer complex between cytochrome c6 and photosystem I from Phaeodactylum has been analyzed by computational docking and compared to that of green lineage and mixed systems. Taking together, the results explain why the Phaeodactylum system shows a lower efficiency than the green systems, both in the formation of the properly arranged [cytochrome c6-photosystem I] complex and in the electron transfer itself. Copyright © 2015 Elsevier B.V. All rights reserved.

Time-resolved spectroscopic studies of photosynthetic reaction centers and tetrapyrrole chromophores for biomedical and solar-energy applications

NASA Astrophysics Data System (ADS)

Kee, Hooi Ling

2008-10-01

The photophysical properties of diverse tetrapyrrole chromophores as well as energy and electron transfer processes in tetrapyrrole dyads are investigated using static and time-resolved (femtoseconds to seconds) absorption and fluorescence spectroscopy. The goal of these studies is to elucidate the molecular design principals necessary to construct chromophores with the specific and tunable properties that will enhance applications in optical molecular imaging, photodynamic therapy, and solar-energy conversion. The kinetic properties of the transient intermediate P+H B- involving the bacteriopheophytin molecule HB on the normally inactive (B) cofactor branch of the bacterial photosynthetic reaction center are examined in Rhodobacter capsulatus mutants. Using nanosecond flash photolysis and F(L181)Y/Y(M208)F/L(M212)H mutant, the decay pathways and yields of P+HB- were measured, giving an overall yield of 13% for B-side charge separation P* → P+HB- → P+ QB- in this mutant. The goal of these studies is to understand the fundamental differences in the rates, yields, and mechanisms of charge separation and charge recombination along the two parallel electron-transport chains in the bacterial reaction center.

A laser flash photolysis and quantum chemical study of the fluorinated derivatives of singlet phenylnitrene.

PubMed

Gritsan, N P; Gudmundsdóttir, A D; Tigelaar, D; Zhu, Z; Karney, W L; Hadad, C M; Platz, M S

2001-03-07

Laser flash photolysis (LFP, Nd:YAG laser, 35 ps, 266 nm, 10 mJ or KrF excimer laser, 10 ns, 249 nm, 50 mJ) of 2-fluoro, 4-fluoro, 3,5-difluoro, 2,6-difluoro, and 2,3,4,5,6-pentafluorophenyl azides produces the corresponding singlet nitrenes. The singlet nitrenes were detected by transient absorption spectroscopy, and their spectra are characterized by sharp absorption bands with maxima in the range of 300-365 nm. The kinetics of their decay were analyzed as a function of temperature to yield observed decay rate constants, k(OBS). The observed rate constant in inert solvents is the sum of k(R) + k(ISC) where k(R) is the absolute rate constant of rearrangement of singlet nitrene to an azirine and k(ISC) is the absolute rate constant of nitrene intersystem crossing (ISC). Values of k(R) and k(ISC) were deduced after assuming that k(ISC) is independent of temperature. Barriers to cyclization of 4-fluoro-, 3,5-difluoro-, 2-fluoro-, 2,6-difluoro-, and 2,3,4,5,6-pentafluorophenylnitrene in inert solvents are 5.3 +/- 0.3, 5.5 +/- 0.3, 6.7 +/- 0.3, 8.0 +/- 1.5, and 8.8 +/- 0.4 kcal/mol, respectively. The barrier to cyclization of parent singlet phenylnitrene is 5.6 +/- 0.3 kcal/mol. All of these values are in good quantitative agreement with CASPT2 calculations of the relative barrier heights for the conversion of fluoro-substituted singlet aryl nitrenes to benzazirines (Karney, W. L. and Borden, W. T. J. Am. Chem. Soc. 1997, 119, 3347). A single ortho-fluorine substituent exerts a small but significant bystander effect on remote cyclization that is not steric in origin. The influence of two ortho-fluorine substituents on the cyclization is pronounced. In the case of the singlet 2-fluorophenylnitrene system, evidence is presented that the benzazirine is an intermediate and that the corresponding singlet nitrene and benzazirine interconvert. Ab initio calculations at different levels of theory on a series of benzazirines, their isomeric ketenimines, and the transition states converting the benzazirines to ketenimines were performed. The computational results are in good qualitative and quantitative agreement with the experimental findings.

Intracavity Laser Absorption Spectroscopy of Platinum Nitride in the Near Infrared

NASA Astrophysics Data System (ADS)

O'Brien, Leah C.; Harris, Rachel A.; Whittemore, Sean; O'Brien, James J.

2009-06-01

A new electronic transition of PtN has been recorded using intracavity laser absorption spectroscopy. Four red-degraded branches are observed, with a bandheads located at 11733 and 11725 wn. The results of the analysis will be presented and compared with ab initio calculations.

Atomic Absorption Spectroscopy. The Present and the Future.

ERIC Educational Resources Information Center

Slavin, Walter

1982-01-01

The status of current techniques and methods of atomic absorption (AA) spectroscopy (flame, hybrid, and furnace AA) is discussed, including limitations. Technological opportunities and how they may be used in AA are also discussed, focusing on automation, microprocessors, continuum AA, hybrid analyses, and others. (Author/JN)

GALEX Grism Spectroscopy of the Globular Cluster Omega Centauri

NASA Astrophysics Data System (ADS)

Sweigart, Allen

We propose to obtain GALEX FUV-only grism spectroscopy of the hot stars in omega Centauri, the most massive globular cluster in our Galaxy. Previous UIT imagery of omega Cen showed that it contains about 2000 hot horizontal branch (HB) stars, and we estimate that GALEX spectra can be obtained for about 500 of these stars in the outer regions of the cluster, including about 50 of the hot ``blue hook'' stars discovered with UIT. The blue hook stars appear to be both hotter (35,000 K) and less luminous in the UIT color-magnitude diagram than predicted by canonical HB models and, indeed, are unexplained by standard evolutionary theory. Brown et al. (2001) have suggested that the blue hook stars are the progeny of stars which mixed their surface hydrogen into their hot He-burning interior during a delayed helium flash subsequent to leaving the red giant branch. This ``flash-mixing'' results in a hot hydrogen-deficient star with a typical surface abundance of 96% He and 4% C by mass. The GALEX spectral region includes the strong lines of C III 1426, 1578 A, C IV 1550 A, and He II 1640 A which will allow this predicted carbon and helium enrichment to be detected. These observations will therefore provide a crucial test of the Brown et al. flash-mixing hypothesis and will determine if flash mixing represents a new evolutionary channel for populating the hot HB. The GALEX spectra will also address other questions concerning the hot HB in omega Cen including (1) the metallicity distribution of HB stars with 9,000 K < Teff < 11,000 K, (2) the effect of radiative levitation on the UV spectra of stars with Teff > 11,000 K, and (3) the origin of the subluminous HB stars found in the UIT photometry with 15,000K < Teff < 30,000 K.

Flash Mixing of the White Dwarf Cooling Curve Spectroscopic Confirmation in NGC 2808

NASA Technical Reports Server (NTRS)

Brown, Thomas M.; Lanz, Thierry; Sweigart, Allen V.; Cracraft, Misty; Hubeny, Ivan; Landsman, Wayne B.

2009-01-01

We present new HST far-UV spectroscopy of two dozen hot evolved stars in NGC 2808, a massive globular cluster with a large population of "blue-hook" stars. The blue-hook stars are found in ultraviolet color-magnitude diagrams of the most massive globular clusters, where they fall at luminosities immediately below the hot end of the horizontal branch (HB), in a region of the HR diagram unexplained by canonical stellar evolution theory. Using new theoretical evolutionary and atmospheric models, we have shown that these subluminous HB stars are very likely the progeny of stars that undergo extensive internal mixing during a late He-core flash on the white dwarf cooling curve. This flash mixing leads to hotter temperatures and an enormous enhancement of the surface He and C abundances; the hotter temperatures and associated decrease in the hydrogen opacity shortward of the Lyman limit makes the stars brighter in the extreme UV but appear sub luminous in the UV and optical. Our far-UV spectroscopy demonstrates that, relative to normal HB stars at the same color, the blue-hook stars of NGC 2808 are hotter and greatly enhanced in He and C, thus providing unambiguous evidence of flash mixing in the subluminous population. Although the C abundance in the blue-hook stars is orders of magnitude larger than that in the normal HB stars, the atmospheric C abundance in both the blue-hook and normal HB stars appears to be affected by gravitational settling. The abundance variations seen in C, Si, and the Fe-peak elements indicate that atmospheric diffusion is at play in our sample, with all of our hot subdwarfs at 25,000 K to 50,000 K exhibiting large enhancements of the iron-peak elements. The hottest subdwarfs in our blue-hook sample may be pulsators, given that they fall in the temperature range of newly-discovered pulsating subdwarfs in omega Cen.

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

PubMed

Polovov, Ilya B; Volkovich, Vladimir A; Charnock, John M; Kralj, Brett; Lewin, Robert G; Kinoshita, Hajime; May, Iain; Sharrad, Clint A

2008-09-01

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.

Diffuse-light absorption spectroscopy by fiber optics for detecting and quantifying the adulteration of extra virgin olive oil

NASA Astrophysics Data System (ADS)

Mignani, A. G.; Ciaccheri, L.; Ottevaere, H.; Thienpont, H.; Conte, L.; Marega, M.; Cichelli, A.; Attilio, C.; Cimato, A.

2010-09-01

A fiber optic setup for diffuse-light absorption spectroscopy in the wide 400-1700 nm spectral range is experimented for detecting and quantifying the adulteration of extra virgin olive oil caused by lower-grade olive oils. Absorption measurements provide spectral fingerprints of authentic and adulterated oils. A multivariate processing of spectroscopic data is applied for discriminating the type of adulterant and for predicting its fraction.

Adsorption and photodecomposition of Mo(CO)[sub 6] on Si(111) 7[times]7: An infrared reflection absorption spectroscopy study

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

Richter, L.J.; Buntin, S.A.; Chu, P.M.

1994-02-15

The adsorption and photodecomposition of Mo(CO)[sub 6] adsorbed on Si(111) 7[times]7 surfaces has been studied with Auger electron spectroscopy, temperature programmed desorption, low energy electron diffraction and infrared reflection absorption spectroscopy in a single external reflection configuration. The external-reflection technique is demonstrated to have adequate sensitivity to characterize submonolayer coverages of photogenerated Mo(CO)[sub [ital x

Visualizing the Solute Vaporization Interference in Flame Atomic Absorption Spectroscopy

ERIC Educational Resources Information Center

Dockery, Christopher R.; Blew, Michael J.; Goode, Scott R.

2008-01-01

Every day, tens of thousands of chemists use analytical atomic spectroscopy in their work, often without knowledge of possible interferences. We present a unique approach to study these interferences by using modern response surface methods to visualize an interference in which aluminum depresses the calcium atomic absorption signal. Calcium…

Wafer-scale metasurface for total power absorption, local field enhancement and single molecule Raman spectroscopy

PubMed Central

Wang, Dongxing; Zhu, Wenqi; Best, Michael D.; Camden, Jon P.; Crozier, Kenneth B.

2013-01-01

The ability to detect molecules at low concentrations is highly desired for applications that range from basic science to healthcare. Considerable interest also exists for ultrathin materials with high optical absorption, e.g. for microbolometers and thermal emitters. Metal nanostructures present opportunities to achieve both purposes. Metal nanoparticles can generate gigantic field enhancements, sufficient for the Raman spectroscopy of single molecules. Thin layers containing metal nanostructures (“metasurfaces”) can achieve near-total power absorption at visible and near-infrared wavelengths. Thus far, however, both aims (i.e. single molecule Raman and total power absorption) have only been achieved using metal nanostructures produced by techniques (high resolution lithography or colloidal synthesis) that are complex and/or difficult to implement over large areas. Here, we demonstrate a metasurface that achieves the near-perfect absorption of visible-wavelength light and enables the Raman spectroscopy of single molecules. Our metasurface is fabricated using thin film depositions, and is of unprecedented (wafer-scale) extent. PMID:24091825

Analyte-induced spectral filtering in femtosecond transient absorption spectroscopy

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

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

Here, we discuss the influence of spectral filtering by samples in femtosecond transient absorption measurements. Commercial instruments for transient absorption spectroscopy (TA) have become increasingly available to scientists in recent years and TA is becoming an established technique to measure the dynamics of photoexcited systems. Furthermore, we show that absorption of the excitation pulse by the sample can severely alter the spectrum and consequently the temporal pulse shape. This “spectral self-filtering” effect can lead to systematic errors and misinterpretation of data, most notably in concentration dependent measurements. Finally, the combination of narrow absorption peaks in the sample with ultrafast broadbandmore » excitation pulses is especially prone to this effect.« less

Analyte-induced spectral filtering in femtosecond transient absorption spectroscopy

DOE PAGES

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

2017-03-06

Here, we discuss the influence of spectral filtering by samples in femtosecond transient absorption measurements. Commercial instruments for transient absorption spectroscopy (TA) have become increasingly available to scientists in recent years and TA is becoming an established technique to measure the dynamics of photoexcited systems. Furthermore, we show that absorption of the excitation pulse by the sample can severely alter the spectrum and consequently the temporal pulse shape. This “spectral self-filtering” effect can lead to systematic errors and misinterpretation of data, most notably in concentration dependent measurements. Finally, the combination of narrow absorption peaks in the sample with ultrafast broadbandmore » excitation pulses is especially prone to this effect.« less

Fermi GBM Observations of Terrestrial Gamma Flashes

NASA Technical Reports Server (NTRS)

Wilson-Hodge, Colleen A.; Briggs, M. S.; Fishman, G. J.; Bhat, P. N.; Paciesas, W. S.; Preece, R.; Kippen, R. M.; von Kienlin, A.; Dwyer, J. R.; Smith, D. M.;

Using resonance light scattering and UV/vis absorption spectroscopy to study the interaction between gliclazide and bovine serum albumin.

PubMed

Zhang, Qiu-Ju; Liu, Bao-Sheng; Li, Gai-Xia; Han, Rong

2016-08-01

At different temperatures (298, 310 and 318 K), the interaction between gliclazide and bovine serum albumin (BSA) was investigated using fluorescence quenching spectroscopy, resonance light scattering spectroscopy and UV/vis absorption spectroscopy. The first method studied changes in the fluorescence of BSA on addition of gliclazide, and the latter two methods studied the spectral change in gliclazide while BSA was being added. The results indicated that the quenching mechanism between BSA and gliclazide was static. The binding constant (Ka ), number of binding sites (n), thermodynamic parameters, binding forces and Hill's coefficient were calculated at three temperatures. Values for the binding constant obtained using resonance light scattering and UV/vis absorption spectroscopy were much greater than those obtained from fluorescence quenching spectroscopy, indicating that methods monitoring gliclazide were more accurate and reasonable. In addition, the results suggest that other residues are involved in the reaction and the mode 'point to surface' existed in the interaction between BSA and gliclazide. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

A study of structural differences between TBM patients' and non-TBM persons' CSF using UV-Vis absorption spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Fangcheng; Wang, Xin; Xu, Huajia; Wang, Kai

2016-01-01

Tuberculous meningitis (TBM) is a very common infectious disease in the central nervous system. The delay of diagnosing and treating TBM will lead to high disability and mortality of TBM. Hence, it is very important to promptly diagnose TBM early. In this work, we proposed a new method for diagnosing TBM with CSF samples by using UV-Vis absorption spectroscopy. CSF samples from TBM patients and non-TBM persons were compared, and the sensitivity, specificity, accuracy, positive predictive value reached 83.6%, 69.8%, 77.2%, 76.1% respectively. Our work indicated investigation of CSF using UV-Vis absorption spectroscopy might become a potentially useful method for TBM diagnosis.

Circuit Board Analysis for Lead by Atomic Absorption Spectroscopy in a Course for Nonscience Majors

ERIC Educational Resources Information Center

Weidenhammer, Jeffrey D.

2007-01-01

A circuit board analysis of the atomic absorption spectroscopy, which is used to measure lead content in a course for nonscience majors, is being presented. The experiment can also be used to explain the potential environmental hazards of unsafe disposal of various used electronic equipments.

Laser-based absorption spectroscopy as a technique for rapid in-line analysis of respired gas concentrations of O2 and CO2

PubMed Central

Cummings, Beth; Hamilton, Michelle L.; Ciaffoni, Luca; Pragnell, Timothy R.; Peverall, Rob; Ritchie, Grant A. D.; Hancock, Gus

2011-01-01

The use of sidestream analyzers for respired gas analysis is almost universal. However, they are not ideal for measurements of respiratory gas exchange because the analyses are both temporally dissociated from measurements of respiratory flow and also not generally conducted under the same physical conditions. This study explores the possibility of constructing an all optical, fast response, in-line breath analyzer for oxygen and carbon dioxide. Using direct absorption spectroscopy with a diode laser operating at a wavelength near 2 μm, measurements of expired carbon dioxide concentrations were obtained with an absolute limit of detection of 0.04% at a time resolution of 10 ms. Simultaneously, cavity enhanced absorption spectroscopy at a wavelength near 760 nm was employed to obtain measurements of expired oxygen concentrations with an absolute limit of detection of 0.26% at a time resolution of 10 ms. We conclude that laser-based absorption spectroscopy is a promising technology for in-line analysis of respired carbon dioxide and oxygen concentrations. PMID:21512147

Laser-based absorption spectroscopy as a technique for rapid in-line analysis of respired gas concentrations of O2 and CO2.

PubMed

Cummings, Beth; Hamilton, Michelle L; Ciaffoni, Luca; Pragnell, Timothy R; Peverall, Rob; Ritchie, Grant A D; Hancock, Gus; Robbins, Peter A

2011-07-01

The use of sidestream analyzers for respired gas analysis is almost universal. However, they are not ideal for measurements of respiratory gas exchange because the analyses are both temporally dissociated from measurements of respiratory flow and also not generally conducted under the same physical conditions. This study explores the possibility of constructing an all optical, fast response, in-line breath analyzer for oxygen and carbon dioxide. Using direct absorption spectroscopy with a diode laser operating at a wavelength near 2 μm, measurements of expired carbon dioxide concentrations were obtained with an absolute limit of detection of 0.04% at a time resolution of 10 ms. Simultaneously, cavity enhanced absorption spectroscopy at a wavelength near 760 nm was employed to obtain measurements of expired oxygen concentrations with an absolute limit of detection of 0.26% at a time resolution of 10 ms. We conclude that laser-based absorption spectroscopy is a promising technology for in-line analysis of respired carbon dioxide and oxygen concentrations.

Raman structural studies of the nickel electrode

NASA Technical Reports Server (NTRS)

Cornilsen, Bahne C.

1994-01-01

The objectives of this investigation have been to define the structures of charged active mass, discharged active mass, and related precursor materials (alpha-phases), with the purpose of better understanding the chemical and electrochemical reactions, including failure mechanisms and cobalt incorporation, so that the nickel electrode may be improved. Although our primary tool has been Raman spectroscopy, the structural conclusions drawn from the Raman data have been supported and augmented by three other analysis methods: infrared spectroscopy, powder X-ray Diffraction (XRD), and x-ray absorption spectroscopy (in particular EXAFS, Extended X-ray Absorption Fine Structure spectroscopy).

Optical Detection and Probing of Single Dopant Molecules of Pentacene in a p-Terphenyl Crystal by Means of Absorption Spectroscopy

DTIC Science & Technology

1989-08-31

Pentacene in a p-Terphenyl Host Crystal bY !eT=s of bsorotion Spectroscopy 12 PERSONAl AU- OR(S) L. Kador, W.E. Moerner & D.E. Horne 1 3a 7 P; OF REPORT...G(OP SUB-GROUP Single Molecule Detection FM Spectroscopy Pentacene in p-terphenyl 19 AtiSTRACT {Continue on reverse it necessary and identity Oy block...OF PENTACENE IN A p-TERPIIENYL IIOST CRYSTAL BY MEANS OF ABSORPTION SPECTROSCOPY L. Kador , 1). E. I lorne, and W. lF. Moerner IM Research )ivision

Energy-absorption spectroscopy of unitary Fermi gases in a uniform potential

NASA Astrophysics Data System (ADS)

Zhang, Pengfei; Yu, Zhenhua

2018-04-01

We propose to use the energy absorption spectroscopy to measure the kinetic coefficients of unitary Fermi gases in a uniform potential. We show that, in our scheme, the energy absorption spectrum is proportional to the dynamic structure factor of the system. The profile of the spectrum depends on the shear viscosity η , the thermal conductivity κ , and the superfluid bulk viscosity ξ3. We show that extraction of these coefficients from the spectrum is achievable in present experiments.

X-ray absorption spectroscopy investigations on oxidized Ni/Au contacts to p-GaN.

PubMed

Jan, J C; Asokan, K; Chiou, J W; Pong, W F; Tseng, P K; Chen, L C; Chen, F R; Lee, J F; Wu, J S; Lin, H J; Chen, C T

2001-03-01

X-ray absorption spectroscopy was used to investigate the electronic structure of as-deposited and oxidized Ni/Au contacts to p-GaN and to elucidate the mechanism responsible for low impedance. X-ray absorption near edge spectra of Ni K- and L3,2-edges clearly indicate formation of NiO on the sample surface after annealing. The reason for low impedance may be attributed to increase in hole concentration and existence of p-NiO layer on the surface.

Actively coupled cavity ringdown spectroscopy with low-power broadband sources.

PubMed

Petermann, Christian; Fischer, Peer

2011-05-23

We demonstrate a coupling scheme for cavity enhanced absorption spectroscopy that makes use of an intracavity acousto-optical modulator to actively switch light into (and out of) a resonator. This allows cavity ringdown spectroscopy (CRDS) to be implemented with broadband nonlaser light sources with spectral power densities of less than 30μW/nm. Although the acousto-optical element reduces the ultimate detection limit by introducing additional losses, it permits absorptivities to be measured with a high dynamic range, especially in lossy environments. Absorption measurements for the forbidden transition of gaseous oxygen in air at ∼760nm are presented using a low-coherence cw-superluminescent diode. The same setup was electronically configured to cover absorption losses from 1.8×10^-8cm^-1 to 7.5% per roundtrip. This could be of interest in process analytical applications.

Molecular dispersion spectroscopy based on Fabry-Perot quantum cascade lasers.

PubMed

Sterczewski, Lukasz A; Westberg, Jonas; Wysocki, Gerard

2017-01-15

Two Fabry-Perot quantum cascade lasers are used in a differential dual comb configuration to perform rapidly swept dispersion spectroscopy of low-pressure nitrous oxide with <1  ms acquisition time. Active feedback control of the laser injection current enables simultaneous wavelength modulation of both lasers at kilohertz rates. The system demonstrates similar performance in both absorption and dispersion spectroscopy modes and achieves a noise-equivalent absorption figure of merit in the low 10^-4/Hz range.

On the Mechanism of Microwave Flash Sintering of Ceramics

PubMed Central

Bykov, Yury V.; Egorov, Sergei V.; Eremeev, Anatoly G.; Kholoptsev, Vladislav V.; Plotnikov, Ivan V.; Rybakov, Kirill I.; Sorokin, Andrei A.

2016-01-01

The results of a study of ultra-rapid (flash) sintering of oxide ceramic materials under microwave heating with high absorbed power per unit volume of material (10–500 W/cm3) are presented. Ceramic samples of various compositions—Al2O3; Y2O3; MgAl2O4; and Yb(LaO)2O3—were sintered using a 24 GHz gyrotron system to a density above 0.98–0.99 of the theoretical value in 0.5–5 min without isothermal hold. An analysis of the experimental data (microwave power; heating and cooling rates) along with microstructure characterization provided an insight into the mechanism of flash sintering. Flash sintering occurs when the processing conditions—including the temperature of the sample; the properties of thermal insulation; and the intensity of microwave radiation—facilitate the development of thermal runaway due to an Arrhenius-type dependency of the material’s effective conductivity on temperature. The proper control over the thermal runaway effect is provided by fast regulation of the microwave power. The elevated concentration of defects and impurities in the boundary regions of the grains leads to localized preferential absorption of microwave radiation and results in grain boundary softening/pre-melting. The rapid densification of the granular medium with a reduced viscosity of the grain boundary phase occurs via rotation and sliding of the grains which accommodate their shape due to fast diffusion mass transport through the (quasi-)liquid phase. The same mechanism based on a thermal runaway under volumetric heating can be relevant for the effect of flash sintering of various oxide ceramics under a dc/ac voltage applied to the sample. PMID:28773807

Optical spectroscopy of interplanetary dust collected in the earth's stratosphere

NASA Technical Reports Server (NTRS)

Fraundorf, P.; Patel, R. I.; Shirck, J.; Walker, R. M.; Freeman, J. J.

1980-01-01

Optical absorption spectra of interplanetary dust particles 2-30 microns in size collected in the atmosphere at an altitude of 20 km by inertial impactors mounted on NASA U-2 aircraft are reported. Fourier transform absorption spectroscopy of crushed samples of the particles reveals a broad feature in the region 1300-800 kaysers which has also been found in meteorite and cometary dust spectra, and a weak iron crystal field absorption band at approximately 9800 kaysers, as is observed in meteorites. Work is currently in progress to separate the various components of the interplanetary dust particles in order to evaluate separately their contributions to the absorption.

Time-Resolved IR-Absorption Spectroscopy of Hot-Electron Dynamics in Satellite and Upper Conduction Bands in GaP

NASA Technical Reports Server (NTRS)

Cavicchia, M. A.; Alfano, R. R.

1995-01-01

The relaxation dynamics of hot electrons in the X6 and X7 satellite and upper conduction bands in GaP was directly measured by femtosecond UV-pump-IR-probe absorption spectroscopy. From a fit to the induced IR-absorption spectra the dominant scattering mechanism giving rise to the absorption at early delay times was determined to be intervalley scattering of electrons out of the X7 upper conduction-band valley. For long delay times the dominant scattering mechanism is electron-hole scattering. Electron transport dynamics of the upper conduction band of GaP has been time resolved.

Investigation of Diode Pumped Alkali Laser Atmospheric Transmission Using Tunable Diode Laser Absorption Spectroscopy

DTIC Science & Technology

2012-09-01

atmosphere”. Applied Physics B: Lasers and Optics, 82(1):133–140, 2006. 11. Barrass, S., Y. Grard, R.J. Holdsworth, and P.A. Martin . “Near-infrared tun...15. Brown, M. S., S. Williams, C. D. Lindstrom , and D. L. Barone. Progress in Applying Tunable Diode Laser Absorption Spectroscopy to Scramjet

A Simplified Digestion Protocol for the Analysis of Hg in Fish by Cold Vapor Atomic Absorption Spectroscopy

ERIC Educational Resources Information Center

Kristian, Kathleen E.; Friedbauer, Scott; Kabashi, Donika; Ferencz, Kristen M.; Barajas, Jennifer C.; O'Brien, Kelly

2015-01-01

Analysis of mercury in fish is an interesting problem with the potential to motivate students in chemistry laboratory courses. The recommended method for mercury analysis in fish is cold vapor atomic absorption spectroscopy (CVAAS), which requires homogeneous analyte solutions, typically prepared by acid digestion. Previously published digestion…

The identification of hydrophobic sites on the surface of proteins using absorption difference spectroscopy of bromophenol blue.

PubMed

Bertsch, M; Mayburd, A L; Kassner, R J

2003-02-15

Hydrophobic sites on the surface of protein molecules are thought to have important functional roles. The identification of such sites can provide information about the function and mode of interaction with other cellular components. While the fluorescence enhancement of polarity-sensitive dyes has been useful in identifying hydrophobic sites on a number of targets, strong intrinsic quenching of Nile red and ANSA dye fluorescence is observed on binding to a cytochrome c('). Fluorescence quenching is also observed to take place in the presence of a variety of other biologically important molecules which can compromise the quantitative determination of binding constants. Absorption difference spectroscopy is shown not to be sensitive to the presence of fluorescence quenchers but sensitive enough to measure binding constants. The dye BPB is shown to bind to the same hydrophobic sites on proteins as polarity-sensitive fluorescence probes. The absorption spectrum of BPB is also observed to be polarity sensitive. A binding constant of 3x10(6)M(-1) for BPB to BSA has been measured by absorption difference spectroscopy. An empirical correlation is observed between the shape of the absorption difference spectrum of BPB and the polarity of the environment. The results indicate that absorption difference spectroscopy of BPB provides a valuable supplement to fluorescence for determining the presence of hydrophobic sites on the surface of proteins as well as a method for measuring binding constants.

Development of picosecond time-resolved X-ray absorption spectroscopy by high-repetition-rate laser pump/X-ray probe at Beijing Synchrotron Radiation Facility.

PubMed

Wang, Hao; Yu, Can; Wei, Xu; Gao, Zhenhua; Xu, Guang Lei; Sun, Da Rui; Li, Zhenjie; Zhou, Yangfan; Li, Qiu Ju; Zhang, Bing Bing; Xu, Jin Qiang; Wang, Lin; Zhang, Yan; Tan, Ying Lei; Tao, Ye

2017-05-01

A new setup and commissioning of transient X-ray absorption spectroscopy are described, based on the high-repetition-rate laser pump/X-ray probe method, at the 1W2B wiggler beamline at the Beijing Synchrotron Radiation Facility. A high-repetition-rate and high-power laser is incorporated into the setup with in-house-built avalanche photodiodes as detectors. A simple acquisition scheme was applied to obtain laser-on and laser-off signals simultaneously. The capability of picosecond transient X-ray absorption spectroscopy measurement was demonstrated for a photo-induced spin-crossover iron complex in 6 mM solution with 155 kHz repetition rate.

Laser absorption spectroscopy of oxygen confined in highly porous hollow sphere xerogel.

PubMed

Yang, Lin; Somesfalean, Gabriel; He, Sailing

2014-02-10

An Al2O3 xerogel with a distinctive microstructure is studied for the application of laser absorption spectroscopy of oxygen. The xerogel has an exceptionally high porosity (up to 88%) and a large pore size (up to 3.6 µm). Using the method of gas-in-scattering media absorption spectroscopy (GASMAS), a long optical path length (about 3.5m) and high enhancement factor (over 300 times) are achieved as the result of extremely strong multiple-scattering when the light is transmitted through the air-filled, hollow-sphere alumina xerogel. We investigate how the micro-physical feature influences the optical property. As part of the optical sensing system, the material's gas exchange dynamics are also experimentally studied.

Observation of nanosecond laser induced fluorescence of in vitro seawater phytoplankton

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

Bensky, Thomas J.; Clemo, Lisa; Gilbert, Chris

2008-08-01

Seawater has been irradiated using a train of 70 ns flashes from a 440 nm laser source. This wavelength is on resonance with the blue absorption peak of Chlorophyll pigment associated with the photosystem of in vitro phytoplankton. The resulting fluorescence at 685 nm is instantaneously recorded during each laser pulse using a streak camera. Delayed fluorescence is observed, yielding clues about initiation of the photosynthetic process on a nanosecond time scale. Further data processing allows for determination of the functional absorption cross section, found to be 0.0095 ?{sup 2}, which is the first reporting of this number for inmore » vitro phytoplankton. Unlike other flash-pump studies of Chlorophyll, using a LED or flashlamp-based sources, the short laser pulse used here does not reveal any pulse-to-pulse hysteresis (i.e., variable fluorescence), indicating that the laser pulses used here are not able to drive the photosynthetic process to completion. This is attributed to competition from a back reaction between the photoexcited photosystem II and the intermediate electron acceptor. The significance of this work as a new type of deployable ocean fluorimeter is discussed, and it is believed the apparatus will have applications in thin-layer phytoplankton research.« less

Simulation of medical Q-switch flash-pumped Er:YAG laser

NASA Astrophysics Data System (ADS)

-Yan-lin, Wang; Huang-Chuyun; Yao-Yucheng; Xiaolin, Zou

2011-01-01

Er: YAG laser, the wavelength is 2940nm, can be absorbed strongly by water. The absorption coefficient is as high as 13000 cm-1. As the water strong absorption, Erbium laser can bring shallow penetration depth and smaller surrounding tissue injury in most soft tissue and hard tissue. At the same time, the interaction between 2940nm radiation and biological tissue saturated with water is equivalent to instantaneous heating within limited volume, thus resulting in the phenomenon of micro-explosion to removal organization. Different parameters can be set up to cut enamel, dentin, caries and soft tissue. For the development and optimization of laser system, it is a practical choice to use laser modeling to predict the influence of various parameters for laser performance. Aim at the status of low Erbium laser output power, flash-pumped Er: YAG laser performance was simulated to obtain optical output in theory. the rate equation model was obtained and used to predict the change of population densities in various manifolds and use the technology of Q-switch the simulate laser output for different design parameters and results showed that Er: YAG laser output energy can achieve the maximum average output power of 9.8W under the given parameters. The model can be used to find the potential laser systems that meet application requirements.

Reconstruction of combustion temperature and gas concentration distributions using line-of-sight tunable diode laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Zhirong; Sun, Pengshuai; Pang, Tao; Xia, Hua; Cui, Xiaojuan; Li, Zhe; Han, Luo; Wu, Bian; Wang, Yu; Sigrist, Markus W.; Dong, Fengzhong

2016-07-01

Spatial temperature and gas concentration distributions are crucial for combustion studies to characterize the combustion position and to evaluate the combustion regime and the released heat quantity. Optical computer tomography (CT) enables the reconstruction of temperature and gas concentration fields in a flame on the basis of line-of-sight tunable diode laser absorption spectroscopy (LOS-TDLAS). A pair of H2O absorption lines at wavelengths 1395.51 and 1395.69 nm is selected. Temperature and H2O concentration distributions for a flat flame furnace are calculated by superimposing two absorption peaks with a discrete algebraic iterative algorithm and a mathematical fitting algorithm. By comparison, direct absorption spectroscopy measurements agree well with the thermocouple measurements and yield a good correlation. The CT reconstruction data of different air-to-fuel ratio combustion conditions (incomplete combustion and full combustion) and three different types of burners (one, two, and three flat flame furnaces) demonstrate that TDLAS has the potential of short response time and enables real-time temperature and gas concentration distribution measurements for combustion diagnosis.

Non-Destructive and Discriminating Identification of Illegal Drugs by Transient Absorption Spectroscopy in the Visible and Near-IR Wavelength Range

NASA Astrophysics Data System (ADS)

Sato, Chie; Furube, Akihiro; Katoh, Ryuzi; Nonaka, Hidehiko; Inoue, Hiroyuki

2008-11-01

We have tested the possibility of identifying illegal drugs by means of nanosecond transient absorption spectroscopy with a 10-ns UV-laser pulse for the excitation light and visible-to-near-IR light for the probe light. We measured the transient absorption spectra of acetonitrile solutions of d-methamphetamine, dl-3,4-methylenedioxymethamphetamine hydrochloride (MDMA), and dl-N-methyl-1-(1,3-benzodioxol-5-yl)-2-butanamine hydrochloride (MBDB), which are illegal drugs widely consumed in Japan. Transient absorption signals of these drugs were observed between 400 and 950 nm, a range in which they are transparent in the ground state. By analyzing the spectra in terms of exponential and Gaussian functions, we could identify the drugs and discriminate them from chemical substances having similar structures. We propose that transient absorption spectroscopy will be a useful, non-destructive method of inspecting for illegal drugs, especially when they are dissolved in liquids. Such a method may even be used for drugs packed in opaque materials if it is further extended to utilize intense femtosecond laser pulses.

Laser flash-photolysis and gas discharge in N2O-containing mixture: kinetic mechanism

NASA Astrophysics Data System (ADS)

Kosarev, Ilya; Popov, Nikolay; Starikovskaia, Svetlana; Starikovskiy, Andrey; mipt Team

2011-10-01

The paper is devoted to further experimental and theoretical analysis of ignition by ArF laser flash-photolysis and nanosecond discharge in N2O-containing mixture has been done. Additional experiments have been made to assure that laser emission is distributed uniformly throughout the cross-section. The series of experiments was proposed and carried out to check validity of O(1D) determination in experiments on plasma assisted ignition initiated by flash-photolysis. In these experiments, ozone density in the given mixture (mixture composition and kinetics has been preliminary analyzed) was measured using UV light absorption in Hartley band. Good coincidence between experimental data and results of calculations have been obtained Temporal behavior of energy input, electric field and electric current has been measured and analyzed. These data are considered as initial conditions for numerical modeling of the discharge in O2:N2O:H2:Ar = 0.3:1:3:5 mixture. Ion-molecular reactions and reactions of active species production in Ar:H2:O2:N2O mixture were analyzed. The set of reactions to describe chemical transformation in the system due to the discharge action has been selected.

Communication using eye roll reflective signalling

USGS Publications Warehouse

Flamarique, I.N.; Mueller, G.A.; Cheng, C.L.; Figiel, C.R.

2007-01-01

Body reflections in the ultraviolet (UV) are a common occurrence in nature. Despite the abundance of such signals and the presence of UV cones in the retinas of many vertebrates, the function of UV cones in the majority of taxa remains unclear. Here, we report on an unusual communication system in the razorback sucker, Xyrauchen texanus, that involves flash signals produced by quick eye rolls. Behavioural experiments and field observations indicate that this form of communication is used to signal territorial presence between males. The flash signal shows highest contrast in the UV region of fhe visual spectrum (??max???380 nm), corresponding to the maximum wavelength of absorption of the UV cone mechanism in suckers. Furthermore, these cones are restricted to the dorsal retina of the animal and the upwelling light background is such that their relative sensitivity would be enhanced by chromatic adaptation of the other cone mechanisms. Thus, the UV cones in the sucker have optimal characteristics (both in terms of absorbance and retinal topography) to constitute the main detectors of the flash signal. Our findings provide the first ecological evidence for restricted distribution of UV cones in the retina of a vertebrate. ?? 2007 The Royal Society.

Signal-to-solar clutter calculations of AK-47 muzzle flash at various spectral bandpasses near the potassium D1/D2 doublet

NASA Astrophysics Data System (ADS)

Klett, Karl K., Jr.

2010-04-01

An analysis was performed, using MODTRAN, to determine the best filters to use for detecting the muzzle flash of an AK-47 in daylight conditions in the desert. Filters with bandwidths of 0.05, 0.1, 0.5, 1.0, 3.0, and 5.0 nanometers (nm) were analyzed to understand how the optical bandwidth affects the signal-to-solar clutter ratio. These filters were evaluated near the potassium D1 and D2 doublet emission lines that occur at 769.89 and 766.49 nm respectively that are observed where projectile propellants are used. The maximum spectral radiance, from the AK-47 muzzle flash, is 1.88 x 10-2 W/cm2 str micron, and is approximately equal to the daytime atmospheric spectral radiance. The increased emission, due to the potassium doublet lines, and decreased atmospheric transmission, due to oxygen absorption, combine to create a condition where the signal-to-solar clutter ratio is greater than 1. The 3 nm filter, has a signal-to-solar clutter ratio of 2.09 when centered at 765.37 nm and provides the best combination of both cost and signal sensitivity.

The extraction of gold nanoparticles from oat and wheat biomasses using sodium citrate and cetyltrimethylammonium bromide, studied by x-ray absorption spectroscopy, high-resolution transmission electron microscopy, and UV-visible spectroscopy.

PubMed

Armendariz, Veronica; Parsons, Jason G; Lopez, Martha L; Peralta-Videa, Jose R; Jose-Yacaman, Miguel; Gardea-Torresdey, Jorge L

2009-03-11

Gold (Au) nanoparticles can be produced through the interaction of Au(III) ions with oat and wheat biomasses. This paper describes a procedure to recover gold nanoparticles from oat and wheat biomasses using cetyltrimethylammonium bromide or sodium citrate. Extracts were analyzed using UV-visible spectroscopy, high-resolution transmission electron microscopy (HRTEM), and x-ray absorption spectroscopy. The HRTEM data demonstrated that smaller nanoparticles are extracted first, followed by larger nanoparticles. In the fourth extraction, coating of chelating agents is visible on the extracted nanoparticles.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole L.

We demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security applications.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

DOE PAGES

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole; ...

2017-06-19

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

Direct Absorption Spectroscopy with Electro-Optic Frequency Combs

NASA Astrophysics Data System (ADS)

Fleisher, Adam J.; Long, David A.; Plusquellic, David F.; Hodges, Joseph T.

2017-06-01

The application of electro-optic frequency combs to direct absorption spectroscopy has increased research interest in high-agility, modulator-based comb generation. This talk will review common architectures for electro-optic frequency comb generators as well as describe common self-heterodyne and multi-heterodyne (i.e., dual-comb) detection approaches. In order to achieve a sufficient signal-to-noise ratio on the recorded interferogram while allowing for manageable data volumes, broadband electro-optic frequency combs require deep coherent averaging, preferably in real-time. Applications such as cavity-enhanced spectroscopy, precision atomic and molecular spectroscopy, as well as time-resolved spectroscopy will be introduced. D.A. Long et al., Opt. Lett. 39, 2688 (2014) A.J. Fleisher et al., Opt. Express 24, 10424 (2016)

Low laser power micro-Raman study of Co{sub (1−x)}Mn{sub (x)}Fe{sub 2}O{sub 4} prepared by flash combustion method

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

Baraliya, J. D.

2016-05-23

Manganese substituted Cobalt ferrites of composition with nominal formula Co{sub (1−x)}Mn{sub (x)}Fe{sub 2}O{sub 4} (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) prepared by the Flash Combustion Method(FCM). The single phase spinel formation of nano ferrites was confirmed by X-ray diffraction techniques and micro - Raman spectroscopy. The particle size calculated from the Scherrer formula varied within 13 to 17 nm. Lattice parameter, nano particle size, and cation distribution were quantified as a function of the Mn-content in the range x = 0.0 to 1.0. Micro-Raman spectroscopic studies yielded convincing evidence for a transformation of the structure.

[The Diagnostics of Detonation Flow External Field Based on Multispectral Absorption Spectroscopy Technology].

PubMed

Lü, Xiao-jing; Li, Ning; Weng, Chun-sheng

2016-03-01

Compared with traditional sampling-based sensing method, absorption spectroscopy technology is well suitable for detonation flow diagnostics, since it can provide with us fast response, nonintrusive, sensitive solution for situ measurements of multiple flow-field parameters. The temperature and concentration test results are the average values along the laser path with traditional absorption spectroscopy technology, while the boundary of detonation flow external field is unknown and it changes all the time during the detonation engine works, traditional absorption spectroscopy technology is no longer suitable for detonation diagnostics. The trend of line strength with temperature varies with different absorption lines. By increasing the number of absorption lines in the test path, more information of the non-uniform flow field can be obtained. In this paper, based on multispectral absorption technology, the reconstructed model of detonation flow external field distribution was established according to the simulation results of space-time conservation element and solution element method, and a diagnostic method of detonation flow external field was given. The model deviation and calculation error of the least squares method adopted were studied by simulation, and the maximum concentration and temperature calculation error was 20.1% and 3.2%, respectively. Four absorption lines of H2O were chosen and detonation flow was scanned at the same time. The detonation external flow testing system was set up for the valveless gas-liquid continuous pulse detonation engine with the diameter of 80 mm. Through scanning H2O absorption lines with a high frequency of 10 kHz, the on-line detection of detonation external flow was realized by direct absorption method combined with time-division multiplexing technology, and the reconstruction of dynamic temperature distribution was realized as well for the first time, both verifying the feasibility of the test method. The test results show that both of the temperature and H2O concentration rose with the arrival of detonation wave. With the increase of the vertical distance between the detonation tube nozzle and the laser path, the time of temperature and concentration coming to the peak delayed, and the temperature variation trend tended to slow down. At 20 cm from detonation tube nozzle, the maximum temperature hit 1 329 K and the maximum H2O concentration of 0.19 occurred at 4 ms after ignition. The research can provide with us the support for expanding the detonation test field with absorption spectroscopy technology, and can also help to promote the detonation mechanism research and to enhance the level of detonation engine control technology.

Using of laser spectroscopy and chemometrics methods for identification of patients with lung cancer, patients with COPD and healthy people from absorption spectra of exhaled air

NASA Astrophysics Data System (ADS)

Bukreeva, Ekaterina B.; Bulanova, Anna A.; Kistenev, Yury V.; Kuzmin, Dmitry A.; Nikiforova, Olga Yu.; Ponomarev, Yurii N.; Tuzikov, Sergei A.; Yumov, Evgeny L.

2014-11-01

The results of application of the joint use of laser photoacoustic spectroscopy and chemometrics methods in gas analysis of exhaled air of patients with chronic respiratory diseases (chronic obstructive pulmonary disease and lung cancer) are presented. The absorption spectra of exhaled breath of representatives of the target groups and healthy volunteers were measured; the selection by chemometrics methods of the most informative absorption coefficients in scan spectra in terms of the separation investigated nosology was implemented.

Developing a Transdisciplinary Teaching Implement for Atomic Absorption Spectroscopy

ERIC Educational Resources Information Center

Drew, John

2008-01-01

In this article I explain why I wrote the set of teaching notes on Atomic Absorption Spectroscopy (AAS) and why they look the way they do. The notes were intended as a student reference to question, highlight and write over as much as they wish during an initial practical demonstration of the threshold concept being introduced, in this case…

The Use of a Microprocessor-Controlled, Video Output Atomic Absorption Spectrometer as an Educational Tool in a Two-Year Technical Curriculum.

ERIC Educational Resources Information Center

Kerfoot, Henry B.

Based on instructional experiences at Charles County Community College, Maryland, this report examines the pedagogical advantage of teaching atomic absorption (AA) spectroscopy with an AA spectrophotometer that is equipped with a microprocessor and video output mechanism. The report first discusses the growing importance of AA spectroscopy in…

Rapid, Time-Division Multiplexed, Direct Absorption- and Wavelength Modulation-Spectroscopy

PubMed Central

Klein, Alexander; Witzel, Oliver; Ebert, Volker

2014-01-01

We present a tunable diode laser spectrometer with a novel, rapid time multiplexed direct absorption- and wavelength modulation-spectroscopy operation mode. The new technique allows enhancing the precision and dynamic range of a tunable diode laser absorption spectrometer without sacrificing accuracy. The spectroscopic technique combines the benefits of absolute concentration measurements using calibration-free direct tunable diode laser absorption spectroscopy (dTDLAS) with the enhanced noise rejection of wavelength modulation spectroscopy (WMS). In this work we demonstrate for the first time a 125 Hz time division multiplexed (TDM-dTDLAS-WMS) spectroscopic scheme by alternating the modulation of a DFB-laser between a triangle-ramp (dTDLAS) and an additional 20 kHz sinusoidal modulation (WMS). The absolute concentration measurement via the dTDLAS-technique allows one to simultaneously calibrate the normalized 2f/1f-signal of the WMS-technique. A dTDLAS/WMS-spectrometer at 1.37 μm for H2O detection was built for experimental validation of the multiplexing scheme over a concentration range from 50 to 3000 ppmV (0.1 MPa, 293 K). A precision of 190 ppbV was achieved with an absorption length of 12.7 cm and an averaging time of two seconds. Our results show a five-fold improvement in precision over the entire concentration range and a significantly decreased averaging time of the spectrometer. PMID:25405508

Real-time trace gas sensor using a multimode diode laser and multiple-line integrated cavity enhanced absorption spectroscopy.

PubMed

Karpf, Andreas; Rao, Gottipaty N

2015-07-01

We describe and demonstrate a highly sensitive trace gas sensor based on a simplified design that is capable of measuring sub-ppb concentrations of NO2 in tens of milliseconds. The sensor makes use of a relatively inexpensive Fabry-Perot diode laser to conduct off-axis cavity enhanced spectroscopy. The broad frequency range of a multimode Fabry-Perot diode laser spans a large number of absorption lines, thereby removing the need for a single-frequency tunable laser source. The use of cavity enhanced absorption spectroscopy enhances the sensitivity of the sensor by providing a pathlength on the order of 1 km in a small volume. Off-axis alignment excites a large number of cavity modes simultaneously, thereby reducing the sensor's susceptibility to vibration. Multiple-line integrated absorption spectroscopy (where one integrates the absorption spectra over a large number of rovibronic transitions of the molecular species) further improves the sensitivity of detection. Relatively high laser power (∼400  mW) is used to compensate for the low coupling efficiency of a broad linewidth laser to the optical cavity. The approach was demonstrated using a 407 nm diode laser to detect trace quantities of NO2 in zero air. Sensitivities of 750 ppt, 110 ppt, and 65 ppt were achieved using integration times of 50 ms, 5 s, and 20 s respectively.

A search for intervening HI absorption

NASA Astrophysics Data System (ADS)

Reeves, Sarah N.; Sadler, Elaine M.; Allison, James R.; Koribalski, Baerbel S.; Curran, Stephen J.

2013-03-01

HI absorption-line studies provide a unique probe of the gas distribution and kinematics in galaxies well beyond the local universe (z ≳ 0.3). HI absorption-line surveys with next-generation radio telescopes will provide the first large-scale studies of HI in a redshift regime which is poorly understood. However, we currently lack the understanding to infer galaxy properties from absorption-line observations alone. To address this issue, we are conducting a search for intervening HI absorption in a sample of 20 nearby galaxies. Our aim is to investigate how the detection rate varies with distance from the galaxy. We target sight-lines to bright continuum sources, which intercept known gas-rich galaxies, selected from the HIPASS Bright Galaxy Catalogue (Koribalski et al. 2004). In our pilot sample, six galaxies with impact parameters < 20 kpc, we do not detect any absorption lines - although all are detected in 21cm emission. This indicates that an absorption non-detection cannot simply be interpreted as an absence of neutral gas - see Fig. 1. Our detection rate is low compared to previous surveys e.g. Gupta et al. (2010). This is, at least partially, due to the high resolution of the observations reducing the flux of the background source, which will also be an issue in future surveys, such as ASKAP-FLASH.

Intensity-Stabilized Fast-Scanned Direct Absorption Spectroscopy Instrumentation Based on a Distributed Feedback Laser with Detection Sensitivity down to 4 × 10−6

PubMed Central

Zhao, Gang; Tan, Wei; Jia, Mengyuan; Hou, Jiajuan; Ma, Weiguang; Dong, Lei; Zhang, Lei; Feng, Xiaoxia; Wu, Xuechun; Yin, Wangbao; Xiao, Liantuan; Axner, Ove; Jia, Suotang

2016-01-01

A novel, intensity-stabilized, fast-scanned, direct absorption spectroscopy (IS-FS-DAS) instrumentation, based on a distributed feedback (DFB) diode laser, is developed. A fiber-coupled polarization rotator and a fiber-coupled polarizer are used to stabilize the intensity of the laser, which significantly reduces its relative intensity noise (RIN). The influence of white noise is reduced by fast scanning over the spectral feature (at 1 kHz), followed by averaging. By combining these two noise-reducing techniques, it is demonstrated that direct absorption spectroscopy (DAS) can be swiftly performed down to a limit of detection (LOD) (1σ) of 4 × 10−6, which opens up a number of new applications. PMID:27657082

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

PubMed Central

Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

2015-01-01

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

Pyrolysis of the Simplest Carbohydrate, Glycolaldehyde (CHO-CH2OH), and Glyoxal in a Heated Microreactor.

PubMed

Porterfield, Jessica P; Baraban, Joshua H; Troy, Tyler P; Ahmed, Musahid; McCarthy, Michael C; Morgan, Kathleen M; Daily, John W; Nguyen, Thanh Lam; Stanton, John F; Ellison, G Barney

2016-04-14

Both glycolaldehyde and glyoxal were pyrolyzed in a set of flash-pyrolysis microreactors. The pyrolysis products resulting from CHO-CH2OH and HCO-CHO were detected and identified by vacuum ultraviolet (VUV) photoionization mass spectrometry. Complementary product identification was provided by argon matrix infrared absorption spectroscopy. Pyrolysis pressures in the microreactor were about 100 Torr, and contact times with the microreactors were roughly 100 μs. At 1200 K, the products of glycolaldehyde pyrolysis are H atoms, CO, CH2═O, CH2═C═O, and HCO-CHO. Thermal decomposition of HCO-CHO was studied with pulsed 118.2 nm photoionization mass spectrometry and matrix infrared absorption. Under these conditions, glyoxal undergoes pyrolysis to H atoms and CO. Tunable VUV photoionization mass spectrometry provides a lower bound for the ionization energy (IE)(CHO-CH2OH) ≥ 9.95 ± 0.05 eV. The gas-phase heat of formation of glycolaldehyde was established by a sequence of calorimetric experiments. The experimental result is ΔfH298(CHO-CH2OH) = -75.8 ± 1.3 kcal mol(-1). Fully ab initio, coupled cluster calculations predict ΔfH0(CHO-CH2OH) of -73.1 ± 0.5 kcal mol(-1) and ΔfH298(CHO-CH2OH) of -76.1 ± 0.5 kcal mol(-1). The coupled-cluster singles doubles and noniterative triples correction calculations also lead to a revision of the geometry of CHO-CH2OH. We find that the O-H bond length differs substantially from earlier experimental estimates, due to unusual zero-point contributions to the moments of inertia.

The joy of transient chaos.

PubMed

Tél, Tamás

2015-09-01

We intend to show that transient chaos is a very appealing, but still not widely appreciated, subfield of nonlinear dynamics. Besides flashing its basic properties and giving a brief overview of the many applications, a few recent transient-chaos-related subjects are introduced in some detail. These include the dynamics of decision making, dispersion, and sedimentation of volcanic ash, doubly transient chaos of undriven autonomous mechanical systems, and a dynamical systems approach to energy absorption or explosion.

The influence of a salivary coating on the molecular surface composition of oral streptococci as determined by Fourier transform infrared spectroscopy

NASA Astrophysics Data System (ADS)

van der Mei, H. C.; Noordmans, J.; Busscher, H. J.

In order to determine the influence of saliva treatment on the molecular surface composition of oral streptococci, infrared transmission spectroscopy on freeze-dried cells mixed in KBr was used. All IR spectra show similar absorption bands for the saliva-coated and uncoated strains involved, with the most important absorption bands located at 2930cm -1 (CH), 1653 cm -1 (AmI), 1541 cm -1 (AmII) and two bands at 1236 cm -1 and 1082cm -1, which were assigned to phosphate and sugar groups. However, calculation of absorption band ratios normalized with respect to the CH band around 2930cm -1, showed major differences between the saliva-coated and uncoated strains. All strains demonstrated an increase in the AmI/CH and AmII/CH absorption band ratios after saliva treatment indicative for protein adsorption, except for Streptococcus mitis BA showing a small decrease in the AmI/CH absorption band ratio. Two positive relationships could furthermore be established both between the AmII/CH absorption band ratio with the N/C elemental surface concentration ratio of the strains, previously determined from X-ray Photoelectron Spectroscopy (XPS) as well as between AmI/CH with the fraction of carbon atoms at the surface involved in amide bonds, also determined by XPS. This study clearly demonstrates the possibility of IR spectroscopy to determine the molecular surface properties of freeze-dried micro-organisms, as illustrated here from a comparison between the molecular composition of untreated and saliva-treated oral streptococcal strains.

Measurements of the weak UV absorptions of isoprene and acetone at 261-275 nm using cavity ringdown spectroscopy for evaluation of a potential portable ringdown breath analyzer.

PubMed

Sahay, Peeyush; Scherrer, Susan T; Wang, Chuji

2013-06-26

The weak absorption spectra of isoprene and acetone have been measured in the wavelength range of 261-275 nm using cavity ringdown spectroscopy. The measured absorption cross-sections of isoprene in the wavelength region of 261-266 nm range from 3.65 × 10⁻²¹ cm².molecule⁻¹ at 261 nm to 1.42 × 10⁻²¹ cm².molecule⁻¹ at 266 nm; these numbers are in good agreement with the values reported in the literature. In the longer wavelength range of 270-275 nm, however, where attractive applications using a single wavelength compact diode laser operating at 274 nm is located, isoprene has been reported in the literature to have no absorption (too weak to be detected). Small absorption cross-sections of isoprene in this longer wavelength region are measured using cavity ringdown spectroscopy for the first time in this work, i.e., 6.20 × 10⁻²³ cm².molecule⁻¹ at 275 nm. With the same experimental system, wavelength-dependent absorption cross-sections of acetone have also been measured. Theoretical detection limits of isoprene and comparisons of absorbance of isoprene, acetone, and healthy breath gas in this wavelength region are also discussed.

Characterization of nitride hole lateral transport in a charge trap flash memory by using a random telegraph signal method

NASA Astrophysics Data System (ADS)

Liu, Yu-Heng; Jiang, Cheng-Min; Lin, Hsiao-Yi; Wang, Tahui; Tsai, Wen-Jer; Lu, Tao-Cheng; Chen, Kuang-Chao; Lu, Chih-Yuan

2017-07-01

We use a random telegraph signal method to investigate nitride trapped hole lateral transport in a charge trap flash memory. The concept of this method is to utilize an interface oxide trap and its associated random telegraph signal as an internal probe to detect a local channel potential change resulting from nitride charge lateral movement. We apply different voltages to the drain of a memory cell and vary a bake temperature in retention to study the electric field and temperature dependence of hole lateral movement in a nitride. Thermal energy absorption by trapped holes in lateral transport is characterized. Mechanisms of hole lateral transport in retention are investigated. From the measured and modeled results, we find that thermally assisted trap-to-band tunneling is a major trapped hole emission mechanism in nitride hole lateral transport.

Generation of cavitation luminescence by laser-induced exothermic chemical reaction

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

Jung Park, Han; Diebold, Gerald J.

2013-08-14

Absorption of high power laser radiation by aqueous carbon suspensions is known to result in the formation of highly compressed bubbles of hydrogen and carbon monoxide through the endothermic carbon-steam reaction. The bubbles expand rapidly, overreaching their equilibrium diameter, and then collapse tens to hundreds of microseconds after formation to give a flash of radiation. Here we report on the effects of laser-initiated exothermic chemical reaction on cavitation luminescence. Experiments with hydrogen peroxide added to colloidal carbon suspensions show that both the time of the light flash following the laser pulse and the intensity of luminescence increase with hydrogen peroxidemore » concentration, indicating that large, highly energetic gas bubbles are produced. Additional experiments with colloidal carbon suspensions show the effects of high pressure on the luminescent intensity and its time of appearance following firing of the laser.« less

X-ray absorption spectroscopy using a self-seeded soft X-ray free-electron laser

DOE PAGES

Kroll, Thomas; Kern, Jan; Kubin, Markus; ...

2016-09-19

X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. But, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. We compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based onmore » self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. Lastly, we show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements.« less

In situ differential reflectance spectroscopy of thin crystalline films of PTCDA on different substrates

NASA Astrophysics Data System (ADS)

Proehl, Holger; Nitsche, Robert; Dienel, Thomas; Leo, Karl; Fritz, Torsten

2005-04-01

We report an investigation of the excitonic properties of thin crystalline films of the archetypal organic semiconductor PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) grown on poly- and single crystalline surfaces. A sensitive setup capable of measuring the optical properties of ultrathin organic molecular crystals via differential reflectance spectroscopy (DRS) is presented. This tool allows to carry out measurements in situ, i.e., during the actual film growth, and over a wide spectral range, even on single crystalline surfaces with high symmetry or metallic surfaces, where widely used techniques like reflection anisotropy spectroscopy (RAS) or fluorescence excitation spectroscopy fail. The spectra obtained by DRS resemble mainly the absorption of the films if transparent substrates are used, which simplifies the analysis. In the case of mono- to multilayer films of PTCDA on single crystalline muscovite mica(0001) and Au(111) substrates, the formation of the solid state absorption from monomer to dimer and further to crystal-like absorption spectra can be monitored.

X-ray absorption spectroscopy using a self-seeded soft X-ray free-electron laser

PubMed Central

Kroll, Thomas; Kern, Jan; Kubin, Markus; Ratner, Daniel; Gul, Sheraz; Fuller, Franklin D.; Löchel, Heike; Krzywinski, Jacek; Lutman, Alberto; Ding, Yuantao; Dakovski, Georgi L.; Moeller, Stefan; Turner, Joshua J.; Alonso-Mori, Roberto; Nordlund, Dennis L.; Rehanek, Jens; Weniger, Christian; Firsov, Alexander; Brzhezinskaya, Maria; Chatterjee, Ruchira; Lassalle-Kaiser, Benedikt; Sierra, Raymond G.; Laksmono, Hartawan; Hill, Ethan; Borovik, Andrew; Erko, Alexei; Föhlisch, Alexander; Mitzner, Rolf; Yachandra, Vittal K.; Yano, Junko; Wernet, Philippe; Bergmann, Uwe

2016-01-01

X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. However, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. Here we compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based on self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. We show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements. PMID:27828320

UV-Vis spectroscopy of tyrosine side-groups in studies of protein structure. Part 2: selected applications.

PubMed

Antosiewicz, Jan M; Shugar, David

In Part 2 we discuss application of several different types of UV-Vis spectroscopy, such as normal, difference, and second-derivative UV absorption spectroscopy, fluorescence spectroscopy, linear and circular dichroism spectroscopy, and Raman spectroscopy, of the side-chain of tyrosine residues in different molecular environments. We review the ways these spectroscopies can be used to probe complex protein structures.

UV-Vis spectroscopy of tyrosine side-groups in studies of protein structure. Part 2: selected applications.

PubMed

Antosiewicz, Jan M; Shugar, David

2016-06-01

In Part 2 we discuss application of several different types of UV-Vis spectroscopy, such as normal, difference, and second-derivative UV absorption spectroscopy, fluorescence spectroscopy, linear and circular dichroism spectroscopy, and Raman spectroscopy, of the side-chain of tyrosine residues in different molecular environments. We review the ways these spectroscopies can be used to probe complex protein structures.

The temperature measurement research for high-speed flow based on tunable diode laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Di, Yue; Jin, Yi; Jiang, Hong-liang; Zhai, Chao

2013-09-01

Due to the particularity of the high-speed flow, in order to accurately obtain its' temperature, the measurement system should has some characteristics of not interfereing with the flow, non-contact measurement and high time resolution. The traditional measurement method cannot meet the above requirements, however the measurement method based on tunable diode laser absorption spectroscopy (TDLAS) technology can meet the requirements for high-speed flow temperature measurement. When the near-infared light of a specific frequency is through the media to be measured, it will be absorbed by the water vapor molecules and then the transmission light intensity is detected by the detector. The temperature of the water vapor which is also the high-speed flow temperature, can be accurately obtained by the Beer-Lambert law. This paper focused on the research of absorption spectrum method for high speed flow temperature measurement with the scope of 250K-500K. Firstly, spectral line selection method for low temperature measurement of high-speed flow is discussed. Selected absorption lines should be isolated and have a high peak absorption within the range of 250-500K, at the same time the interference of the other lines should be avoided, so that a high measurement accuracy can be obtained. According to the near-infrared absorption spectra characteristics of water vapor, four absorption lines at the near 1395 nm and 1409 nm are selected. Secondly, a system for the temperature measurement of the water vapor in the high-speed flow is established. Room temperature are measured through two methods, direct absorption spectroscopy (DAS) and wavelength modulation spectroscopy (WMS) ,the results show that this system can realize on-line measurement of the temperature and the measurement error is about 3%. Finally, the system will be used for temperature measurement of the high-speed flow in the shock tunnel, its feasibility of measurement is analyzed.

Photothermally Activated Motion and Ignition Using Aluminum Nanoparticles

DTIC Science & Technology

2013-01-17

In comparison with alternative sources such as spark ignition,19 laser igni- tion,20 plasma ignition,21 plasma -assisted combustion,22 and combustion...energy-dispersive X-ray spectroscopy measurements of motion-only and afterignition products confirm significant Al oxidation occurs through sintering ...significant Al oxidation occurs through sintering and bursting after the flash exposure. Simulations suggest local heat generation is enhanced by LSPR. The

Vibrational Energy in Molecules and Nanoparticles: Applications to Energetic Materials

DTIC Science & Technology

2009-01-30

of vibrational energy in a polyatomic molecule, nitromethane . Work on water and amino acids partially supported by AFOSR are developmental in nature...have characterized the surface vibrations of HMX explosive and their interaction with polymer binders. We have introduced a major improvement in SFG...Vibrational energy in nitromethane and benzene E. Time resolved spectroscopy of chemistry in flash-heated nanoenergetic materials F. Complete

The use of C-near edge X-ray absorption fine structure spectroscopy for the elaboration of chemistry in lignocellulosics

Treesearch

Lucian A. Lucia; Hiroki Nanko; Alan W. Rudie; Doug G. Mancosky; Sue Wirick

2006-01-01

The research presented elucidates the oxidation chemistry occurring in hydrogen peroxide bleached kraft pulp fibers by employing carbon near edge x-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft x-ray technique that selectively interrogates atomic moieties using photoelectrons (Xrays) of variable energies. The X1A beam line at the National...

Revealing electronic structure changes in Chevrel phase cathodes upon Mg insertion using X-ray absorption spectroscopy

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

Wan, Liwen F.; Wright, Joshua; Perdue, Brian R.

Following previous work predicting the electronic response of the Chevrel phase Mo6S8 upon Mg insertion (Thole et al., Phys. Chem. Chem. Phys., 2015, 17, 22548), we provide the experimental proof, evident in X-ray absorption spectroscopy, to illustrate the charge compensation mechanism of the Chevrel phase compound during Mg insertion and de-insertion processes.

Analysis of an Air Conditioning Coolant Solution for Metal Contamination Using Atomic Absorption Spectroscopy: An Undergraduate Instrumental Analysis Exercise Simulating an Industrial Assignment

ERIC Educational Resources Information Center

Baird, Michael J.

2004-01-01

A real-life analytical assignment is presented to students, who had to examine an air conditioning coolant solution for metal contamination using an atomic absorption spectroscopy (AAS). This hands-on access to a real problem exposed the undergraduate students to the mechanism of AAS, and promoted participation in a simulated industrial activity.

Determination of Fe Content of Some Food Items by Flame Atomic Absorption Spectroscopy (FAAS): A Guided-Inquiry Learning Experience in Instrumental Analysis Laboratory

ERIC Educational Resources Information Center

Fakayode, Sayo O.; King, Angela G.; Yakubu, Mamudu; Mohammed, Abdul K.; Pollard, David A.

2012-01-01

This article presents a guided-inquiry (GI) hands-on determination of Fe in food samples including plantains, spinach, lima beans, oatmeal, Frosted Flakes cereal (generic), tilapia fish, and chicken using flame atomic absorption spectroscopy (FAAS). The utility of the GI experiment, which is part of an instrumental analysis laboratory course,…

[Possibilities of ultrasonic spectroscopy of the blood in the diagnosis of early postoperative inflammatory complications in patients with stomach cancer].

PubMed

Moskalenko, O V

1998-01-01

The indexes of ultrasound wave absorption in the blood serum of patients with gastric cancer were studied using ultrasound spectroscopy method. The coefficient of absorption (CA) changes were registered 1-2 days before the first clinical signs occurrence. While inflammatory complications presence CA had lowered, the daily gradient of lowering had raised.

Speciation and Lability of Ag-, AgCl- and Ag2S-Nanoparticles in Soil Determined by X-ray Absorption Spectroscopy and Diffusive Gradients in Thin Films

EPA Science Inventory

Long-term speciation and lability of silver (Ag-), silver chloride (AgCl-) and silver sulfide nanoparticles (Ag₂S-NPs) in soil were studied by X-ray absorption spectroscopy (XAS), and newly developed "nano" Diffusive Gradients in Thin Films (DGT) devices. These nano-D...

Study of nonlinear absorption properties of reduced graphene oxide by Z-scan technique

NASA Astrophysics Data System (ADS)

Sreeja, V. G.; Vinitha, G.; Reshmi, R.; Anila, E. I.; Jayaraj, M. K.

2017-05-01

Graphene has generated enormous research interest during the last decade due to its significant unique properties and wide applications in the field of optoelectronics and photonics. This research studied the structural and nonlinear absorption properties of reduced graphene oxide (rGO) synthesized by Modified Hummer's method. Structural and physiochemical properties of the rGO were explored with the help of Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy (Raman). Nonlinear absorption property in rGO, was investigated by open aperture Z-scan technique by using a continuous wave (CW) laser. The Z-scan results demonstrate saturable absorption property of rGO with a nonlinear absorption coefficient, β, of -2.62 × 10-4 cm/W, making it suitable for applications in Q switching, generation of ultra-fast high energy pulses in laser cavity and mode lockers.

INFRARED TRANSMISSION SPECTROSCOPY OF THE EXOPLANETS HD 209458b AND XO-1b USING THE WIDE FIELD CAMERA-3 ON THE HUBBLE SPACE TELESCOPE

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

Deming, Drake; Wilkins, Ashlee; McCullough, Peter

Exoplanetary transmission spectroscopy in the near-infrared using the Hubble Space Telescope (HST) NICMOS is currently ambiguous because different observational groups claim different results from the same data, depending on their analysis methodologies. Spatial scanning with HST/WFC3 provides an opportunity to resolve this ambiguity. We here report WFC3 spectroscopy of the giant planets HD 209458b and XO-1b in transit, using spatial scanning mode for maximum photon-collecting efficiency. We introduce an analysis technique that derives the exoplanetary transmission spectrum without the necessity of explicitly decorrelating instrumental effects, and achieves nearly photon-limited precision even at the high flux levels collected in spatial scanmore » mode. Our errors are within 6% (XO-1) and 26% (HD 209458b) of the photon-limit at a resolving power of {lambda}/{delta}{lambda} {approx} 70, and are better than 0.01% per spectral channel. Both planets exhibit water absorption of approximately 200 ppm at the water peak near 1.38 {mu}m. Our result for XO-1b contradicts the much larger absorption derived from NICMOS spectroscopy. The weak water absorption we measure for HD 209458b is reminiscent of the weakness of sodium absorption in the first transmission spectroscopy of an exoplanet atmosphere by Charbonneau et al. Model atmospheres having uniformly distributed extra opacity of 0.012 cm{sup 2} g{sup -1} account approximately for both our water measurement and the sodium absorption. Our results for HD 209458b support the picture advocated by Pont et al. in which weak molecular absorptions are superposed on a transmission spectrum that is dominated by continuous opacity due to haze and/or dust. However, the extra opacity needed for HD 209458b is grayer than for HD 189733b, with a weaker Rayleigh component.« less

Infrared Transmission Spectroscopy of the Exoplanets HD 209458b and XO-1b Using the Wide Field Camera-3 on the Hubble Space Telescope

NASA Astrophysics Data System (ADS)

Deming, Drake; Wilkins, Ashlee; McCullough, Peter; Burrows, Adam; Fortney, Jonathan J.; Agol, Eric; Dobbs-Dixon, Ian; Madhusudhan, Nikku; Crouzet, Nicolas; Desert, Jean-Michel; Gilliland, Ronald L.; Haynes, Korey; Knutson, Heather A.; Line, Michael; Magic, Zazralt; Mandell, Avi M.; Ranjan, Sukrit; Charbonneau, David; Clampin, Mark; Seager, Sara; Showman, Adam P.

2013-09-01

Exoplanetary transmission spectroscopy in the near-infrared using the Hubble Space Telescope (HST) NICMOS is currently ambiguous because different observational groups claim different results from the same data, depending on their analysis methodologies. Spatial scanning with HST/WFC3 provides an opportunity to resolve this ambiguity. We here report WFC3 spectroscopy of the giant planets HD 209458b and XO-1b in transit, using spatial scanning mode for maximum photon-collecting efficiency. We introduce an analysis technique that derives the exoplanetary transmission spectrum without the necessity of explicitly decorrelating instrumental effects, and achieves nearly photon-limited precision even at the high flux levels collected in spatial scan mode. Our errors are within 6% (XO-1) and 26% (HD 209458b) of the photon-limit at a resolving power of λ/δλ ~ 70, and are better than 0.01% per spectral channel. Both planets exhibit water absorption of approximately 200 ppm at the water peak near 1.38 μm. Our result for XO-1b contradicts the much larger absorption derived from NICMOS spectroscopy. The weak water absorption we measure for HD 209458b is reminiscent of the weakness of sodium absorption in the first transmission spectroscopy of an exoplanet atmosphere by Charbonneau et al. Model atmospheres having uniformly distributed extra opacity of 0.012 cm2 g-1 account approximately for both our water measurement and the sodium absorption. Our results for HD 209458b support the picture advocated by Pont et al. in which weak molecular absorptions are superposed on a transmission spectrum that is dominated by continuous opacity due to haze and/or dust. However, the extra opacity needed for HD 209458b is grayer than for HD 189733b, with a weaker Rayleigh component.

Mid-infrared laser absorption spectroscopy of NO2 at elevated temperatures

NASA Astrophysics Data System (ADS)

Sur, Ritobrata; Peng, Wen Yu; Strand, Christopher; Mitchell Spearrin, R.; Jeffries, Jay B.; Hanson, Ronald K.; Bekal, Anish; Halder, Purbasha; Poonacha, Samhitha P.; Vartak, Sameer; Sridharan, Arun K.

2017-01-01

A mid-infrared quantum cascade laser absorption sensor was developed for in-situ detection of NO2 in high-temperature gas environments. A cluster of spin-split transitions near 1599.9 cm-1 from the ν3 absorption band of NO2 was selected due to the strength of these transitions and the low spectral interference from water vapor within this region. Temperature- and species-dependent collisional broadening parameters of ten neighboring NO2 transitions with Ar, O2, N2, CO2 and H2O were measured and reported. The spectral model was validated through comparisons with direct absorption spectroscopy measurements of NO2 seeded in various bath gases. The performance of the scanned wavelength modulation spectroscopy (WMS)-based sensor was demonstrated in a combustion exhaust stream seeded with varying flow rates of NO2, achieving reliable detection of 1.45 and 1.6 ppm NO2 by mole at 600 K and 800 K, respectively, with a measurement uncertainty of ±11%. 2σ noise levels of 360 ppb and 760 ppb were observed at 600 K and 800 K, respectively, in an absorption path length of 1.79 m.

Nanoscale infrared absorption spectroscopy of individual nanoparticles enabled by scattering-type near-field microscopy.

PubMed

Stiegler, Johannes M; Abate, Yohannes; Cvitkovic, Antonija; Romanyuk, Yaroslav E; Huber, Andreas J; Leone, Stephen R; Hillenbrand, Rainer

2011-08-23

Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption. © 2011 American Chemical Society

XAS Studies of Arsenic in the Environment

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

Charnock, J. M.; School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Oxford Road, Manchester, M13 9PL; Polya, D. A.

2007-02-02

Arsenic is present in low concentrations in much of the Earth's crust and changes in its speciation are vital to understanding its transport and toxicity in the environment. We have used X-ray absorption spectroscopy to investigate the coordination sites of arsenic in a wide variety of samples, including soil and earthworm tissues from arsenic-contaminated land, and human hair and nail samples from people exposed to arsenic in Cambodia. Our results confirm the effectiveness of using X-ray absorption near edge structure (XANES) and X-ray absorption fine structure (EXAFS) spectroscopy to determine speciation changes in environmental samples.

Terahertz optical properties of nonlinear optical CdSe crystals

NASA Astrophysics Data System (ADS)

Yan, Dexian; Xu, Degang; Li, Jining; Wang, Yuye; Liang, Fei; Wang, Jian; Yan, Chao; Liu, Hongxiang; Shi, Jia; Tang, Longhuang; He, Yixin; Zhong, Kai; Lin, Zheshuai; Zhang, Yingwu; Cheng, Hongjuan; Shi, Wei; Yao, Jianquan; Wu, Yicheng

2018-04-01

We investigate the optical properties of cadmium selenide (CdSe) crystals in a wide terahertz (THz) range from 0.2 to 6 THz by THz time-domain spectroscopy (THz-TDS) and Fourier transform infrared spectroscopy (FTIR). The refractive index, absorption coefficient and transmittance are measured and analyzed. The properties are characterized by several absorption peaks which represent the relevant phonon vibrations modes. The experimental results are in agreement with the theoretical results. The dispersion and absorption properties of CdSe crystal are analyzed in THz range. These properties indicate a good potential for THz sources and THz modulated devices.

Internal standards in fluorescent X-ray spectroscopy1 1 Publication authorized by the Director, U.S. Geological Survey.

USGS Publications Warehouse

Adler, I.; Axelrod, J.M.

1955-01-01

The use of internal standards in the analysis of ores and minerals of widely-varying matrix by means of fluorescent X-ray spectroscopy is frequently the most practical approach. Internal standards correct for absorption and enhancement effects except when an absorption edge falls between the comparison lines or a very strong emission line falls between the absorption edges responsible for the comparison lines. Particle size variations may introduce substantial errors. One method of coping with the particle size problem is grinding the sample with an added abrasive. ?? 1955.

Supramolecularly engineered perylene bisimide assemblies exhibiting thermal transition from columnar to multilamellar structures.

PubMed

Yagai, Shiki; Usui, Mari; Seki, Tomohiro; Murayama, Haruno; Kikkawa, Yoshihiro; Uemura, Shinobu; Karatsu, Takashi; Kitamura, Akihide; Asano, Atsushi; Seki, Shu

2012-05-09

Perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) was functionalized with ditopic cyanuric acid to organize it into complex columnar architectures through the formation of hydrogen-bonded supermacrocycles (rosette) by complexing with ditopic melamines possessing solubilizing alkoxyphenyl substituents. The aggregation study in solution using UV-vis and NMR spectroscopies showed the formation of extended aggregates through hydrogen-bonding and π-π stacking interactions. The cylindrical fibrillar nanostructures were visualized by microscopic techniques (AFM, TEM), and the formation of lyotropic mesophase was confirmed by polarized optical microscopy and SEM. X-ray diffraction study revealed that a well-defined hexagonal columnar (Col(h)) structure was formed by solution-casting of fibrillar assemblies. All of these results are consistent with the formation of hydrogen-bonded PBI rosettes that spontaneously organize into the Col(h) structure. Upon heating the Col(h) structure in the bulk state, a structural transition to a highly ordered lamellar (Lam) structure was observed by variable-temperature X-ray diffraction, differential scanning calorimetry, and AFM studies. IR study showed that the rearrangement of the hydrogen-bonding motifs occurs during the structural transition. These results suggest that such a striking structural transition is aided by the reorganization in the lowest level of self-organization, i.e., the rearrangement of hydrogen-bonded motifs from rosette to linear tape. A remarkable increase in the transient photoconductivity was observed by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements upon converting the Col(h) structure to the Lam structure. Transient absorption spectroscopy revealed that electron transfer from electron-donating alkoxyphenyl groups of melamine components to electron-deficient PBI moieties takes place, resulting in a higher probability of charge carrier generation in the Lam structure compared to the Col(h) structure.

Project LITE - Light Inquiry Through Experiments

NASA Astrophysics Data System (ADS)

Brecher, K.

2004-12-01

Hands-on, inquiry-based, constructivist activity offers students a powerful way to explore, uncover and ultimately gain a feel for the nature of science. In order to make practicable a more genuine approach to learning astronomy, we have undertaken the development of hands-on (and eyes-on) materials that can be used in introductory undergraduate astronomy courses. These materials focus on light and optics. Over the past several years as part of Project LITE (Light Inquiry Through Experiments), we have developed a kit of optical materials that is integrated with a set of Java applets. The combined kit and software allows students to do actual experiments concerning geometrical optics, fluorescence, phosphorescence, polarization and other topics by making use of the photons that are emitted by their computer screens. We have also developed a suite of over 100 Flash applets that allow students to directly explore many aspects of visual perception. A major effort of the project concerns spectroscopy, since it is arguably the most important tool used by astronomers to disentangle the nature of the universe. It is also one of the most challenging subjects to teach in undergraduate astronomy courses. The spectroscopy component of Project LITE includes take-home laboratory materials and experiments that are integrated with web-based software. We have also developed a novel quantitative handheld binocular spectrometer (patent pending). Our major spectroscopic software is called the Spectrum Explorer (SPEX). It allows students to create, manipulate and explore all types of spectra including blackbody, power law, emission and absorption. We are now extending the SPEX capabilities to help students gain easy access to the astronomical spectra included in the NVO databases. All of the Project LITE software can be found http://lite.bu.edu. Project LITE is supported by Grant #DUE-0125992 from the NSF Division of Undergraduate Education.

Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

NASA Technical Reports Server (NTRS)

Estupinan, E. G.; Nicovich, J. M.; Li, J.; Cunnold, D. M.; Wine, P. H.

2002-01-01

Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and they appear to be the first suggested photochemical mechanism that is capable of explaining the altitude dependence of the observed mass -independent isotopic signature.

Characterization and structural properties of iron in plants.

NASA Astrophysics Data System (ADS)

Dewanamuni, Udya; Dehipawala, Sunil; Gafney, Harry

Iron is one of the most abundant metals in the soil and occurs in a wide range of chemical forms. Humans receive iron through either meat products or plants. Non meat eaters depend on plant product for their daily iron requirement. The iron absorption by plants depends on other minerals present in the soil and soil pH value. The amount of iron present in plants grown with different soil compositions were investigated using X-ray absorption spectroscopy (XAS) and Mossbauer spectroscopy. Based on the X-ray absorption data, the amount of iron in plants vary significantly with soil pH value. The Mossbauer spectroscopy reveals that iron present in the samples has the form Fe3+ or electron density at the site of the iron nucleus similar to that of Fe3+. CUNY Research Scholar Program, MSEIP.

Developing Photoacoustic Tomography Devices for Translational Medicine and Basic Science Research

NASA Astrophysics Data System (ADS)

Wong, Terence Tsz Wai

Photoacoustic (PA) tomography (PAT) provides volumetric images of biological tissue with scalable spatial resolutions and imaging depths, while preserving the same imaging contrast--optical absorption. Taking the advantage of its 100% sensitivity to optical absorption, PAT has been widely applied in structural, functional, and molecular imaging, with both endogenous and exogenous contrasts, at superior depths than pure optical methods. Intuitively, hemoglobin has been the most commonly studied biomolecule in PAT due to its strong absorption in the visible wavelength regime. One of the main focuses of this dissertation is to investigate an underexplored wavelength regime--ultraviolet (UV), which allows us to image cell nuclei without labels and generate histology-like images naturally from unprocessed biological tissue. These preparation-free and easy-to-interpret characteristics open up new possibilities for PAT to become readily applicable to other important biomedical problems (e.g., surgical margin analysis, Chapter 2) or basic science studies (e.g., whole-organ imaging, Chapter 3). For instance, we developed and optimized a PA microscopy system with UV laser illumination (UV-PAM) to achieve fast, label-free, multilayered, and histology-like imaging of human breast cancer in Chapter 2. These imaging abilities are essential to intraoperative surgical margin analysis, which enables promptly directed re-excision and reduces the number of repeat surgeries. We have incorporated the Gruneisen relaxation (GR) effect with UV-PAM to improve the performance of our UV-PAM system (e.g., the axial resolution), thus providing more accurate three-dimensional (3D) information (Chapter 4). The nonlinear PA signals caused by the GR effect enable optical sectioning capability, revealing important 3D cell nuclear distributions and internal structures for cancer diagnosis. In the final focus of this dissertation, we have implemented a low-cost PA computed tomography (PACT) system with a single xenon flash lamp as the illumination source (Chapter 5). Lasers have been commonly used as illumination light sources in PACT. However, lasers are usually expensive and bulky, limiting their applicability in many clinical usages. Therefore, the use of a single xenon flash lamp as an alternative light source was explored. We found that PACT images acquired with flash lamp illumination were comparable to those acquired with laser illumination. This low-cost and portable PACT system opens up new potentials, such as low-cost skin melanoma imaging in undeveloped countries.

Intrinsic Raman spectroscopy for quantitative biological spectroscopy Part II

PubMed Central

Bechtel, Kate L.; Shih, Wei-Chuan; Feld, Michael S.

2009-01-01

We demonstrate the effectiveness of intrinsic Raman spectroscopy (IRS) at reducing errors caused by absorption and scattering. Physical tissue models, solutions of varying absorption and scattering coefficients with known concentrations of Raman scatterers, are studied. We show significant improvement in prediction error by implementing IRS to predict concentrations of Raman scatterers using both ordinary least squares regression (OLS) and partial least squares regression (PLS). In particular, we show that IRS provides a robust calibration model that does not increase in error when applied to samples with optical properties outside the range of calibration. PMID:18711512

Indirect absorption spectroscopy using quantum cascade lasers: mid-infrared refractometry and photothermal spectroscopy.

PubMed

Pfeifer, Marcel; Ruf, Alexander; Fischer, Peer

2013-11-04

We record vibrational spectra with two indirect schemes that depend on the real part of the index of refraction: mid-infrared refractometry and photothermal spectroscopy. In the former, a quantum cascade laser (QCL) spot is imaged to determine the angles of total internal reflection, which yields the absorption line via a beam profile analysis. In the photothermal measurements, a tunable QCL excites vibrational resonances of a molecular monolayer, which heats the surrounding medium and changes its refractive index. This is observed with a probe laser in the visible. Sub-monolayer sensitivities are demonstrated.

Characterization of photo-induced valence tautomerism in a cobalt-dioxolene complex by ultrafast spectroscopy

NASA Astrophysics Data System (ADS)

Beni, A.; Bogani, L.; Bussotti, L.; Dei, A.; Gentili, P. L.; Righini, R.

2005-01-01

The valence tautomerism of low-spin CoIII(Cat-N-BQ)(Cat-N-SQ) was investigated by means of UV-vis pump-probe transient absorption spectroscopy in chloroform. By exciting the CT transition of the complex at 480 nm, an intramolecular electron transfer process is selectively triggered. The photo-induced charge transfer is pursued by a cascade of two main molecular events characterized by the ultrafast transient absorption spectroscopy: the first gives rise to the metastable high-spin CoII(Cat-N-BQ)2 that, secondly, reaches the chemical equilibrium with the reactant species.

Ultrafast relaxation dynamics of nitric oxide synthase studied by visible broadband transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S.

2017-09-01

Ultrafast dynamics of endothelial nitric oxide synthase (eNOS) oxygenase domain was studied by transient absorption spectroscopy pumping at Soret band. The broadband visible probe spectrum has visualized the relaxation dynamics from the Soret band to Q-band and charge transfer (CT) band. Supported by two-dimensional correlation spectroscopy, global fitting analysis has successfully concluded the relaxation dynamics from the Soret band to be (1) electronic transition to Q-band (0.16 ps), (2) ligand dissociation and CT (0.94 ps), (3) relaxation of the CT state (4.0 ps), and (4) ligand rebinding (59 ps).

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

DOE PAGES

Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2016-06-06

Copper ferrite, CuFe 2 O 4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe 2 O 4. A phase pure tetragonal CuFe 2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structuremore » (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(II) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(III) cations to octahedral positions previously occupied by copper(II). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

PubMed

Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

2016-06-22

Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

NASA Technical Reports Server (NTRS)

Cooper, David E.

1986-01-01

Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.

Novel visualization studies of lignocellulosic oxidation chemistry by application of C-near edge X-ray absorption fine structure spectroscopy

Treesearch

Douglas G. Mancosky; Lucian A. Lucia; Hiroki Nanko; Sue Wirick; Alan W. Rudie; Robert Braun

2005-01-01

The research presented herein is the first attempt to probe the chemical nature of lignocellulosic samples by the application of carbon near edge X-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft X-ray technique that principally provides selective interrogation of discrete atomic moieties using photoelectrons of variable energies. The X1A beam...

Label free detection of phospholipids by infrared absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ahmed, Tahsin; Foster, Erick; Vigil, Genevieve; Khan, Aamir A.; Bohn, Paul; Howard, Scott S.

2014-08-01

We present our study on compact, label-free dissolved lipid sensing by combining capillary electrophoresis separation in a PDMS microfluidic chip online with mid-infrared (MIR) absorption spectroscopy for biomarker detection. On-chip capillary electrophoresis is used to separate the biomarkers without introducing any extrinsic contrast agent, which reduces both cost and complexity. The label free biomarker detection could be done by interrogating separated biomarkers in the channel by MIR absorption spectroscopy. Phospholipids biomarkers of degenerative neurological, kidney, and bone diseases are detectable using this label free technique. These phospholipids exhibit strong absorption resonances in the MIR and are present in biofluids including urine, blood plasma, and cerebrospinal fluid. MIR spectroscopy of a 12-carbon chain phosphatidic acid (PA) (1,2-dilauroyl-snglycero- 3-phosphate (sodium salt)) dissolved in N-methylformamide, exhibits a strong amide peak near wavenumber 1660 cm-1 (wavelength 6 μm), arising from the phosphate headgroup vibrations within a low-loss window of the solvent. PA has a similar structure to many important phospholipids molecules like phosphatidylcholine (PC), phosphatidylinositol (PI), phosphatidylethanolamine (PE), phosphatidylglycerol (PG), and phosphatidylserine (PS), making it an ideal molecule for initial proof-of-concept studies. This newly proposed detection technique can lead us to minimal sample preparation and is capable of identifying several biomarkers from the same sample simultaneously.

Quantitative analysis by UV-Vis absorption spectroscopy of amino groups attached to the surface of carbon-based nanoparticles

NASA Astrophysics Data System (ADS)

Saraswati, T. E.; Astuti, A. R.; Rismana, N.

2018-03-01

Carbon-based nanoparticles must be modified due to their wide array of applications, especially when they are used as biomaterials. After modifying, quantitative analysis of the functional group is essential to evaluate a number of the available functional groups applied for further functionalization. In this study, we modified the carbon-based nanoparticles by amino group using submerged arc discharge in different liquids. The attached amino groups were then characterised and quantified by UV-Vis spectroscopy. This amino group functionalization was also confirmed by Fourier transform infrared (FTIR) spectra. The FTIR spectra of amine-modified nanoparticles show the definitive absorption peaks of N—H amine, C—H, C=O, C—N and Fe—O at 3418.97; 3000–2850 1700–1600 1400–1100 and 480-550 cm-1, respectively. The amine groups have different performance signals between the amine-modified and unmodified nanoparticles. The FTIR spectra results were correlated with the UV-Vis absorption spectroscopy method using acidic methyl orange. The UV-Vis absorption spectroscopy shows that the absorbance of methyl orange represented to amino groups number was 1.3 times higher when the pH of the solution was increased. The absorbance intensity was then used to estimate the quantity of amine groups attached.

Flash microwave synthesis and sintering of nanosized La{sub 0.75}Sr{sub 0.25}Cr{sub 0.93}Ru{sub 0.07}o{sub 3-{delta}} for fuel cell application

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

Combemale, L., E-mail: lionel.combemale@u-bourgogne.f; Caboche, G.; Stuerga, D.

2009-10-15

Perovskite-oxide nanocrystals of La{sub 0.75}Sr{sub 0.25}Cr{sub 0.93}Ru{sub 0.07}O{sub 3-{delta}} with a mean size around 10 nm were prepared by microwave flash synthesis. This reaction was performed in alcoholic solution using metallic salts, sodium ethoxide and microwave autoclave. The obtained powder was characterised after purification by energy dispersive X-ray analysis (EDX), X-ray powder diffraction (XRD), BET adsorption technique, photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM). The results show that integrated perovskite-type phase and uniform particle size were obtained in the microwave treated samples. At last the synthesised powder was directly used in a sintering process. A porous solid, inmore » accordance with the expected applications, was then obtained at low sintering temperature (1000 deg. C) without use of pore forming agent. - Graphical abstract: TEM photograph of La{sub 0.75}Sr{sub 0.25}Cr{sub 0.93}Ru{sub 0.07}O{sub 3-{delta}} obtained by microwave flash synthesis. This picture confirms the nanometric size of the ceramic particles.« less

Vibrational energy on surfaces: Ultrafast flash-thermal conductance of molecular monolayers

NASA Astrophysics Data System (ADS)

Dlott, Dana

2008-03-01

Vibrational energy flow through molecules remains a perennial problem in chemical physics. Usually vibrational energy dynamics are viewed through the lens of time-dependent level populations. This is natural because lasers naturally pump and probe vibrational transitions, but it is also useful to think of vibrational energy as being conducted from one location in a molecule to another. We have developed a new technique where energy is driven into a specific part of molecules adsorbed on a metal surface, and ultrafast nonlinear coherent vibrational spectroscopy is used to watch the energy arrive at another part. This technique is the analog of a flash thermal conductance apparatus, except it probes energy flow with angstrom spatial and femtosecond temporal resolution. Specific examples to be presented include energy flow along alkane chains, and energy flow into substituted benzenes. Ref: Z. Wang, J. A. Carter, A. Lagutchev, Y. K. Koh, N.-H. Seong, D. G. Cahill, and D. D. Dlott, Ultrafast flash thermal conductance of molecular chains, Science 317, 787-790 (2007). This material is based upon work supported by the National Science Foundation under award DMR 0504038 and the Air Force Office of Scientific Research under award FA9550-06-1-0235.

Characterization of Lignin in Situ by Photoacoustic Spectroscopy

PubMed Central

Gould, J. Michael

1982-01-01

Photoacoustic spectroscopy is a recently developed nondestructive analytical technique that provides ultraviolet, visible, and infrared absorption spectra from intensely light scattering, solid, and/or optically opaque materials not suitable for conventional spectrophotometric analysis. In wood and other lignocellulosics, the principal ultraviolet absorption bands, in the absence of photosynthetic pigments, arise from the aromatic lignin component of the cell walls. Photoacoustic spectra of extracted lignin fragments (milled wood lignin) and synthetic lignin-like polymers contain a single major absorption band at 280 nanometers with an absorption tail extending beyond 400 nanometers. Photoacoustic spectra of pine, maple, and oak lignin in situ contain a broad primary absorption band at 300 nanometers and a longer wavelength shoulder around 370 nanometers. Wheat lignin in situ, on the other hand, exhibits two principle absorption peaks, at 280 nanometers and 320 nanometers. The presence of absorption bands at wavelengths greater than 300 nanometers in intact lignin could result from (a) interacting, nonconjugated chromophores, or (b) the presence of more highly conjugated structural components formed as the result of oxidation of the polymer. Evidence for the latter comes from the observation that, on the outer surface of senescent, field-dried wheat culms (stems), new absorption bands in the 350 to 400 nanometer region predominate. These new bands are less apparent on the outer surface of presenescent wheat culms and are virtually absent on the inner surface of either senescent or presenescent culms, suggesting that the appearance of longer wavelength absorption bands in senescent wheat is the result of accumulated photochemical modifications of the ligin polymer. These studies also demonstrate photoacoustic spectroscopy to be an important new tool for the investigation of insoluble plant components. PMID:16662709

Rotational and Vibrational Temperature Measurements in the LDR High Enthalpy Shock Tunnel HEG Using LIF and Flash Lamp Absorption

DTIC Science & Technology

2000-04-01

somewhat by using wavelength [nm] other materials than steel (the source of Fe), such as copper alloys , but generally it can’t be fullyFig. 12 Emission...dhedNO AX (1-0) /,k-^ "’’-emcted abs~rt ~ 0.5 -- eraged measured NOabooo - Calc (T-•700Tt’r2500 K) -.7,1 No (1.4% 17S) 44050 44100 44150 44200 44250 44300

The yield of N/2D/ atoms in the dissociative recombination of NO/+/

NASA Technical Reports Server (NTRS)

Kley, D.; Lawrence, G. M.; Stone, E. J.

1977-01-01

The quantum yield or branching ratio of N(2D) atoms formed in the reaction e + NO(+) yields N + O was measured to be 76% plus or minus 6%. Photoionization of buffered nitric oxide by a flash lamp was studied using time-resolved atomic absorption. Atoms were produced both by direct photodissociation and by dissociative recombination, and these two effects were separated by means of SF6 as an electron scavenger.

Ignition Characteristics of Single-Walled Carbon Nanotubes (SWCNTs) Utilizing a Camera Flash for Distributed Ignition of Liquid Sprays (Preprint)

DTIC Science & Technology

2008-10-01

acoustic phenomenon. Our results indicate that the shorter pulse width (with lower energy/pulse) required ~30-35 mJ/pulse to initiate ignition of... acoustic behavior and some other novel phenomena associated with radiation absorption by SWCNTs. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17...pressure level (SPL) from the photo acoustic phenomenon. Our results indicate that the shorter pulse width (with lower energy/pulse) required ~30-35

Laser absorption spectroscopy applied to monitoring of short-lived climate pollutants (SLCPs)

NASA Astrophysics Data System (ADS)

Wang, Gaoxuan; Shen, Fengjiao; Yi, Hongming; Hubert, Patrice; Deguine, Alexandre; Petitprez, Denis; Maamary, Rabih; Augustin, Patrick; Fourmentin, Marc; Fertein, Eric; Sigrist, Markus W.; Ba, Tong-Nguyen; Chen, Weidong

2018-06-01

Enhanced mitigation of short-lived climate pollutants (SLCPs) has been recently paid more attention in order to provide more sizeable short-term reductions of global warming effects over the next several decades. We overview in this article our recent progress in the development of spectroscopic instruments for optical monitoring of major SLCPs based on laser absorption spectroscopy. Methane (CH4) and black carbon (BC) are the most important SLCPs contributing to the human enhancement of the global greenhouse effect after CO2. We present optical sensing of these two climate-change related atmospheric species to illustrate how "classical" spectroscopy can help to address today's challenging issues: (1) Photoacoustic measurements of BC optical absorption coefficient in order to determine its radiative-forcing related optical parameters (such as mass absorption coefficient, absorption Ångström coefficient) with higher precision (∼7.4% compared to 12-30% for filter-based methods routinely used nowadays). The 1σ (SNR = 1) minimum measurable volumetric mass density of 21 ng/m3 (in 60 s) for black carbon. (2) Direct absorption spectroscopy-based monitoring of methane (CH4) in field campaign to identify pollution source in conjunction with air mass back-trajectory modeling. Using a White-type multipass cell (an effective path-length of 175 m), a 1σ detection limit of 33.3 ppb in 218 s was achieved with a relative measurement precision of 1.1% and an overall measurement uncertainty of about 5.1%. Performance of the custom, lab-based instruments (in terms of detection limits, measurement precision, temporal response, etc.), spectroscopic measurement aspects, experimental details, spectral data processing, analysis and modeling of the observed environmental episode will be presented and discussed.

Titanium-silicon oxide film structures for polarization-modulated infrared reflection absorption spectroscopy

PubMed Central

Dunlop, Iain E.; Zorn, Stefan; Richter, Gunther; Srot, Vesna; Kelsch, Marion; van Aken, Peter A.; Skoda, Maximilian; Gerlach, Alexander; Spatz, Joachim P.; Schreiber, Frank

2010-01-01

We present a titanium-silicon oxide film structure that permits polarization modulated infrared reflection absorption spectroscopy on silicon oxide surfaces. The structure consists of a ~6 nm sputtered silicon oxide film on a ~200 nm sputtered titanium film. Characterization using conventional and scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy and X-ray reflectometry is presented. We demonstrate the use of this structure to investigate a selectively protein-resistant self-assembled monolayer (SAM) consisting of silane-anchored, biotin-terminated poly(ethylene glycol) (PEG). PEG-associated IR bands were observed. Measurements of protein-characteristic band intensities showed that this SAM adsorbed streptavidin whereas it repelled bovine serum albumin, as had been expected from its structure. PMID:20418963

Fluorescent quantification of melanin.

PubMed

Fernandes, Bruno; Matamá, Teresa; Guimarães, Diana; Gomes, Andreia; Cavaco-Paulo, Artur

2016-11-01

Melanin quantification is reportedly performed by absorption spectroscopy, commonly at 405 nm. Here, we propose the implementation of fluorescence spectroscopy for melanin assessment. In a typical in vitro assay to assess melanin production in response to an external stimulus, absorption spectroscopy clearly overvalues melanin content. This method is also incapable of distinguishing non-melanotic/amelanotic control cells from those that are actually capable of performing melanogenesis. Therefore, fluorescence spectroscopy is the best method for melanin quantification as it proved to be highly specific and accurate, detecting even small variations in the synthesis of melanin. This method can also be applied to the quantification of melanin in more complex biological matrices like zebrafish embryos and human hair. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Ultrafast carrier dynamics of titanic acid nanotubes investigated by transient absorption spectroscopy.

PubMed

Wang, Li; Zhao, Hui; Pan, Lin Yun; Weng, Yu Xiang; Nakato, Yoshihiro; Tamai, Naoto

2010-12-01

Carrier dynamics of titanic acid nanotubes (phase of H2Ti2O5.H2O) deposited on a quartz plate was examined by visible/near-IR transient absorption spectroscopy with an ultraviolet excitation. The carrier dynamics of titanic acid nanotubes follows the fast trapping process which attributed to the intrinsic tubular structure, the relaxation of shallow trapped carriers and the recombination as a second-order kinetic process. Transient absorption of titanic acid nanotubes was dominated by the absorption of surface-trapped holes in visible region around 500 nm, which was proved by the faster decay dynamics in the presence of polyvinyl alcohol as a hole-scavenger. However, the slow relaxation of free carriers was much more pronounced in the TiO2 single crystals, as compared with the transient absorption spectra of titanic acid nanotubes under the similar excitation.

Reflectance-mode interferometric near-infrared spectroscopy quantifies brain absorption, scattering, and blood flow index in vivo.

PubMed

Borycki, Dawid; Kholiqov, Oybek; Srinivasan, Vivek J

2017-02-01

Interferometric near-infrared spectroscopy (iNIRS) is a new technique that measures time-of-flight- (TOF-) resolved autocorrelations in turbid media, enabling simultaneous estimation of optical and dynamical properties. Here, we demonstrate reflectance-mode iNIRS for noninvasive monitoring of a mouse brain in vivo. A method for more precise quantification with less static interference from superficial layers, based on separating static and dynamic components of the optical field autocorrelation, is presented. Absolute values of absorption, reduced scattering, and blood flow index (BFI) are measured, and changes in BFI and absorption are monitored during a hypercapnic challenge. Absorption changes from TOF-resolved iNIRS agree with absorption changes from continuous wave NIRS analysis, based on TOF-integrated light intensity changes, an effective path length, and the modified Beer-Lambert Law. Thus, iNIRS is a promising approach for quantitative and noninvasive monitoring of perfusion and optical properties in vivo.

Diagnosis of a two wire X-pinch by X-ray absorption spectroscopy utilizing a doubly curved ellipsoidal crystal

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

Cahill, A. D., E-mail: adc87@cornell.edu; Hoyt, C. L., E-mail: adc87@cornell.edu; Shelkovenko, T. A., E-mail: adc87@cornell.edu

2014-12-15

X-ray absorption spectroscopy is a powerful tool for the diagnosis of plasmas over a wide range of both temperature and density. However, such a measurement is often limited to probing plasmas with temperatures well below that of the x-ray source in order to avoid object plasma emission lines from obscuring important features of the absorption spectrum. This has excluded many plasmas from being investigated by this technique. We have developed an x-ray spectrometer that provides the ability to record absorption spectra from higher temperature plasmas than the usual approach allows without the risk of data contamination by line radiation emittedmore » by the plasma under study. This is accomplished using a doubly curved mica crystal which is bent both elliptically and cylindrically. We present here initial absorption spectra obtained from an aluminum x-pinch plasma.« less

Effects of γ-ray irradiation on optical absorption and laser damage performance of KDP crystals containing arsenic impurities.

PubMed

Guo, D C; Jiang, X D; Huang, J; Wang, F R; Liu, H J; Xiang, X; Yang, G X; Zheng, W G; Zu, X T

2014-11-17

The effects of γ-irradiation on potassium dihydrogen phosphate crystals containing arsenic impurities are investigated with different optical diagnostics, including UV-VIS absorption spectroscopy, photo-thermal common-path interferometer and photoluminescence spectroscopy. The optical absorption spectra indicate that a new broad absorption band near 260 nm appears after γ-irradiation. It is found that the intensity of absorption band increases with the increasing irradiation dose and arsenic impurity concentration. The simulation of radiation defects show that this absorption is assigned to the formation of AsO₄⁴⁻ centers due to arsenic ions substituting for phosphorus ions. Laser-induced damage threshold test is conducted by using 355 nm nanosecond laser pulses. The correlations between arsenic impurity concentration and laser induced damage threshold are presented. The results indicate that the damage performance of the material decreases with the increasing arsenic impurity concentration. Possible mechanisms of the irradiation-induced defects formation under γ-irradiation of KDP crystals are discussed.

Modeling Studies of Inhomogeneity Effects during Laser Flash Photolysis Experiments: A Reaction-Diffusion Approach.

PubMed

Dóka, Éva; Lente, Gábor

2017-04-13

This work presents a rigorous mathematical study of the effect of unavoidable inhomogeneities in laser flash photolysis experiments. There are two different kinds of inhomegenities: the first arises from diffusion, whereas the second one has geometric origins (the shapes of the excitation and detection light beams). Both of these are taken into account in our reported model, which gives rise to a set of reaction-diffusion type partial differential equations. These equations are solved by a specially developed finite volume method. As an example, the aqueous reaction between the sulfate ion radical and iodide ion is used, for which sufficiently detailed experimental data are available from an earlier publication. The results showed that diffusion itself is in general too slow to influence the kinetic curves on the usual time scales of laser flash photolysis experiments. However, the use of the absorbances measured (e.g., to calculate the molar absorption coefficients of transient species) requires very detailed mathematical consideration and full knowledge of the geometrical shapes of the excitation laser beam and the separate detection light beam. It is also noted that the usual pseudo-first-order approach to evaluating the kinetic traces can be used successfully even if the usual large excess condition is not rigorously met in the reaction cell locally.

Structure-Kinetics Correlations in Isostructural Crystals of α-(ortho-Tolyl)-acetophenones: Pinning Down Electronic Effects Using Laser-Flash Photolysis in the Solid State.

PubMed

Ayitou, Anoklase J-L; Flynn, Kristen; Jockusch, Steffen; Khan, Saeed I; Garcia-Garibay, Miguel A

2016-03-02

Aqueous suspensions of nanocrystals in the 200-500 nm size range of isostructural α-(ortho-tolyl)-acetophenone (1a) and α-(ortho-tolyl)-para-methylacetophenone (1b) displayed good absorption characteristics for flash photolysis experiments in a flow system, with transient spectra and decay kinetics with a quality that is similar to that recorded in solution. In contrast to solution measurements, reactions in the solid state were characterized by a rate limiting hydrogen transfer reaction from the triplet excited state and a very short-lived biradical intermediate, which does not accumulate. Notably, the rate for δ-hydrogen atom transfer of 1a (2.7 × 10(7) s(-1)) in the crystalline phase is 18-fold larger than that of 1b (1.5 × 10(6) s(-1)). With nearly identical molecular and crystal structures, this decrease in the rate of δ-hydrogen abstraction can be assigned unambiguously to an electronic effect by the para-methyl group in 1b, which increases the contribution of the (3)π,π* configuration relative to the reactive (3)n,π* configuration in the lowest triplet excited state. These results highlight the potential of relating single crystal X-ray structural data with absolute kinetics from laser flash photolysis.

Sensitized and heavy atom induced production of acenaphthylene triplet: A laser flash photolysis study

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

Samanta, A.; Fessenden, R.W.

1989-07-27

The triplet state of acenaphthylene has been examined by nanosecond laser flash photolysis using sensitization and heavy atom perturbation techniques. Although acenaphthylene does not form any observable triplet upon direct flash excitation, a transient with microsecond lifetime ({lambda}{sub max} = 315 nm) is observable when a solution of the sample is excited by sensitizers (benzophenone, thioxanthone, benzil). This transient is ascribed to the triplet of acenaphthylene on the basis of its quenching behavior toward oxygen, ferrocene, azulene, and {beta}-carotene. Quantitative data concerning the triplet-triplet absorption and quenching constants are presented. The triplet energy is estimated to lie between 46 andmore » 47 kcal/mol. The triplet can also be produced by direct excitation in solvents containing heavy atoms (ethyl bromide, ethyl iodide). The triplet yield is found to increase with an increase of the amount of the heavy atom containing solvent. No saturation limit is obtained. These facts together with the effect of heavy atoms on the T{sub 1} {yields} S{sub 0} process allow the differing behavior of ethyl bromide and ethyl iodide on the photodimerization process of acenaphthylene to be explained. Triplet-state parameters (extinction coefficient and triplet yield) have been estimated in these solvents by the energy-transfer technique and actinometry.« less

A Comparative Study on the Photophysics and Photochemistry of Xanthene Dyes in the Presence of Polyamidoamine (PAMAM) Dendrimers.

PubMed

Arbeloa, Ernesto Maximiliano; Previtali, Carlos Mario; Bertolotti, Sonia Graciela

2018-04-17

The photophysical and photochemical properties of the xanthene dyes Eosin Y, Erythrosin B, and Rose Bengal are evaluated in the presence of amino-terminated polyamidoamine (PAMAM) dendrimers of relatively high generation (G3-G5) in alkaline aqueous solution. UV/Vis absorption and fluorescence spectra of the dyes show bathochromic shifts, which correlate with the size of the dendrimer. Binding constants (K bind ) are calculated from absorption data. The resulting high K bind values indicate strong interactions between both molecules. Triplet-triplet absorption spectra of the dyes are recorded by laser flash photolysis, and a decrease in the triplet lifetimes is observed in the presence of dendrimers. At the same time, an increase in the absorption of the semireduced form of the dyes is observed. Rate constants for triplet quenching ( 3 k q ) and radical quantum yields (Φ R ) are obtained. The results are explained by a very efficient electron-transfer process from PAMAM to xanthene dyes for all of the dye/dendrimer couples that are evaluated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurements of the Weak UV Absorptions of Isoprene and Acetone at 261–275 nm Using Cavity Ringdown Spectroscopy for Evaluation of a Potential Portable Ringdown Breath Analyzer

PubMed Central

Sahay, Peeyush; Scherrer, Susan T.; Wang, Chuji

2013-01-01

The weak absorption spectra of isoprene and acetone have been measured in the wavelength range of 261–275 nm using cavity ringdown spectroscopy. The measured absorption cross-sections of isoprene in the wavelength region of 261–266 nm range from 3.65 × 10−21 cm2·molecule−1 at 261 nm to 1.42 × 10−21 cm2·molecule−1 at 266 nm; these numbers are in good agreement with the values reported in the literature. In the longer wavelength range of 270–275 nm, however, where attractive applications using a single wavelength compact diode laser operating at 274 nm is located, isoprene has been reported in the literature to have no absorption (too weak to be detected). Small absorption cross-sections of isoprene in this longer wavelength region are measured using cavity ringdown spectroscopy for the first time in this work, i.e., 6.20 × 10−23 cm2·molecule−1 at 275 nm. With the same experimental system, wavelength-dependent absorption cross-sections of acetone have also been measured. Theoretical detection limits of isoprene and comparisons of absorbance of isoprene, acetone, and healthy breath gas in this wavelength region are also discussed. PMID:23803787

Flash Photolysis Experiment of o-Methyl Red as a Function of pH: A Low-Cost Experiment for the Undergraduate Physical Chemistry Lab

ERIC Educational Resources Information Center

Larsen, Molly C.; Perkins, Russell J.

2016-01-01

A low-cost, time-resolved spectroscopy experiment appropriate for third year physical chemistry students is presented. Students excite o-methyl red in basic solutions with a laser pointer and use a modular spectrometer with a CCD array detector to monitor the transient spectra as the higher-energy cis conformer of the molecule converts back to the…

Laser induced photoluminescence spectroscopy of cometary radicals

NASA Technical Reports Server (NTRS)

Jackson, W. M.; Cody, R. J.; Sabety-Dzvonik, M.

1976-01-01

Flash photolysis together with laser excitation of the product fragments was used in laboratory studies of cometary radicals. The LIPS method has been applied to the CN radical to determine: (1) Radiative lifetimes of individual rotational levels in the zeroth vibrational level of the B state; (2) energy partitioning during photodissociation of C2N2; and (3) vibrational and rotational excitation during formation of CN radicals in the photodissociation of dicyanoacetylene.

Acceptor and Excitation Density Dependence of the Ultrafast Polaron Absorption Signal in Donor-Acceptor Organic Solar Cell Blends.

PubMed

Zarrabi, Nasim; Burn, Paul L; Meredith, Paul; Shaw, Paul E

2016-07-21

Transient absorption spectroscopy on organic semiconductor blends for solar cells typically shows efficient charge generation within ∼100 fs, accounting for the majority of the charge carriers. In this Letter, we show using transient absorption spectroscopy on blends containing a broad range of acceptor content (0.01-50% by weight) that the rise of the polaron signal is dependent on the acceptor concentration. For low acceptor content (<10% by weight), the polaron signal rises gradually over ∼1 ps with most polarons generated after 200 fs, while for higher acceptor concentrations (>10%) most polarons are generated within 200 fs. The rise time in blends with low acceptor content was also found to be sensitive to the pump fluence, decreasing with increasing excitation density. These results indicate that the sub-100 fs rise of the polaron signal is a natural consequence of both the high acceptor concentrations in many donor-acceptor blends and the high excitation densities needed for transient absorption spectroscopy, which results in a short average distance between the exciton and the donor-acceptor interface.

Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

DOE PAGES

Riddle, Catherine; Czerwinski, Kenneth; Kim, Eunja; ...

2016-01-18

We studied the speciation of pentavalent and hexavalent americium (Am) complexes in nitric acidicby X-ray absorption fine structure spectroscopy (XAFS), UV-visible spectroscopy, and density functional theory (DFT). Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results were consistent with the presence of a mixture of AmO 2 + and AmO 2 2+ with only a small amount AmO 2 present. The resulting average bond distances we found were 1.71 Å for Am=O and 2.44 Å for Am-O. All-electron scalar relativistic calculations were also carried out using DFT to predict the equilibrium geometries and properties ofmore » the AmO 2 + and AmO 2 2+ aquo complexes. Calculated bond distances for the Am(VI) complex are in reasonable agreement with EXAFS data and the computed energy gaps between frontier molecular orbitals suggest a slightly higher kinetic stability and chemical hardness of Am(VI) compared to Am(V).« less

Continuous Wave Ring-Down Spectroscopy for Velocity Distribution Measurements in Plasma

NASA Astrophysics Data System (ADS)

McCarren, Dustin W.

Cavity Ring-Down Spectroscopy CRDS is a proven, ultra-sensitive, cavity enhanced absorption spectroscopy technique. When combined with a continuous wavelength (CW) diode laser that has a sufficiently narrow line width, the Doppler broadened absorption line, i.e., the velocity distribution functions (VDFs) of the absorbing species, can be measured. Measurements of VDFs can be made using established techniques such as laser induced fluorescence (LIF). However, LIF suffers from the requirement that the initial state of the LIF sequence have a substantial density and that the excitation scheme fluoresces at an easily detectable wavelength. This usually limits LIF to ions and atoms with large metastable state densities for the given plasma conditions. CW-CRDS is considerably more sensitive than LIF and can potentially be applied to much lower density populations of ion and atom states. Also, as a direct absorption technique, CW-CRDS measurements only need to be concerned with the species' absorption wavelength and provide an absolute measure of the line integrated initial state density. Presented in this work are measurements of argon ion and neutral VDFs in a helicon plasma using CW-CRDS and LIF.

Near- and Extended-Edge X-Ray-Absorption Fine-Structure Spectroscopy Using Ultrafast Coherent High-Order Harmonic Supercontinua

NASA Astrophysics Data System (ADS)

Popmintchev, Dimitar; Galloway, Benjamin R.; Chen, Ming-Chang; Dollar, Franklin; Mancuso, Christopher A.; Hankla, Amelia; Miaja-Avila, Luis; O'Neil, Galen; Shaw, Justin M.; Fan, Guangyu; Ališauskas, Skirmantas; Andriukaitis, Giedrius; Balčiunas, Tadas; Mücke, Oliver D.; Pugzlys, Audrius; Baltuška, Andrius; Kapteyn, Henry C.; Popmintchev, Tenio; Murnane, Margaret M.

2018-03-01

Recent advances in high-order harmonic generation have made it possible to use a tabletop-scale setup to produce spatially and temporally coherent beams of light with bandwidth spanning 12 octaves, from the ultraviolet up to x-ray photon energies >1.6 keV . Here we demonstrate the use of this light for x-ray-absorption spectroscopy at the K - and L -absorption edges of solids at photon energies near 1 keV. We also report x-ray-absorption spectroscopy in the water window spectral region (284-543 eV) using a high flux high-order harmonic generation x-ray supercontinuum with 109 photons/s in 1% bandwidth, 3 orders of magnitude larger than has previously been possible using tabletop sources. Since this x-ray radiation emerges as a single attosecond-to-femtosecond pulse with peak brightness exceeding 1026 photons/s /mrad2/mm2/1 % bandwidth, these novel coherent x-ray sources are ideal for probing the fastest molecular and materials processes on femtosecond-to-attosecond time scales and picometer length scales.

Evaluation of Optical Depths and Self-Absorption of Strontium and Aluminum Emission Lines in Laser-Induced Breakdown Spectroscopy (LIBS).

PubMed

Alfarraj, Bader A; Bhatt, Chet R; Yueh, Fang Yu; Singh, Jagdish P

2017-04-01

Laser-induced breakdown spectroscopy (LIBS) is a widely used laser spectroscopic technique in various fields, such as material science, forensic science, biological science, and the chemical and pharmaceutical industries. In most LIBS work, the analysis is performed using radiative transitions from atomic emissions. In this study, the plasma temperature and the product [Formula: see text] (the number density N and the absorption path length [Formula: see text]) were determined to evaluate the optical depths and the self-absorption of Sr and Al lines. A binary mixture of strontium nitrate and aluminum oxide was used as a sample, consisting of variety of different concentrations in powder form. Laser-induced breakdown spectroscopy spectra were collected by varying various parameters, such as laser energy, gate delay time, and gate width time to optimize the LIBS signals. Atomic emission from Sr and Al lines, as observed in the LIBS spectra of different sample compositions, was used to characterize the laser induced plasma and evaluate the optical depths and self-absorption of LIBS.

Research on atmospheric CO2 remote sensing with open-path tunable diode laser absorption spectroscopy and comparison methods

NASA Astrophysics Data System (ADS)

Xin, Fengxin; Guo, Jinjia; Sun, Jiayun; Li, Jie; Zhao, Chaofang; Liu, Zhishen

2017-06-01

An open-path atmospheric CO2 measurement system was built based on tunable diode laser absorption spectroscopy (TDLAS). The CO2 absorption line near 2 μm was selected, measuring the atmospheric CO2 with direct absorption spectroscopy and carrying on the comparative experiment with multipoint measuring instruments of the open-path. The detection limit of the TDLAS system is 1.94×10-6. The calibration experiment of three AZ-7752 handheld CO2 measuring instruments was carried out with the Los Gatos Research gas analyzer. The consistency of the results was good, and the handheld instrument could be used in the TDLAS system after numerical calibration. With the contrast of three AZ-7752 and their averages, the correlation coefficients are 0.8828, 0.9004, 0.9079, and 0.9393 respectively, which shows that the open-path TDLAS has the best correlation with the average of three AZ-7752 and measures the concentration of atmospheric CO2 accurately. Multipoint measurement provides a convenient comparative method for open-path TDLAS.

Dynamic Optoelectronic Properties in Perovskite Oxide Thin Films Measured with Ultrafast Transient Absorption & Reflectance Spectroscopy

NASA Astrophysics Data System (ADS)

Smolin, Sergey Y.

Ultrafast transient absorption and reflectance spectroscopy are foundational techniques for studying photoexcited carrier recombination mechanisms, lifetimes, and charge transfer rates. Because quantifying photoexcited carrier dynamics is central to the intelligent design and improvement of many solid state devices, these transient optical techniques have been applied to a wide range of semiconductors. However, despite their promise, interpretation of transient absorption and reflectance data is not always straightforward and often relies on assumptions of physical processes, especially with respect to the influence of heating. Studying the material space of perovskite oxides, the careful collection, interpretation, and analysis of ultrafast data is presented here as a guide for future research into novel semiconductors. Perovskite oxides are a class of transition metal oxides with the chemical structure ABO3. Although traditionally studied for their diverse physical, electronic, and magnetic properties, perovskite oxides have gained recent research attention as novel candidates for light harvesting applications. Indeed, strong tunable absorption, unique interfacial properties, and vast chemical flexibility make perovskite oxides a promising photoactive material system. However, there is limited research characterizing dynamic optoelectronic properties, such as recombination lifetimes, which are critical to know in the design of any light-harvesting device. In this thesis, ultrafast transient absorption and reflectance spectroscopy was used to understand these dynamic optoelectronic properties in highquality, thin (<50 nm) perovskite oxide films grown by molecular beam epitaxy. Starting with epitaxial LaFeO3 (LFO) grown on (LaAlO 3)0.3(Sr2AlTaO6)0.7 (LSAT), transient absorption spectroscopy reveals two photoinduced absorption features at the band gap of LFO at 2.4 eV and at the higher energy absorption edge at 3.5 eV. Using a combination of temperature-dependent, variable-angle spectroscopic ellipsometry and time-resolved ultrafast optical spectroscopy on a type I heterostructure, we clarify thermal and electronic contributions to spectral transients in LaFeO3. Upon comparison to thermally-derived static spectra of LaFeO3, we find that thermal contributions dominate the transient absorption and reflectance spectra above the band gap. A transient photoinduced absorption feature below the band gap at 1.9 eV is not reproduced in the thermally derived spectra and has significantly longer decay kinetics from the thermallyinduced features; therefore, this long lived photoinduced absorption is likely derived, at least partially, from photoexcited carriers with lifetimes much longer than 3 nanoseconds. LaFeO3 has a wide band gap of 2.4 eV but its absorption can be decreased with chemical substitution of Sr for Fe to make it more suitable for various applications. This type of A-site substitution is a common route to change static optical absorption in perovskite oxides, but there are no systematic studies looking at how A-site substitution changes dynamic optoelectronic properties. To understand the relationship between composition and static and dynamic optical properties we worked with the model system of La1-xSrxFeO 3-delta epitaxial films grown on LSAT, uncovering the effects of A-site cation substitution and oxygen stoichiometry. Variable-angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy with broadband visible (1.6 eV to 4 eV) and near-infrared (0.9 eV to 1.5 eV) probes. The sign of the reflectance change in the near-infrared region in LSFO is indicative of carrier bandfilling of newly created electronic states by photoexcited carriers. Moreover, we find that similar transient spectral trends can be induced with A-site substitution or through oxygen vacancies, which is a surprising result. Probing the near-infrared region reveals similar nanosecond (1-3 ns) photoexcited carrier lifetimes for oxygen deficient and stoichiometric films. These results demonstrate that while the static optical absorption is strongly dependent on nominal Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in long lived recombination kinetics. Although this thesis represents one of the first comprehensive studies using broad band transient absorption and reflectance spectroscopy to study dynamic optoelectronic phenomena in perovskite oxides, it can also serve as a guide for the implementation and interpretation of ultrafast spectroscopy in other material systems. Moreover, the ultrafast work on perovskite oxides indicates that these materials have long nanosecond lifetimes required for light harvesting devices and should be investigated further.

New Developments of Broadband Cavity Enhanced Spectroscopic Techniques

NASA Astrophysics Data System (ADS)

Walsh, A.; Zhao, D.; Linnartz, H.; Ubachs, W.

2013-06-01

In recent years, cavity enhanced spectroscopic techniques, such as cavity ring-down spectroscopy (CRDS), cavity enhanced absorption spectroscopy (CEAS), and broadband cavity enhanced absorption spectroscopy (BBCEAS), have been widely employed as ultra-sensitive methods for the measurement of weak absorptions and in the real-time detection of trace species. In this contribution, we introduce two new cavity enhanced spectroscopic concepts: a) Optomechanical shutter modulated BBCEAS, a variant of BBCEAS capable of measuring optical absorption in pulsed systems with typically low duty cycles. In conventional BBCEAS applications, the latter substantially reduces the signal-to-noise ratio (S/N), consequently also reducing the detection sensitivity. To overcome this, we incorporate a fast optomechanical shutter as a time gate, modulating the detection scheme of BBCEAS and increasing the effective duty cycle reaches a value close to unity. This extends the applications of BBCEAS into pulsed samples and also in time-resolved studies. b) Cavity enhanced self-absorption spectroscopy (CESAS), a new spectroscopic concept capable of studying light emitting matter (plasma, flames, combustion samples) simultaneously in absorption and emission. In CESAS, a sample (plasma, flame or combustion source) is located in an optically stable cavity consisting of two high reflectivity mirrors, and here it acts both as light source and absorbing medium. A high detection sensitivity of weak absorption is reached without the need of an external light source, such as a laser or broadband lamp. The performance is illustrated by the first CESAS result on a supersonically expanding hydrocarbon plasma. We expect CESAS to become a generally applicable analytical tool for real time and in situ diagnostics. A. Walsh, D. Zhao, W. Ubachs, H. Linnartz, J. Phys. Chem. A, {dx.doi.org/10.1021/jp310392n}, in press, 2013. A. Walsh, D. Zhao, H. Linnartz Rev. Sci. Instrum. {84}(2), 021608 2013. A. Walsh, D. Zhao, H. Linnartz Appl. Phys. Lett. {101}(9), 091111 2012.

UV-Vis spectroscopy of tyrosine side-groups in studies of protein structure. Part 1: basic principles and properties of tyrosine chromophore.

PubMed

Antosiewicz, Jan M; Shugar, David

Spectroscopic properties of tyrosine residues may be employed in structural studies of proteins. Here we discuss several different types of UV-Vis spectroscopy, like normal, difference and second-derivative UV absorption spectroscopy, fluorescence spectroscopy, linear and circular dichroism spectroscopy, and Raman spectroscopy, and corresponding optical properties of the tyrosine chromophore, phenol, which are used to study protein structure.

UV-Vis spectroscopy of tyrosine side-groups in studies of protein structure. Part 1: basic principles and properties of tyrosine chromophore.

PubMed

Antosiewicz, Jan M; Shugar, David

2016-06-01

Spectroscopic properties of tyrosine residues may be employed in structural studies of proteins. Here we discuss several different types of UV-Vis spectroscopy, like normal, difference and second-derivative UV absorption spectroscopy, fluorescence spectroscopy, linear and circular dichroism spectroscopy, and Raman spectroscopy, and corresponding optical properties of the tyrosine chromophore, phenol, which are used to study protein structure.

Intracavity Laser Absorption Spectroscopy of Platinum Nitride in the Near Infrared

NASA Astrophysics Data System (ADS)

O'Brien, Leah C.; Womack, Kaitlin A.; O'Brien, James J.; Whittemore, Sean

2013-06-01

The (2,0) band of the A^{2}Σ^{-} - X^{2}Π_{1/2} electronic transition of PtN has been recorded using intracavity laser absorption spectroscopy. Transitions from ^{194}PtN, ^{195}PtN, and ^{196}PtN isotopologues are observed, as well as the nuclear hyperfine splitting due to ^{195}Pt with I=1/2. The results of the analysis will be presented and compared with ab initio calculations.

Birge-Sponer Estimation of the C-H Bond Dissociation Energy in Chloroform Using Infrared, Near-Infrared, and Visible Absorption Spectroscopy: An Experiment in Physical Chemistry

ERIC Educational Resources Information Center

Myrick, M. L.; Greer, A. E.; Nieuwland, A. A.; Priore, R. J.; Scaffidi, J.; Andreatta, Danielle; Colavita, Paula

2008-01-01

The fundamental and overtone vibrational absorption spectroscopy of the C-H unit in CHCl[subscript 3] is measured for transitions from the v = 0 energy level to v = 1 through v = 5 energy levels. The energies of the transitions exhibit a linearly-decreasing spacing between adjacent vibrational levels as the vibrational quantum number increases.…

Excitation energy dependence of excited states dynamics in all- trans-carotenes determined by femtosecond absorption and fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Kosumi, Daisuke; Yanagi, Kazuhiro; Nishio, Tomohiro; Hashimoto, Hideki; Yoshizawa, Masayuki

2005-06-01

Ultrafast relaxation kinetics in β-carotene and lycopene has been investigated by femtosecond absorption and fluorescence spectroscopies using tunable excitation pulses. The transient signals induced by the photoexcitation with larger excess energy have broader bands and longer lifetimes both in the 11Bu+and21Ag- excited states. The excess vibrational energy remains longer than several picoseconds and slows the relaxation kinetics in carotenoids.

Confocal depth-resolved fluorescence micro-X-ray absorption spectroscopy for the study of cultural heritage materials: a new mobile endstation at the Beijing Synchrotron Radiation Facility

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

Chen, Guang; Chu, Shengqi; Sun, Tianxi

A confocal fluorescence endstation for depth-resolved micro-X-ray absorption spectroscopy is described. A polycapillary half-lens defines the incident beam path and a second polycapillary half-lens at 90° defines the probe sample volume. An automatic alignment program based on an evolutionary algorithm is employed to make the alignment procedure efficient. This depth-resolved system was examined on a general X-ray absorption spectroscopy (XAS) beamline at the Beijing Synchrotron Radiation Facility. Sacrificial red glaze (AD 1368–1644) china was studied to show the capability of the instrument. As a mobile endstation to be applied on multiple beamlines, the confocal system can improve the function andmore » flexibility of general XAS beamlines, and extend their capabilities to a wider user community.« less

In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

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

McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.

2010-12-03

Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example,more » this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.« less

Gas trace detection with cavity enhanced absorption spectroscopy: a review of its process in the field

NASA Astrophysics Data System (ADS)

Liu, Siqi; Luo, Zhifu; Tan, Zhongqi; Long, Xingwu

2016-11-01

Cavity-enhanced absorption spectroscopy (CEAS) is a technology in which the intracavity absorption is deduced from the intensity of light transmitted by the high finesse optical cavity. Then the samples' parameters, such as their species, concentration and absorption cross section, would be detection. It was first proposed and demonstrated by Engeln R. [1] and O'Keefe[2] in 1998. This technology has extraordinary detection sensitivity, high resolution and good practicability, so it is used in many fields , such as clinical medicine, gas detection and basic physics research. In this paper, we focus on the use of gas trace detection, including the advance of CEAS over the past twenty years, the newest research progresses, and the prediction of this technology's development direction in the future.

The visible absorption spectrum of NO3 measured by high-resolution Fourier transform spectroscopy

NASA Astrophysics Data System (ADS)

Orphal, J.; Fellows, C. E.; Flaud, P.-M.

2003-02-01

The visible absorption spectrum of the nitrate radical NO3 has been measured using high-resolution Fourier transform spectroscopy. The spectrum was recorded at 294 K using a resolution of 0.6 cm-1 (corresponding to 0.026 nm at 662 nm) and covers the 12600-21500 cm-1 region (465-794 nm). Compared to absorption spectra of NO3 recorded previously, the new data show improvements concerning absolute wavelength calibration (uncertainty 0.02 cm-1), and spectral resolution. A new interpretation and model of the temperature dependence of the strong (0-0) band around 662 nm are proposed. The results are important for long-path tropospheric absorption measurements of NO3 and optical remote sensing of the Earth's atmosphere from space.

Low-lying singlet states of carotenoids having 8-13 conjugated double bonds as determined by electronic absorption spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Peng; Nakamura, Ryosuke; Kanematsu, Yasuo; Koyama, Yasushi; Nagae, Hiroyoshi; Nishio, Tomohiro; Hashimoto, Hideki; Zhang, Jian-Ping

2005-07-01

Electronic absorption spectra were recorded at room temperature in solutions of carotenoids having different numbers of conjugated double bonds, n = 8-13, including a spheroidene derivatives, neurosporene, spheroidene, lycopene, anhydrorhodovibrin and spirilloxanthin. The vibronic states of 1Bu+(v=0-4), 2Ag-(v=0-3), 3Ag- (0) and 1Bu- (0) were clearly identified. The arrangement of the four electronic states determined by electronic absorption spectroscopy was identical to that determined by measurement of resonance Raman excitation profiles [K. Furuichi et al., Chem. Phys. Lett. 356 (2002) 547] for carotenoids in crystals.

Practical Problems in the Cement Industry Solved by Modern Research Techniques

ERIC Educational Resources Information Center

Daugherty, Kenneth E.; Robertson, Les D.

1972-01-01

Practical chemical problems in the cement industry are being solved by such techniques as infrared spectroscopy, gas chromatography-mass spectrometry, X-ray diffraction, atomic absorption and arc spectroscopy, thermally evolved gas analysis, Mossbauer spectroscopy, transmission and scanning electron microscopy. (CP)

Breath Analysis Using Laser Spectroscopic Techniques: Breath Biomarkers, Spectral Fingerprints, and Detection Limits

PubMed Central

Wang, Chuji; Sahay, Peeyush

2009-01-01

Breath analysis, a promising new field of medicine and medical instrumentation, potentially offers noninvasive, real-time, and point-of-care (POC) disease diagnostics and metabolic status monitoring. Numerous breath biomarkers have been detected and quantified so far by using the GC-MS technique. Recent advances in laser spectroscopic techniques and laser sources have driven breath analysis to new heights, moving from laboratory research to commercial reality. Laser spectroscopic detection techniques not only have high-sensitivity and high-selectivity, as equivalently offered by the MS-based techniques, but also have the advantageous features of near real-time response, low instrument costs, and POC function. Of the approximately 35 established breath biomarkers, such as acetone, ammonia, carbon dioxide, ethane, methane, and nitric oxide, 14 species in exhaled human breath have been analyzed by high-sensitivity laser spectroscopic techniques, namely, tunable diode laser absorption spectroscopy (TDLAS), cavity ringdown spectroscopy (CRDS), integrated cavity output spectroscopy (ICOS), cavity enhanced absorption spectroscopy (CEAS), cavity leak-out spectroscopy (CALOS), photoacoustic spectroscopy (PAS), quartz-enhanced photoacoustic spectroscopy (QEPAS), and optical frequency comb cavity-enhanced absorption spectroscopy (OFC-CEAS). Spectral fingerprints of the measured biomarkers span from the UV to the mid-IR spectral regions and the detection limits achieved by the laser techniques range from parts per million to parts per billion levels. Sensors using the laser spectroscopic techniques for a few breath biomarkers, e.g., carbon dioxide, nitric oxide, etc. are commercially available. This review presents an update on the latest developments in laser-based breath analysis. PMID:22408503

Underresolved absorption spectroscopy of OH radicals in flames using broadband UV LEDs

NASA Astrophysics Data System (ADS)

White, Logan; Gamba, Mirko

2018-04-01

A broadband absorption spectroscopy diagnostic based on underresolution of the spectral absorption lines is evaluated for the inference of species mole fraction and temperature in combustion systems from spectral fitting. The approach uses spectrally broadband UV light emitting diodes and leverages low resolution, small form factor spectrometers. Through this combination, the method can be used to develop high precision measurement sensors. The challenges of underresolved spectroscopy are explored and addressed using spectral derivative fitting, which is found to generate measurements with high precision and accuracy. The diagnostic is demonstrated with experimental measurements of gas temperature and OH mole fraction in atmospheric air/methane premixed laminar flat flames. Measurements exhibit high precision, good agreement with 1-D flame simulations, and high repeatability. A newly developed model of uncertainty in underresolved spectroscopy is applied to estimate two-dimensional confidence regions for the measurements. The results of the uncertainty analysis indicate that the errors in the outputs of the spectral fitting procedure are correlated. The implications of the correlation between uncertainties for measurement interpretation are discussed.

Infrared spectroscopy of molecular submonolayers on surfaces by infrared scanning tunneling microscopy: tetramantane on Au111.

PubMed

Pechenezhskiy, Ivan V; Hong, Xiaoping; Nguyen, Giang D; Dahl, Jeremy E P; Carlson, Robert M K; Wang, Feng; Crommie, Michael F

2013-09-20

We have developed a new scanning-tunneling-microscopy-based spectroscopy technique to characterize infrared (IR) absorption of submonolayers of molecules on conducting crystals. The technique employs a scanning tunneling microscope as a precise detector to measure the expansion of a molecule-decorated crystal that is irradiated by IR light from a tunable laser source. Using this technique, we obtain the IR absorption spectra of [121]tetramantane and [123]tetramantane on Au(111). Significant differences between the IR spectra for these two isomers show the power of this new technique to differentiate chemical structures even when single-molecule-resolved scanning tunneling microscopy (STM) images look quite similar. Furthermore, the new technique was found to yield significantly better spectral resolution than STM-based inelastic electron tunneling spectroscopy, and to allow determination of optical absorption cross sections. Compared to IR spectroscopy of bulk tetramantane powders, infrared scanning tunneling microscopy (IRSTM) spectra reveal narrower and blueshifted vibrational peaks for an ordered tetramantane adlayer. Differences between bulk and surface tetramantane vibrational spectra are explained via molecule-molecule interactions.

Two-Photon Absorption Spectroscopy of Rubidium with a Dual-Comb Tequnique

NASA Astrophysics Data System (ADS)

Nishiyama, Akiko; Yoshida, Satoru; Hariki, Takuya; Nakajima, Yoshiaki; Minoshima, Kaoru

2017-06-01

Dual-comb spectroscopies have great potential for high-resolution molecular and atomic spectroscopies, thanks to the broadband comb spectrum consisting of dense narrow modes. In this study, we apply the dual-comb system to Doppler-free two-photon absorption spectroscopy. The outputs of two frequency combs excite several two-photon transitions of rubidium, and we obtained broadband Doppler-free spectra from dual-comb fluorescence signals. The fluorescence detection scheme circumvents the sensitivity limit which is effectively determined by the dynamic range of photodetectors in absorption-based dual-comb spectroscopies. Our system realized high-sensitive, Doppler-free high-resolution and broadband atomic spectroscopy. A part of observed spectra of 5S_{1/2} - 5D_{5/2} transition is shown in the figure. The hyperfine structures of the F" = 1 - F' = 3,2,1 transitions are fully-resolved and the spectral widths are approximately 5 MHz. The absolute frequency axis is precisely calibrated from comb mode frequencies which were stabilized to a GPS-disciplined clock. This work was supported by JST through the ERATO MINOSHIMA Intelligent Optical Synthesizer Project and Grant-in-Aid for JSPS Fellows (16J02345). A. Nishiyama, S. Yoshida, Y. Nakajima, H. Sasada, K. Nakagawa, A. Onae, K. and Minoshima, Opt. Express 24, 25894 (2016). A. Hipke, S. A. Meek, T. Ideguchi, T.W. Hänsch, and N. Picqué, Phys. Rev. A 90, 011805(R) (2014).

Single-ended retroreflection sensors for absorption spectroscopy in high-temperature environments

NASA Astrophysics Data System (ADS)

Melin, Scott T.; Wang, Ze; Neal, Nicholas J.; Rothamer, David A.; Sanders, Scott T.

2017-04-01

Novel single-ended sensor arrangements are demonstrated for in situ absorption spectroscopy in combustion and related test articles. A single-ended optical access technique based on back-reflection from a polished test article surface is presented. H2O vapor absorption spectra were measured at 10 kHz in a homogeneous-charge compression-ignition engine using a sensor of this design collecting back-reflection from a polished piston surface. The measured spectra show promise for high-repetition-rate measurements in practical combustion devices. A second sensor was demonstrated based on a modification to this optical access technique. The sensor incorporates a nickel retroreflective surface as back-reflector to reduce sensitivity to beam steering and misalignment. In a propane-fired furnace, H2O vapor absorption spectra were obtained over the range 7315-7550 cm- 1 at atmospheric pressure and temperatures up to 775 K at 20 Hz using an external-cavity diode laser spectrometer. Gas properties of temperature and mole fraction were obtained from this furnace data using a band-shape spectral fitting technique. The temperature accuracy of the band-shape fitting was demonstrated to be ±1.3 K for furnace measurements at atmospheric pressure. These results should extend the range of applications in which absorption spectroscopy sensors are attractive candidates.

Study of the laser-induced decomposition of energetic materials at static high-pressure by time-resolved absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hebert, Philippe; Saint-Amans, Charles

2013-06-01

A detailed description of the reaction rates and mechanisms occurring in shock-induced decomposition of condensed explosives is very important to improve the predictive capabilities of shock-to-detonation transition models. However, direct measurements of such experimental data are difficult to perform during detonation experiments. By coupling pulsed laser ignition of an explosive in a diamond anvil cell (DAC) with time-resolved streak camera recording of transmitted light, it is possible to make direct observations of deflagration phenomena at detonation pressure. We have developed an experimental set-up that allows combustion front propagation rates and time-resolved absorption spectroscopy measurements. The decomposition reactions are initiated using a nanosecond YAG laser and their kinetics is followed by time-resolved absorption spectroscopy. The results obtained for two explosives, nitromethane (NM) and HMX are presented in this paper. For NM, a change in reactivity is clearly seen around 25 GPa. Below this pressure, the reaction products are essentially carbon residues whereas at higher pressure, a transient absorption feature is first observed and is followed by the formation of a white amorphous product. For HMX, the evolution of the absorption as a function of time indicates a multi-step reaction mechanism which is found to depend on both the initial pressure and the laser fluence.

TimepixCam: a fast optical imager with time-stamping

NASA Astrophysics Data System (ADS)

Fisher-Levine, M.; Nomerotski, A.

2016-03-01

We describe a novel fast optical imager, TimepixCam, based on an optimized silicon pixel sensor with a thin entrance window, read out by a Timepix ASIC. TimepixCam is able to record and time-stamp light flashes in excess of 1,000 photons with high quantum efficiency in the 400-1000nm wavelength range with 20ns timing resolution, corresponding to an effective rate of 50 Megaframes per second. The camera was used for imaging ions impinging on a microchannel plate followed by a phosphor screen. Possible applications include spatial and velocity map imaging of ions in time-of-flight mass spectroscopy; coincidence imaging of ions and electrons, and other time-resolved types of imaging spectroscopy.

Characterization of CuHal-intercalated carbon nanotubes with x-ray absorption spectroscopy combined with x-ray photoelectron and resonant photoemission spectroscopies

NASA Astrophysics Data System (ADS)

Brzhezinskaya, M.; Generalov, A.; Vinogdradov, A.; Eliseev, A.

2013-04-01

Encapsulated single-walled carbon nanotubes (SWCNTs) with inner channels filled by different compounds present the new class of composite materials. Such CNTs give opportunity to form 1D nanocrystals as well as quantum nanowires with new physical and chemical properties inside the tubes. The present study is aimed to characterize the possible chemical interaction between CuHal (Hal=I, Cl, Br) and SWCNTs in CuHal@SWCNTs and electronic structure of the latter using high-resolution near edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with high-resolution X-ray photoelectron spectroscopy and resonant photoemission spectroscopy. The present study has shown that there is a chemical interaction between the filler and π-electron subsystem of CNTs which is accompanied by changes of the atomic and electronic structure of the filler during the encapsulating it inside CNTs.

Mesures spectroscopiques de constituants et de polluants atmosphériques par techniques in situ et à distance, au sol ou embarquéesSpectroscopic measurements of atmospheric constituents and pollutants by in situ and remote techniques from the ground and in flight

NASA Astrophysics Data System (ADS)

Camy-Peyret, Claude; Payan, Sébastien; Jeseck, Pascal; Té, Yao

2001-09-01

Infrared spectroscopy is a powerful tool for precise measurements of atmospheric trace species concentrations through the use of characteristic spectral signatures of the different molecular species and their associated vibration-rotation bands in the mid- or near-infrared. Different methods based on quantitative spectroscopy permit tropospheric or stratospheric measurements: in situ long path absorption, atmospheric absorption/emission by Fourier transform spectroscopy with high spectral resolution instruments on the ground, airborne, balloon-borne or satellite-borne.

Investigation of periodically driven systems by x-ray absorption spectroscopy using asynchronous data collection mode

NASA Astrophysics Data System (ADS)

Singh, H.; Donetsky, D.; Liu, J.; Attenkofer, K.; Cheng, B.; Trelewicz, J. R.; Lubomirsky, I.; Stavitski, E.; Frenkel, A. I.

2018-04-01

We report the development, testing, and demonstration of a setup for modulation excitation spectroscopy experiments at the Inner Shell Spectroscopy beamline of National Synchrotron Light Source - II. A computer algorithm and dedicated software were developed for asynchronous data processing and analysis. We demonstrate the reconstruction of X-ray absorption spectra for different time points within the modulation pulse using a model system. This setup and the software are intended for a broad range of functional materials which exhibit structural and/or electronic responses to the external stimulation, such as catalysts, energy and battery materials, and electromechanical devices.

Photoacoustic spectroscopy of condensed matter

NASA Technical Reports Server (NTRS)

Somoano, R. B.

1978-01-01

Photoacoustic spectroscopy is a new analytical tool that provides a simple nondestructive technique for obtaining information about the electronic absorption spectrum of samples such as powders, semisolids, gels, and liquids. It can also be applied to samples which cannot be examined by conventional optical methods. Numerous applications of this technique in the field of inorganic and organic semiconductors, biology, and catalysis have been described. Among the advantages of photoacoustic spectroscopy, the signal is almost insensitive to light scattering by the sample and information can be obtained about nonradiative deactivation processes. Signal saturation, which can modify the intensity of individual absorption bands in special cases, is a drawback of the method.

[Acoustic detection of absorption of millimeter-band electromagnetic waves in biological objects].

PubMed

Polnikov, I G; Putvinskiĭ, A V

1988-01-01

Principles of photoacoustic spectroscopy were applied to elaborate a new method for controlling millimeter electromagnetic waves absorption in biological objects. The method was used in investigations of frequency dependence of millimeter wave power absorption in vitro and in vivo in the commonly used experimental irradiation systems.

Direct and Quantitative Photothermal Absorption Spectroscopy of Individual Particulates

DTIC Science & Technology

2013-01-01

1(a). By taking the ratio of the spectral absorption efficiency of the microwire to the corresponding volumetri - cally equivalent thin film, an...of D¼ 983 nm. For further comparison, the theoretical spectral absorption efficiency for a volumetri - cally equivalent (t¼ 983p/4 nm) thin film, Qabs

40 CFR Appendix D to Part 136 - Precision and Recovery Statements for Methods for Measuring Metals

Code of Federal Regulations, 2010 CFR

2010-07-01

... Spectroscopy (Direction Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal... Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road... Absorption Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285...

Laser techniques for spectroscopy of core-excited atomic levels

NASA Technical Reports Server (NTRS)

Harris, S. E.; Young, J. F.; Falcone, R. W.; Rothenberg, J. E.; Willison, J. R.

1982-01-01

We discuss three techniques which allow the use of tunable lasers for high resolution and picosecond time scale spectroscopy of core-excited atomic levels. These are: anti-Stokes absorption spectroscopy, laser induced emission from metastable levels, and laser designation of selected core-excited levels.

Photochemistry and photooxidation of tetraphenyl-p-dioxin

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

George, M.V.; Kumar, C.V.; Scaiano, J.C.

1979-09-20

Laser flash photolysis studies of tetraphenyl-p-dioxin have led to the characterization of its triplet state. The T-T absorption spectra shows maxima at 350 and 545 nm; the triplet has a lifetime of 535 ns in methanol and can be quenched by di-tert-butyl nitroxide, paraquat dications, oxygen, and di-tert-butyl selenoketone. The interaction of the triplet with oxygen leads to the formation of singlet oxygen which in turn reacts with the title compound to yield benzil.

Origin and enhancement of the 1.3 μm luminescence from GaAs treated by ion-implantation and flash lamp annealing

NASA Astrophysics Data System (ADS)

Gao, Kun; Prucnal, S.; Skorupa, W.; Helm, M.; Zhou, Shengqiang

2013-09-01

GaAs and GaAs based materials have outstanding optoelectronic properties and are widely used as light emitting media in devices. Many approaches have been applied to GaAs to generate luminescence at 0.88, 1.30, and 1.55 μm which are transmission windows of optical fibers. In this paper, we present the photoluminescence at 1.30 μm from deep level defects in GaAs treated by ion-implantation and flash lamp annealing (FLA). Such emission, which exhibits superior temperature stability, can be obtained from FLA treated virgin GaAs as well as doped GaAs. Indium-doping in GaAs can greatly enhance the luminescence. By photoluminescence, Raman measurements, and positron annihilation spectroscopy, we conclude that the origin of the 1.30 μm emission is from transitions between the VAs-donor and X-acceptor pairs.

Time- and Space-Resolved Spectroscopic Investigation on Pi-Conjugated Nanostructures - 2

DTIC Science & Technology

2016-01-12

15. SUBJECT TERMS Materials Characterization, Materials Chemistry, Nonlinear Optical Materials, Spectroscopy 16. SECURITY CLASSIFICATION...nanostructures will translate into new ground-breaking developments that not only allow the structure-property relationships to be probed in greater detail... spectroscopy . I. Experimental method 1. Steady-state Spectroscopy - UV-Vis-NIR Absorption & Emission Steady-state Spectroscopy - NIR

Intense pulsed light annealing of copper zinc tin sulfide nanocrystal coatings

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

Williams, Bryce A.; Smeaton, Michelle A.; Holgate, Collin S.

2016-09-15

A promising method for forming the absorber layer in copper zinc tin sulfide [Cu{sub 2}ZnSnS{sub 4} (CZTS)] thin film solar cells is thermal annealing of coatings cast from dispersions of CZTS nanocrystals. Intense pulsed light (IPL) annealing utilizing xenon flash lamps is a potential high-throughput, low-cost, roll-to-roll manufacturing compatible alternative to thermal annealing in conventional furnaces. The authors studied the effects of flash energy density (3.9–11.6 J/cm{sup 2}) and number of flashes (1–400) during IPL annealing on the microstructure of CZTS nanocrystal coatings cast on molybdenum-coated soda lime glass substrates (Mo-coated SLG). The annealed coatings exhibited cracks with two distinct linearmore » crack densities, 0.01 and 0.2 μm{sup −1}, depending on the flash intensity and total number of flashes. Low density cracking (0.01 μm{sup −1}, ∼1 crack per 100 μm) is caused by decomposition of CZTS at the Mo-coating interface. Vapor decomposition products at the interface cause blisters as they escape the coating. Residual decomposition products within the blisters were imaged using confocal Raman spectroscopy. In support of this hypothesis, replacing the Mo-coated SLG substrate with quartz eliminated blistering and low-density cracking. High density cracking is caused by rapid thermal expansion and contraction of the coating constricted on the substrate as it is heated and cooled during IPL annealing. Finite element modeling showed that CZTS coatings on low thermal diffusivity materials (i.e., SLG) underwent significant differential heating with respect to the substrate with rapid rises and falls of the coating temperature as the flash is turned on and off, possibly causing a build-up of tensile stress within the coating prompting cracking. Use of a high thermal diffusivity substrate, such as a molybdenum foil (Mo foil), reduces this differential heating and eliminates the high-density cracking. IPL annealing in presence of sulfur vapor prevented both low- and high-density cracking as well as blistering. However, grain growth was limited even after annealing with 400 flashes. This lack of grain growth is attributed to a difficulty of maintaining high sulfur vapor pressure and absence of alkali metal impurities when Mo foil substrates are used.« less

Sub-Thz Vibrational Spectroscopy for Analysis of Ovarian Cancer Cells

NASA Astrophysics Data System (ADS)

Ferrance, Jerome P.; Sizov, Igor; Jazaeri, Amir; Moyer, Aaron; Gelmont, Boris; Globus, Tatiana

2016-06-01

Sub-THz vibrational spectroscopy utilizes wavelengths in the submillimeter-wave range ( 1.5-30 wn), beyond those traditionally used for chemical and biomolecular analysis. This low energy radiation excites low-frequency internal molecular motions (vibrations) involving hydrogen bonds and other weak connections within these molecules. The ability of sub-THz spectroscopy to identify and quantify biological molecules is based on detection of signature resonance absorbance at specific frequencies between 0.05 and 1 THz, for each molecule. The long wavelengths of this radiation, mean that it can even pass through entire cells, detecting the combinations of proteins and nucleic acids that exist within the cell. This research introduces a novel sub-THz resonance spectroscopy instrument with spectral resolution sufficient to identify individual resonance absorption peaks, for the analysis of ovarian cancer cells. In vitro cell cultures of SK-OV-3 and ES-2 cells, two human ovarian cancer subtypes, were characterized and compared with a normal non-transformed human fallopian tube epithelial cell line (FT131). A dramatic difference was observed between the THz absorption spectra of the cancer and normal cell sample materials with much higher absorption intensity and a very strong absorption peak at a frequency of 13 wn dominating the cancer sample spectra. Comparison of experimental spectra with molecular dynamic simulated spectroscopic signatures suggests that the high intensity spectral peak could originate from overexpressed mi-RNA molecules specific for ovarian cancer. Ovarian cancer cells are utilized as a proof of concept, but the sub-THz spectroscopy method is very general and could also be applied to other types of cancer.

Crystallography with online optical and X-ray absorption spectroscopies demonstrates an ordered mechanism in copper nitrite reductase.

PubMed

Hough, Michael A; Antonyuk, Svetlana V; Strange, Richard W; Eady, Robert R; Hasnain, S Samar

2008-04-25

Nitrite reductases are key enzymes that perform the first committed step in the denitrification process and reduce nitrite to nitric oxide. In copper nitrite reductases, an electron is delivered from the type 1 copper (T1Cu) centre to the type 2 copper (T2Cu) centre where catalysis occurs. Despite significant structural and mechanistic studies, it remains controversial whether the substrates, nitrite, electron and proton are utilised in an ordered or random manner. We have used crystallography, together with online X-ray absorption spectroscopy and optical spectroscopy, to show that X-rays rapidly and selectively photoreduce the T1Cu centre, but that the T2Cu centre does not photoreduce directly over a typical crystallographic data collection time. Furthermore, internal electron transfer between the T1Cu and T2Cu centres does not occur, and the T2Cu centre remains oxidised. These data unambiguously demonstrate an 'ordered' mechanism in which electron transfer is gated by binding of nitrite to the T2Cu. Furthermore, the use of online multiple spectroscopic techniques shows their value in assessing radiation-induced redox changes at different metal sites and demonstrates the importance of ensuring the correct status of redox centres in a crystal structure determination. Here, optical spectroscopy has shown a very high sensitivity for detecting the change in T1Cu redox state, while X-ray absorption spectroscopy has reported on the redox status of the T2Cu site, as this centre has no detectable optical absorption.

Elucidating light-induced charge accumulation in an artificial analogue of methane monooxygenase enzymes using time-resolved X-ray absorption spectroscopy

DOE PAGES

Moonshiram, Dooshaye; Picon, Antonio; Vazquez-Mayagoitia, Alvaro; ...

2017-02-08

Here, we report the use of time-resolved X-ray absorption spectroscopy in the ns–μs time scale to track the light induced two electron transfer processes in a multi-component photocatalytic system, consisting of [Ru(bpy) 3] 2+/ a diiron(III,III) model/triethylamine. EXAFS analysis with DFT calculations confirms the structural configurations of the diiron(III,III) and reduced diiron(II,II) states.

Elucidating light-induced charge accumulation in an artificial analogue of methane monooxygenase enzymes using time-resolved X-ray absorption spectroscopy

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

Moonshiram, Dooshaye; Picon, Antonio; Vazquez-Mayagoitia, Alvaro

Here, we report the use of time-resolved X-ray absorption spectroscopy in the ns–μs time scale to track the light induced two electron transfer processes in a multi-component photocatalytic system, consisting of [Ru(bpy) 3] 2+/ a diiron(III,III) model/triethylamine. EXAFS analysis with DFT calculations confirms the structural configurations of the diiron(III,III) and reduced diiron(II,II) states.

Diiodobodipy-styrylbodipy Dyads: Preparation and Study of the Intersystem Crossing and Fluorescence Resonance Energy Transfer.

PubMed

Wang, Zhijia; Xie, Yun; Xu, Kejing; Zhao, Jianzhang; Glusac, Ksenija D

2015-07-02

2,6-Diiodobodipy-styrylbodipy dyads were prepared to study the competing intersystem crossing (ISC) and the fluorescence-resonance-energy-transfer (FRET), and its effect on the photophysical property of the dyads. In the dyads, 2,6-diiodobodipy moiety was used as singlet energy donor and the spin converter for triplet state formation, whereas the styrylbodipy was used as singlet and triplet energy acceptors, thus the competition between the ISC and FRET processes is established. The photophysical properties were studied with steady-state UV-vis absorption and fluorescence spectroscopy, electrochemical characterization, and femto/nanosecond time-resolved transient absorption spectroscopies. FRET was confirmed with steady state fluorescence quenching and fluorescence excitation spectra and ultrafast transient absorption spectroscopy (kFRET = 5.0 × 10(10) s(-1)). The singlet oxygen quantum yield (ΦΔ = 0.19) of the dyad was reduced as compared with that of the reference spin converter (2,6-diiodobodipy, ΦΔ = 0.85), thus the ISC was substantially inhibited by FRET. Photoinduced intramolecular electron transfer (ET) was studied by electrochemical data and fluorescence quenching. Intermolecular triplet energy transfer was studied with nanosecond transient absorption spectroscopy as an efficient (ΦTTET = 92%) and fast process (kTTET = 5.2 × 10(4) s(-1)). These results are useful for designing organic triplet photosensitizers and for the study of the photophysical properties.

Fiber optic gas sensor

NASA Technical Reports Server (NTRS)

Chen, Peng (Inventor); Buric, Michael P. (Inventor); Swinehart, Philip R. (Inventor); Maklad, Mokhtar S. (Inventor)

2010-01-01

A gas sensor includes an in-fiber resonant wavelength device provided in a fiber core at a first location. The fiber propagates a sensing light and a power light. A layer of a material is attached to the fiber at the first location. The material is able to absorb the gas at a temperature dependent gas absorption rate. The power light is used to heat the material and increases the gas absorption rate, thereby increasing sensor performance, especially at low temperatures. Further, a method is described of flash heating the gas sensor to absorb more of the gas, allowing the sensor to cool, thereby locking in the gas content of the sensor material, and taking the difference between the starting and ending resonant wavelengths as an indication of the concentration of the gas in the ambient atmosphere.

Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy below 100 eV: probing first-row transition-metal M-edges in chemical complexes

PubMed Central

Wang, Hongxin; Young, Anthony T.; Guo, Jinghua; Cramer, Stephen P.; Friedrich, Stephan; Braun, Artur; Gu, Weiwei

2013-01-01

X-ray absorption and scattering spectroscopies involving the 3d transition-metal K- and L-edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M-edges, which are below 100 eV. Synchrotron-based X-ray sources can have higher energy resolution at M-edges. M-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) could therefore provide complementary information to K- and L-edge spectroscopies. In this study, M 2,3-edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M 2,3-edge RIXS on NiO, NiF2 and two other covalent complexes have been performed and different d–d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M-edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high-sensitivity and high-resolution superconducting tunnel junction X-ray detectors below 100 eV is also illustrated and discussed. PMID:23765304

Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy below 100 eV: probing first-row transition-metal M-edges in chemical complexes.

PubMed

Wang, Hongxin; Young, Anthony T; Guo, Jinghua; Cramer, Stephen P; Friedrich, Stephan; Braun, Artur; Gu, Weiwei

2013-07-01

X-ray absorption and scattering spectroscopies involving the 3d transition-metal K- and L-edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M-edges, which are below 100 eV. Synchrotron-based X-ray sources can have higher energy resolution at M-edges. M-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) could therefore provide complementary information to K- and L-edge spectroscopies. In this study, M2,3-edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M2,3-edge RIXS on NiO, NiF2 and two other covalent complexes have been performed and different d-d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M-edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high-sensitivity and high-resolution superconducting tunnel junction X-ray detectors below 100 eV is also illustrated and discussed.

Combined "dual" absorption and fluorescence smartphone spectrometers.

PubMed

Arafat Hossain, Md; Canning, John; Ast, Sandra; Cook, Kevin; Rutledge, Peter J; Jamalipour, Abbas

2015-04-15

A combined "dual" absorption and fluorescence smartphone spectrometer is demonstrated. The optical sources used in the system are the white flash LED of the smartphone and an orthogonally positioned and interchangeable UV (λ_ex=370  nm) and blue (λ_ex=450  nm) LED. The dispersive element is a low-cost, nano-imprinted diffraction grating coated with Au. Detection over a 300 nm span with 0.42 nm/pixel resolution was carried out with the camera CMOS chip. By integrating the blue and UV excitation sources into the white LED circuitry, the entire system is self-contained within a 3D printed case and powered from the smartphone battery; the design can be scaled to add further excitation sources. Using a customized app, acquisition of absorption and fluorescence spectra are demonstrated using a blue-absorbing and green-emitting pH-sensitive amino-naphthalimide-based fluorescent probe and a UV-absorbing and blue-emitting Zn²⁺-sensitive fluoro-ionophore.

Modular Electronics for Flash Memory Production

DTIC Science & Technology

2011-12-28

DEFENSE TECHNICAL INFORMATION CENTER ImuM ktkUmlimäj DTICfhas determined on oc öf^H AJI that this Technical Document has the Distribution...the second harmonic (8I2/8V2), and a normalization to remove the scale of the measured current. The red dashed lines represent notable vibrational...superimposed as red dashed lines. The agreement between the two spectroscopies is conclusive that we have successfully put our OPE derivative into the gap

Miniaturized King furnace permits absorption spectroscopy of small samples

NASA Technical Reports Server (NTRS)

Ercoli, B.; Tompkins, F. S.

1968-01-01

Miniature King-type furnace, consisting of an inductively heated, small diameter tantalum tube supported in a radiation shield eliminates the disadvantages of the conventional furnace in obtaining absorption spectra of metal vapors.

NIR remission spectroscopy of turbid media

NASA Astrophysics Data System (ADS)

Krauter, P.; Foschum, F.; Kienle, A.

2013-06-01

We present a method for the determination of absorption spectra in VIS and NIR spectra of turbid media without the need for calibration. Measurements of the absorption spectra of a phantom and butter are presented.

Absorption spectroscopy setup for determination of whole human blood and blood-derived materials spectral characteristics

NASA Astrophysics Data System (ADS)

Wróbel, M. S.; Gnyba, M.; Milewska, D.; Mitura, K.; Karpienko, K.

2015-09-01

A dedicated absorption spectroscopy system was set up using tungsten-halogen broadband source, optical fibers, sample holder, and a commercial spectrometer with CCD array. Analysis of noise present in the setup was carried out. Data processing was applied to the absorption spectra to reduce spectral noise, and improve the quality of the spectra and to remove the baseline level. The absorption spectra were measured for whole blood samples, separated components: plasma, saline, washed erythrocytes in saline and human whole blood with biomarkers - biocompatible nanodiamonds (ND). Blood samples had been derived from a number of healthy donors. The results prove a correct setup arrangement, with adequate preprocessing of the data. The results of blood-ND mixtures measurements show no toxic effect on blood cells, which proves the NDs as a potential biocompatible biomarkers.

A broadband Tm/Ho-doped fiber laser tunable from 1.8 to 2.09 µm for intracavity absorption spectroscopy

NASA Astrophysics Data System (ADS)

Fjodorow, Peter; Hellmig, Ortwin; Baev, Valery M.

2018-04-01

A broadband tunable Tm/Ho-doped fiber laser is developed for sensitive in situ measurements of intracavity absorption spectra in the spectral range of 4780-5560 cm-1. This spectral range includes an atmospheric transmission window enabling sensitive measurements of various species. The spectral bandwidth of laser emission varies from 20 to 60 cm-1 and is well suitable for multicomponent spectroscopy. The sensitivity achieved in cw operation corresponds to an effective absorption path length of L eff = 20 km, with a spectral noise of less than 1%. The spectroscopic system is applied for measurements of absorption spectra of H2O, NH3 and for simultaneous in situ detection of three isotopes of CO2 in human breath, which is important for medical diagnostics procedures.

Toroidal Optical Microresonators as Single-Particle Absorption Spectrometers

NASA Astrophysics Data System (ADS)

Heylman, Kevin D.

Single-particle and single-molecule measurements are invaluable tools for characterizing structural and energetic properties of molecules and nanomaterials. Photothermal microscopy in particular is an ultrasensitive technique capable of single-molecule resolution. In this thesis I introduce a new form of photothermal spectroscopy involving toroidal optical microresonators as detectors and a pair of non-interacting lasers as pump and probe for performing single-target absorption spectroscopy. The first three chapters will discuss the motivation, design principles, underlying theory, and fabrication process for the microresonator absorption spectrometer. With an early version of the spectrometer, I demonstrate photothermal mapping and all-optical tuning with toroids of different geometries in Chapter 4. In Chapter 5, I discuss photothermal mapping and measurement of the absolute absorption cross-sections of individual carbon nanotubes. For the next generation of measurements I incorporate all of the advances described in Chapter 2, including a double-modulation technique to improve detection limits and a tunable pump laser for spectral measurements on single gold nanoparticles. In Chapter 6 I observe sharp Fano resonances in the spectra of gold nanoparticles and describe them with a theoretical model. I continued to study this photonic-plasmonic hybrid system in Chapter 7 and explore the thermal tuning of the Fano resonance phase while quantifying the Fisher information. The new method of photothermal single-particle absorption spectroscopy that I will discuss in this thesis has reached record detection limits for microresonator sensing and is within striking distance of becoming the first single-molecule room-temperature absorption spectrometer.

Trospospheric degradation chemistry of HCFC-123 (CF 3CHCl 2): A proposed replacement chlorofluorocarbon

NASA Astrophysics Data System (ADS)

Hayman, G. D.; Jenkin, M. E.; Murrells, T. P.; Johnson, C. E.

HCFC-123 has been proposed as a replacement for some of the fully halogenated chlorofluorocarbons and other chlorinated hydrocarbons, which are being phased out under the Montreal Protocol. This paper reports laboratory studies which were undertaken to determine kinetic and mechanistic parameters of reactions involved in the atmospheric degradation of HCFC-123 and the use of these parameters in a 2D global model of the troposphere to evaluate the yields of products formed in the degradation. The experimental studies have made use of the laser flash photolysis technique with time-resolved ultra-violet absorption spectroscopy for the kinetic measurements and broad-band ultra-violet absorption spectroscopy for product characterization. Rate coefficients have been determined for the self-reaction of CF 3CCl 2O 2 as (3.6±0.5)×10 -12 cm 3 mol -1 s -1 and for its reactions with HO 2 and NO as (1.9±0.7)×10 -12 cm 3 mol -1 s -1 and (1.5-2.0)×10 -11 cm 3 mol -1 s -1, respectively, at room temperature. Kinetic data have also been obtained for the reaction of CF 3CCl 2O 2 with C 2H 5O 2 and two channels have been identified; CF 3CCl 2+O 2+C 2H 5O 2→CF 3CCl 2O+C 2H 5O+ C 2H 5O+O 2, k=(9 +9-5)×10 13 cm 3 mol -1 s -1 and CF 3CCl 2O 2+C 2H 5O 2→CF 3CCl 2OH+CH 3CHO+O 2, k=(3.6±0.5)× 10 -12 cm 3 mol -1 s -1. Studies undertaken using the Cl-initiated oxidation of HCFC-123 suggest that trifluoroacetyl chloride, CF 3COCl, is the major product of the gas-phase degradation. The kinetic and mechanistic data have been used to formulate a chemical module of the degradation of HCFC-123 in the trophosphere. The module has been incorporated into a 2D model of the global troposphere so that the potential atmospheric impact of using HCFC-123 can be assessed.

Discovery of a Significant Acetone•Hydroperoxy Adduct Chaperone Effect and Its Impact on the Determination of Room Temperature Rate Constants for Acetonylperoxy/Hydroperoxy Self-Reactions and Cross Reaction Via Infrared Kinetic Spectroscopy.

NASA Astrophysics Data System (ADS)

Grieman, F. J.; Hui, A. O.; Okumura, M.; Sander, S. P.

2017-12-01

In order to model the upper troposphere/lower stratosphere in regions containing acetone properly, the kinetics of the acetonylperoxy/hydroperoxy self-reactions and cross reaction have been studied over a wide temperature range using Infrared Kinetic Spectroscopy. We report here the determination of different rate constants for the acetonylperoxy chemistry that we obtained at 298 K compared to currently accepted values. A considerable increase in the observed HO2 self-reaction rate constant due to rate enhancement via the chaperone effect from the reaction between HO2 and the (CH3)2CO•HO2 hydrogen-bonded adduct, even at room temperature, was discovered that was previously ignored. Correct determination of the acetonylperoxy and hydroperoxy kinetics must include this dependence of the HO2 self-reaction rate on acetone concentration. Via excimer laser flash photolysis to create the radical reactants, HO2 absorption was monitored in the infrared by diode laser wavelength modulation detection simultaneously with CH3C(O)CH2O2absorption monitored in the ultraviolet at 300 nm as a function of time. Resulting decay curves were fit concurrently first over a short time scale to obtain the rate constants minimizing subsequent product reactions. Modeling/fitting with a complete reaction scheme was then performed to refine the rate constants and test their veracity. Experiments were carried out over a variety of concentrations of acetone and methanol. Although no effect due to methanol concentration was found at room temperature, the rate constant for the hydroperoxy self-reaction was found to increase linearly with acetone concentration which is interpreted as the adduct being formed and resulting in a chaperone mechanism that enhances the self-reaction rate: (CH3)2CO·HO2 + HO2 → H2O2 + O2 + (CH3)2CO Including this effect, the resulting room temperature rate constants for the cross reaction and the acetonylperoxy self-reaction were found to be 2-3 times smaller than previously reported. This complex formation/chaperone mechanism is similar to that found for methanol, but different in that it occurs at room temperature. No precursor concentration dependence was found for the acetonylperoxy radical reactions. The equilibrium constant for the complex formation will also be presented.

Composite fluorescent nanoparticles for biomedical imaging.

PubMed

Pansare, Vikram J; Bruzek, Matthew J; Adamson, Douglas H; Anthony, John; Prud'homme, Robert K

2014-04-01

In the rapidly expanding field of biomedical imaging, there is a need for nontoxic, photostable, and nonquenching fluorophores for fluorescent imaging. We have successfully encapsulated a new, extremely hydrophobic, pentacene-based fluorescent dye within polymeric nanoparticles (NPs) or nanocarriers (NCs) via the Flash NanoPrecipitation (FNP) process. Nanoparticles and dye-loaded micelles were formulated by FNP and characterized by dynamic light scattering, fluorescence spectroscopy, UV-VIS absorbance spectroscopy, and confocal microscopy. These fluorescent particles were loaded from less than 1% to 78% by weight core loading and the fluorescence maximum was found to be at 2.3 wt.%. The particles were also stably formed at 2.3% core loading from 20 up to 250 nm in diameter with per-particle fluorescence scaling linearly with the NC core volume. The major absorption peaks are at 458, 575, and 625 nm, and the major emission peaks at 635 and 695 nm. In solution, the Et-TP5 dye displays a strong concentration-dependent ratio of the emission intensities of the first two emission peaks, whereas in the nanoparticle core the spectrum is independent of concentration over the entire concentration range. A model of the fluorescence quenching was consistent with Förster resonant energy transfer as the cause of the quenching observed for Et-TP5. The Förster radius calculated from the absorption and emission spectra of Et-TP5 is 4.1 nm, whereas the average dye spacing in the particles at the maximum fluorescence is 3.9 nm. We have successfully encapsulated Et-TP5, a pentacene derivative dye previously only used in light-emitting diode applications, within NCs via the FNP process. The extreme hydrophobicity of the dye keeps it encapsulated in the NC core, its extended pentacene structure gives it relatively long wavelength emission at 695 nm, and the pentacene structure, without oxygen or nitrogen atoms in its core, makes it highly resistant to photobleaching. Its bulky side groups minimize self-quenching and localization within the nanoparticle core prevents interaction of the dye with biological surfaces, or molecules in diagnostic assays. Loading of dye in the NP core allows 25 times more dye to be delivered than if it were conjugated onto the nanocarrier surface. The utility of the dye for quantifying nanoparticle binding is demonstrated. Studies to extend the wavelength range of these pentacene dyes into the near infra-red are underway.

Measurement of temperature profiles in flames by emission-absorption spectroscopy

NASA Technical Reports Server (NTRS)

Simmons, F. S.; Arnold, C. B.; Lindquist, G. H.

1972-01-01

An investigation was conducted to explore the use of infrared and ultraviolet emission-absorption spectroscopy for determination of temperature profiles in flames. Spectral radiances and absorptances were measured in the 2.7-micron H2O band and the 3064-A OH band in H2/O2 flames for several temperature profiles which were directly measured by a sodium line-reversal technique. The temperature profiles, determined by inversion of the infrared and ultraviolet spectra, showed an average disagreement with line-reversal measurements of 50 K for the infrared and 200 K for the ultraviolet at a temperature of 2600 K. The reasons for these discrepancies are discussed in some detail.

Quantum state-resolved probing of strong-field-ionized xenon atoms using femtosecond high-order harmonic transient absorption spectroscopy.

PubMed

Loh, Zhi-Heng; Khalil, Munira; Correa, Raoul E; Santra, Robin; Buth, Christian; Leone, Stephen R

2007-04-06

Femtosecond high-order harmonic transient absorption spectroscopy is used to resolve the complete |j,m quantum state distribution of Xe+ produced by optical strong-field ionization of Xe atoms at 800 nm. Probing at the Xe N4/5 edge yields a population distribution rhoj,|m| of rho3/2,1/2ratiorho1/2,1/2ratiorho3/2,3/2=75+/-6 :12+/-3 :13+/-6%. The result is compared to a tunnel ionization calculation with the inclusion of spin-orbit coupling, revealing nonadiabatic ionization behavior. The sub-50-fs time resolution paves the way for tabletop extreme ultraviolet absorption probing of ultrafast dynamics.

Mid-infrared multi-mode absorption spectroscopy, MUMAS, using difference frequency generation

NASA Astrophysics Data System (ADS)

Northern, Henry; O'Hagan, Seamus; Hamilton, Michelle L.; Ewart, Paul

2015-03-01

Multi-mode absorption spectroscopy of ammonia and methane at 3.3 μm has been demonstrated using a source of multi-mode mid-infrared radiation based on difference frequency generation. Multi-mode radiation at 1.56 μm from a diode-pumped Er:Yb:glass laser was mixed with a single-mode Nd:YAG laser at 1.06 μm in a periodically poled lithium niobate crystal to produce multi-mode radiation in the region of 3.3 μm. Detection, by direct multi-mode absorption, of NH3 and CH4 is reported for each species individually and also simultaneously in mixtures allowing measurements of partial pressures of each species.

Differential Optical Absorption Spectroscopy (DOAS) using Targets: SO2 and NO2 Measurements in Montevideo City

NASA Astrophysics Data System (ADS)

Louban, Ilia; Píriz, Gustavo; Platt, Ulrich; Frins, Erna

2008-04-01

SO2 and NO2 were remotely measured in a main street of Montevideo city using Multiaxis-Differential Optical Absorption Spectroscopy (MAX-DOAS) combined with on-field selected targets. Target-based measurements are the basis of a new experimental procedure called Topographic Target Light scattering-DOAS (TOTAL-DOAS) that provides a well define absorption path to measure the near surface distribution of trace gases in the boundary layer. It combines the measurement principles of the long-path DOAS and zenith-scattered sunlight DOAS, within the near UV and VIS spectral range. We give a general description of the procedure and present first results of the 2006 campaign at Montevideo.

Spectroscopy of Reaction Intermediates in Nitramine Decomposition and Combustion

DTIC Science & Technology

1991-06-20

Dakhis and co-workers, s the very strong absorption of MMN near 1332 cm - 1 did not appear. Unassigned absorptions appeared near 930, 1240, 1460, 2990, and...sharp NO2 absorption. In Table I, the positions of these absorptions are compared with the infrared absorptions of MMN reported by Dakhis and co-workers...Chemistry and Physics of Energetic Materials, S. N. Bulusu, Ed., pp. 51-78 (Kluwer Academic Publishers, Dordrecht, 1990). 56. M. I. Dakhis , V. G. Dashevsky

Spectroscopy of Reaction Intermediates in Nitramine Decomposition and Combustion

DTIC Science & Technology

1991-06-20

absorptions of gas-phase MMN reported by Dakhis and co-workers,5 6 the very strong absorption of MMN near 1332 cm - ’ did not appear. Unassigned...sharp NO 2 absorption. In Table I, the positions of these absorptions are compared with the infrared absorptions of MMN reported by Dakhis and co-workers...Chemistry and Physics of Energetic Materials, S. N. Bulusu, Ed., pp. 51-78 (Kluwer Academic Publishers, Dordrecht, 1990). 56. M. I. Dakhis , V. G

An improved loopless mounting method for cryocrystallography

NASA Astrophysics Data System (ADS)

Qi, Jian-Xun; Jiang, Fan

2010-01-01

Based on a recent loopless mounting method, a simplified loopless and bufferless crystal mounting method is developed for macromolecular crystallography. This simplified crystal mounting system is composed of the following components: a home-made glass capillary, a brass seat for holding the glass capillary, a flow regulator, and a vacuum pump for evacuation. Compared with the currently prevalent loop mounting method, this simplified method has almost the same mounting procedure and thus is compatible with the current automated crystal mounting system. The advantages of this method include higher signal-to-noise ratio, more accurate measurement, more rapid flash cooling, less x-ray absorption and thus less radiation damage to the crystal. This method can be extended to the flash-freeing of a crystal without or with soaking it in a lower concentration of cryoprotectant, thus it may be the best option for data collection in the absence of suitable cryoprotectant. Therefore, it is suggested that this mounting method should be further improved and extensively applied to cryocrystallographic experiments.

FEASIBILITY STUDY TO DEMONSTRATE APPLICABILITY OF TUNABLE INFRARED LASER EMISSION SPECTROSCOPY TECHNOLOGY TO MEASURE AIR POLLUTION

EPA Science Inventory

This project involves the real-time measurement of air quality using open-path IR spectroscopy. A prototype open-path tunable laser absorption spectroscopy instrument was designed, built, and successfully operated for several hundred hours between October and December 2000. The...

Oxidation and crystal field effects in uranium

NASA Astrophysics Data System (ADS)

Tobin, J. G.; Yu, S.-W.; Booth, C. H.; Tyliszczak, T.; Shuh, D. K.; van der Laan, G.; Sokaras, D.; Nordlund, D.; Weng, T.-C.; Bagus, P. S.

2015-07-01

An extensive investigation of oxidation in uranium has been pursued. This includes the utilization of soft x-ray absorption spectroscopy, hard x-ray absorption near-edge structure, resonant (hard) x-ray emission spectroscopy, cluster calculations, and a branching ratio analysis founded on atomic theory. The samples utilized were uranium dioxide (U O2) , uranium trioxide (U O3) , and uranium tetrafluoride (U F4) . A discussion of the role of nonspherical perturbations, i.e., crystal or ligand field effects, will be presented.

Theory of fiber-optic, evanescent-wave spectroscopy and sensors

NASA Astrophysics Data System (ADS)

Messica, A.; Greenstein, A.; Katzir, A.

1996-05-01

A general theory for fiber-optic, evanescent-wave spectroscopy and sensors is presented for straight, uncladded, step-index, multimode fibers. A three-dimensional model is formulated within the framework of geometric optics. The model includes various launching conditions, input and output end-face Fresnel transmission losses, multiple Fresnel reflections, bulk absorption, and evanescent-wave absorption. An evanescent-wave sensor response is analyzed as a function of externally controlled parameters such as coupling angle, f number, fiber length, and diameter. Conclusions are drawn for several experimental apparatuses.

Characterization of Infrared Properties of Layered Semiconductors.

DTIC Science & Technology

1987-02-20

candidate -10- V. PUBLICATIONS INCLUDED WITH REPORT 1) R. Braunstein, R. K . Kim, D. Matthews, and M. Braunstein: "Derivative Absorption Spectroscopy of...34Wavelength Modulation Spectra of a-Ag0.7Zn0 .3 Near the Optical Absorption Edge," Phys. Stat. Sol.(b) 131, 659 (1983). 5) R. K . Kim and R. Braunstein...34Infrared Wavelength Modulation Spectroscopy of Some Optical Material," Appl. Optics 23(8), 1166 (1984). 6) C.E. Jones, K . James, J. Merz, R. Braunstein, M

Isothermal crystallization of poly(3-hydroxybutyrate) studied by terahertz two-dimensional correlation spectroscopy

NASA Astrophysics Data System (ADS)

Hoshina, Hiromichi; Ishii, Shinya; Morisawa, Yusuke; Sato, Harumi; Noda, Isao; Ozaki, Yukihiro; Otani, Chiko

2012-01-01

The isothermal crystallization of poly(3-hydroxybutylate) (PHB) was studied by monitoring the temporal evolution of terahertz absorption spectra in conjunction with spectral analysis using two-dimensional correlation spectroscopy. Correlation between the absorption peaks and the sequential order of the changes in spectral intensity extracted from synchronous and asynchronous plots indicated that crystallization of PHB at 90 °C is a two step process, in which C-H...O=C hydrogen bonds are initially formed before well-defined crystal structures are established.

Determination of traces of silicone defoamer in fruit juices by solvent extraction/atomic absorption spectroscopy.

PubMed

Gooch, E G

1993-01-01

Silicone defoamers are used to control foam during the processing of fruit juices. Residual silicones in fruit juices can be separated from the naturally occurring siliceous materials in fruit products and selectively recovered by solvent extraction, after suitable pretreatment. The recovered silicone is measured by atomic absorption spectroscopy. Silicone concentrations as low as about 1 ppm can be measured. The juices are accurately spiked for recovery studies by the addition of silicone dispersed in D-sorbitol.

Concentration measurement of NO using self-absorption spectroscopy of the γ band system in a pulsed corona discharge.

PubMed

Zhai, Xiaodong; Ding, Yanjun; Peng, Zhimin; Luo, Rui

2012-07-10

Nitric oxide (NO) concentrations were measured using the γ band system spectrum based on the strong self-absorption effect of NO in pulsed corona discharges. The radiative transitional intensities of the NO γ band were simulated based on the theory of molecular spectroscopy. The intensities of some bands, especially γ(0,0) and γ(1,0), are weakened by the self-absorption. The correlations between the spectral self-absorption intensities and NO concentration were validated using a modified Beer-Lambert law with a combined factor K relating the branching ratio and the NO concentration, and a nonlinear index α that is applicable to the broadband system. Optical emissive spectra in pulsed corona discharges in NO and N2/He mixtures were used to evaluate the two parameters for various conditions. Good agreement between the experimental and theoretical results verifies the self-absorption behavior seen in the UV spectra of the NO γ bands.

Reflectance-mode interferometric near-infrared spectroscopy quantifies brain absorption, scattering, and blood flow index in vivo

PubMed Central

Borycki, Dawid; Kholiqov, Oybek; Srinivasan, Vivek J.

2017-01-01

Interferometric near-infrared spectroscopy (iNIRS) is a new technique that measures time-of-flight- (TOF-) resolved autocorrelations in turbid media, enabling simultaneous estimation of optical and dynamical properties. Here, we demonstrate reflectance-mode iNIRS for noninvasive monitoring of a mouse brain in vivo. A method for more precise quantification with less static interference from superficial layers, based on separating static and dynamic components of the optical field autocorrelation, is presented. Absolute values of absorption, reduced scattering, and blood flow index (BFI) are measured, and changes in BFI and absorption are monitored during a hypercapnic challenge. Absorption changes from TOF-resolved iNIRS agree with absorption changes from continuous wave NIRS analysis, based on TOF-integrated light intensity changes, an effective path length, and the modified Beer–Lambert Law. Thus, iNIRS is a promising approach for quantitative and non-invasive monitoring of perfusion and optical properties in vivo. PMID:28146535

Absorption Spectroscopy of Mercury's Exosphere During the 2016 Solar Transit

NASA Astrophysics Data System (ADS)

Schmidt, C. A.; Leblanc, F.; Reardon, K.; Killen, R. M.; Gary, D. E.; Ahn, K.

2018-05-01

Solar transits of Mercury provide a rare opportunity to study the exosphere in absorption and a valuable analog to transiting exoplanet studies. This presentation will characterize the sodium exosphere during the 2016 transit.

Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

NASA Astrophysics Data System (ADS)

Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

2016-10-01

We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

Diagnosing the plasma nonuniformity in an iron opacity experiment by spatially resolved Al 1s-2p absorption spectroscopy

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

Zhang Xiaoding; Research Center of Laser Fusion, P. O. Box 919-986, Mianyang 621900; Zhang Jiyan

Generating a well-characterized hot-dense sample is of great importance to high quality opacity measurements. In this paper, we report on an experimental investigation of the plasma nonuniformity in a radiatively heated iron opacity sample by spatially resolved Al 1s-2p absorption spectroscopy. The iron sample was tamped by plastic at both sides and was heated by thermal x-ray radiation generated in a gold Hohlraum, and an Al layer attached to it was used as a tracer for temperature diagnosis. Spatially resolved 1s-2p transition absorption spectra of the Al tracer were measured by the technique of point-projection-spectroscopy, and temperatures in the samplemore » were obtained by comparing the measured spectra with detailed-term-accounting model calculations, with the density of the sample deduced using a combination of side-on radiography and radiative hydrodynamic simulation. The results showed the existence of axial temperature nonuniformity in the sample, and these temperature variations have been used to explain the shift of iron 2p-3d transition absorption feature along the axial direction of the Hohlraum used to heat the sample successfully.« less

Simultaneous Chemical and Refractive Index Sensing in the 1-2.5 μm Near-Infrared Wavelength Range on Nanoporous Gold Disks.

PubMed

Shih, Wei-Chuan; Santos, Greggy M; Zhao, Fusheng; Zenasni, Oussama; Arnob, Md Masud Parvez

2016-07-13

Near-infrared (NIR) absorption spectroscopy provides molecular and chemical information based on overtones and combination bands of the fundamental vibrational modes in the infrared wavelengths. However, the sensitivity of NIR absorption measurement is limited by the generally weak absorption and the relatively poor detector performance compared to other wavelength ranges. To overcome these barriers, we have developed a novel technique to simultaneously obtain chemical and refractive index sensing in 1-2.5 μm NIR wavelength range on nanoporous gold (NPG) disks, which feature high-density plasmonic hot-spots of localized electric field enhancement. For the first time, surface-enhanced near-infrared absorption (SENIRA) spectroscopy has been demonstrated for high sensitivity chemical detection. With a self-assembled monolayer (SAM) of octadecanethiol (ODT), an enhancement factor (EF) of up to ∼10(4) has been demonstrated for the first C-H combination band at 2400 nm using NPG disk with 600 nm diameter. Together with localized surface plasmon resonance (LSPR) extinction spectroscopy, simultaneous sensing of sample refractive index has been achieved for the first time. The performance of this technique has been evaluated using various hydrocarbon compounds and crude oil samples.

Highly vibrationally excited O2 molecules in low-pressure inductively-coupled plasmas detected by high sensitivity ultra-broad-band optical absorption spectroscopy

NASA Astrophysics Data System (ADS)

Foucher, Mickaël; Marinov, Daniil; Carbone, Emile; Chabert, Pascal; Booth, Jean-Paul

2015-08-01

Inductively-coupled plasmas in pure O2 (at pressures of 5-80 mTorr and radiofrequency power up to 500 W) were studied by optical absorption spectroscopy over the spectral range 200-450 nm, showing the presence of highly vibrationally excited O2 molecules (up to vʺ = 18) by Schumann-Runge band absorption. Analysis of the relative band intensities indicates a vibrational temperature up to 10,000 K, but these hot molecules only represent a fraction of the total O2 density. By analysing the (11-0) band at higher spectral resolution the O2 rotational temperature was also determined, and was found to increase with both pressure and power, reaching 900 K at 80 mTorr 500 W. These measurements were achieved using a new high-sensitivity ultra-broad-band absorption spectroscopy setup, based on a laser-plasma light source, achromatic optics and an aberration-corrected spectrograph. This setup allows the measurement of weak broadband absorbances due to a baseline variability lower than 2   ×   10-5 across a spectral range of 250 nm.

Characterization of dissolved organic matter in Dongjianghu Lake by UV-visible absorption spectroscopy with multivariate analysis.

PubMed

Zhu, Yanzhong; Song, Yonghui; Yu, Huibin; Liu, Ruixia; Liu, Lusan; Lv, Chunjian

2017-08-08

UV-visible absorption spectroscopy coupled with principal component analysis (PCA) and hierarchical cluster analysis (HCA) was applied to characterize spectroscopic components, detect latent factors, and investigate spatial variations of dissolved organic matter (DOM) in a large-scale lake. Twelve surface water samples were collected from Dongjianghu Lake in China. DOM contained lignin and quinine moieties, carboxylic acid, microbial products, and aromatic and alkyl groups, which in the northern part of the lake was largely different from the southern part. Fifteen spectroscopic indices were deduced from the absorption spectra to indicate molecular weight or humification degree of DOM. The northern part of the lake presented the smaller molecular weight or the lower humification degree of DOM than the southern part. E 2/4 , E 3/4 , E 2/3 , and S 2 were latent factors of characterizing the molecular weight of DOM, while E 2/5 , E 3/5 , E 2/6 , E 4/5 , E 3/6 , and A 2/1 were latent factors of evaluating the humification degree of DOM. The UV-visible absorption spectroscopy combined with PCA and HCA may not only characterize DOM fractions of lakes, but may be transferred to other types of waterscape.

A new high temperature reactor for operando XAS: Application for the dry reforming of methane over Ni/ZrO2 catalyst.

PubMed

Aguilar-Tapia, Antonio; Ould-Chikh, Samy; Lahera, Eric; Prat, Alain; Delnet, William; Proux, Olivier; Kieffer, Isabelle; Basset, Jean-Marie; Takanabe, Kazuhiro; Hazemann, Jean-Louis

2018-03-01

The construction of a high-temperature reaction cell for operando X-ray absorption spectroscopy characterization is reported. A dedicated cell was designed to operate as a plug-flow reactor using powder samples requiring gas flow and thermal treatment at high temperatures. The cell was successfully used in the reaction of dry reforming of methane (DRM). We present X-ray absorption results in the fluorescence detection mode on a 0.4 wt. % Ni/ZrO 2 catalyst under realistic conditions at 750 °C, reproducing the conditions used for a conventional dynamic microreactor for the DRM reaction. The setup includes a gas distribution system that can be fully remotely operated. The reaction cell offers the possibility of transmission and fluorescence detection modes. The complete setup dedicated to the study of catalysts is permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental sciences (CRG-FAME) and French Absorption spectroscopy beamline in Material and Environmental sciences at Ultra-High Dilution (FAME-UHD) beamlines (BM30B and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

A new high temperature reactor for operando XAS: Application for the dry reforming of methane over Ni/ZrO2 catalyst

NASA Astrophysics Data System (ADS)

Aguilar-Tapia, Antonio; Ould-Chikh, Samy; Lahera, Eric; Prat, Alain; Delnet, William; Proux, Olivier; Kieffer, Isabelle; Basset, Jean-Marie; Takanabe, Kazuhiro; Hazemann, Jean-Louis

2018-03-01

The construction of a high-temperature reaction cell for operando X-ray absorption spectroscopy characterization is reported. A dedicated cell was designed to operate as a plug-flow reactor using powder samples requiring gas flow and thermal treatment at high temperatures. The cell was successfully used in the reaction of dry reforming of methane (DRM). We present X-ray absorption results in the fluorescence detection mode on a 0.4 wt. % Ni/ZrO2 catalyst under realistic conditions at 750 °C, reproducing the conditions used for a conventional dynamic microreactor for the DRM reaction. The setup includes a gas distribution system that can be fully remotely operated. The reaction cell offers the possibility of transmission and fluorescence detection modes. The complete setup dedicated to the study of catalysts is permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental sciences (CRG-FAME) and French Absorption spectroscopy beamline in Material and Environmental sciences at Ultra-High Dilution (FAME-UHD) beamlines (BM30B and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

Gas in scattering media absorption spectroscopy - GASMAS

NASA Astrophysics Data System (ADS)

Svanberg, Sune

2008-09-01

An overview of the new field of Gas in Scattering Media Absorption Spectroscopy (GASMAS) is presented. GASMAS combines narrow-band diode-laser spectroscopy with diffuse media optical propagation. While solids and liquids have broad absorption features, free gas in pores and cavities in the material is characterized by sharp spectral signatures, typically 10,000 times sharper than those of the host material. Many applications in materials science, food packaging, pharmaceutics and medicine have been demonstrated. So far molecular oxygen and water vapour have been studied around 760 and 935 nm, respectively. Liquid water, an important constituent in many natural materials, such as tissue, has a low absorption at such wavelengths, allowing propagation. Polystyrene foam, wood, fruits, food-stuffs, pharmaceutical tablets, and human sinus cavities have been studied. Transport of gas in porous media can readily be studied by first immersing the material in, e.g., pure nitrogen, and then observing the rate at which normal air, containing oxygen, reinvades the material. The conductance of the sinus connective passages can be measured in this way by flushing the nasal cavity with nitrogen. Also other dynamic processes such as drying of materials can be studied. The techniques have also been extended to remote-sensing applications (LIDAR-GASMAS).

High-Sensitivity Optical Techniques for Atmospheric Spectroscopy, Kinetics and Remote Sensing

NASA Technical Reports Server (NTRS)

2005-01-01

A principal objective of the work supported by this Grant has been to use IntraCavity Laser Absorption Spectroscopy (ICLAS) to acquire data on weakly absorbing species of atmospheric interest that are not accessible, or cannot be determined with sufficient precision, using conventional spectroscopic instrumentation. The principal focus has been to adapt the existing instrument to carry out Kinetic studies using IntraCavity Absorption Spectroscopy (KICAS) in order to measure rate parameters for weakly absorbing, environmentally significant species. Additional related work has been carried out in collaboration with Prof. M.J. Molina's program on air pollution in the Mexico City Metropolitan Area on modeling the role of these species in atmospheric chemistry.

Disentangling atomic-layer-specific x-ray absorption spectra by Auger electron diffraction spectroscopy

NASA Astrophysics Data System (ADS)

Matsui, Fumihiko; Matsushita, Tomohiro; Kato, Yukako; Hashimoto, Mie; Daimon, Hiroshi

2009-11-01

In order to investigate the electronic and magnetic structures of each atomic layer at subsurface, we have proposed a new method, Auger electron diffraction spectroscopy, which is the combination of x-ray absorption spectroscopy (XAS) and Auger electron diffraction (AED) techniques. We have measured a series of Ni LMM AED patterns of the Ni film grown on Cu(001) surface for various thicknesses. Then we deduced a set of atomic-layer-specific AED patterns in a numerical way. Furthermore, we developed an algorithm to disentangle XANES spectra from different atomic layers using these atomic-layer-specific AED patterns. Surface and subsurface core level shift were determined for each atomic layer.

Oxygen measurement by multimode diode lasers employing gas correlation spectroscopy.

PubMed

Lou, Xiutao; Somesfalean, Gabriel; Chen, Bin; Zhang, Zhiguo

2009-02-10

Multimode diode laser (MDL)-based correlation spectroscopy (COSPEC) was used to measure oxygen in ambient air, thereby employing a diode laser (DL) having an emission spectrum that overlaps the oxygen absorption lines of the A band. A sensitivity of 700 ppm m was achieved with good accuracy (2%) and linearity (R(2)=0.999). For comparison, measurements of ambient oxygen were also performed by tunable DL absorption spectroscopy (TDLAS) technique employing a vertical cavity surface emitting laser. We demonstrate that, despite slightly degraded sensitivity, the MDL-based COSPEC-based oxygen sensor has the advantages of high stability, low cost, ease-of-use, and relaxed requirements in component selection and instrument buildup compared with the TDLAS-based instrument.

Flash photolysis and pulse radiolysis studies on collagen Type I in acetic acid solution.

PubMed

Sionkowska, Alina

2006-07-03

An investigation of the photochemical properties of collagen Type I in acetic acid solution was carried out using nanosecond laser irradiation. The transient spectra of collagen solution excited at 266 nm show two bands. One of them with maximum at 295 nm and the second one with maximum at 400 nm. The peak at 400 nm is assigned to tyrosyl radicals. The first peak of the transient absorption spectra at 295 nm is probably due to photoionisation producing collagen radical cation. The transient for collagen solution in acetic acid at 640 nm was not observed. It is evidence that there is no hydrated electron in the irradiated collagen solution. The reactions of hydrated electrons and (*)OH radicals with collagen have been studied by pulse radiolysis. In the absorption spectra of products resulting from the reaction of collagen with e(aq)(-) no characteristic maximum absorption in UV and visible light region has been observed. In the absorption spectra of products resulting from the reaction of the hydroxyl radicals with collagen two bands have been observed. The first one at 320 nm and the second one at 405 nm. Reaction of (*)OH radicals with tyrosine residues in collagen chains gives rise to Tyr phenoxyl radicals (absorption at 400 nm).

Enhanced Vibrational Spectroscopies as Tools for Small Molecule Biosensing

PubMed Central

Boujday, Souhir; Lamy de la Chapelle, Marc; Srajer, Johannes; Knoll, Wolfgang

2015-01-01

In this short summary we summarize some of the latest developments in vibrational spectroscopic tools applied for the sensing of (small) molecules and biomolecules in a label-free mode of operation. We first introduce various concepts for the enhancement of InfraRed spectroscopic techniques, including the principles of Attenuated Total Reflection InfraRed (ATR-IR), (phase-modulated) InfraRed Reflection Absorption Spectroscopy (IRRAS/PM-IRRAS), and Surface Enhanced Infrared Reflection Absorption Spectroscopy (SEIRAS). Particular attention is put on the use of novel nanostructured substrates that allow for the excitation of propagating and localized surface plasmon modes aimed at operating additional enhancement mechanisms. This is then be complemented by the description of the latest development in Surface- and Tip-Enhanced Raman Spectroscopies, again with an emphasis on the detection of small molecules or bioanalytes. PMID:26343666

Sensitivity and resolution in frequency comb spectroscopy of buffer gas cooled polyatomic molecules

NASA Astrophysics Data System (ADS)

Changala, P. Bryan; Spaun, Ben; Patterson, David; Doyle, John M.; Ye, Jun

2016-12-01

We discuss the use of cavity-enhanced direct frequency comb spectroscopy in the mid-infrared region with buffer gas cooling of polyatomic molecules for high-precision rovibrational absorption spectroscopy. A frequency comb coupled to an optical enhancement cavity allows us to collect high-resolution, broad-bandwidth infrared spectra of translationally and rotationally cold (10-20 K) gas-phase molecules with high absorption sensitivity and fast acquisition times. The design and performance of the combined apparatus are discussed in detail. Recorded rovibrational spectra in the CH stretching region of several organic molecules, including vinyl bromide (CH_2CHBr), adamantane (C_{10}H_{16}), and diamantane (C_{14}H_{20}) demonstrate the resolution and sensitivity of this technique, as well as the intrinsic challenges faced in extending the frontier of high-resolution spectroscopy to large complex molecules.

Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

PubMed

Lennox, J Christian; Dempsey, Jillian L

2017-11-22

A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

Measurement of Absorption Coefficient of Paraformaldehyde and Metaldehyde with Terahertz Spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, J.; Xia, T.; Chen, Q.; Sun, Q.; Deng, Y.; Wang, C.

2018-03-01

The characteristic absorption spectra of paraformaldehyde and metaldehyde in the terahertz frequency region are obtained by terahertz time-domain spectroscopy (THz-TDS). In order to reduce the absorption of terahertz (THz) wave by water vapor in the air and the background noise, the measurement system was filled with dry air and the measurements were conducted at the temperature of 24°C. Meanwhile, the humidity was controlled within 10% RH. The THz frequency domain spectra of samples and their references from 0 to 2.5 THz were analyzed via Fourier transform. The refractive index and absorption coefficients of the two aldehydes were calculated by the model formulas. From 0.1 to 2.5 THz, there appear two weak absorption peaks at 1.20 and 1.66 THz in the absorption spectra of paraformaldehyde. Only one distinct absorption peak emerges at 1.83 THz for metaldehyde. There are significant differences between the terahertz absorption coefficients of paraformaldehyde and metaldehyde, which can be used as "fingerprints" to identify these substances. Furthermore, the relationship between the average absorption coefficients and mass concentrations was investigated and the average absorption coefficient-mass concentration diagrams of paraformaldehyde and metaldehyde were shown. For paraformaldehyde, there is a linear relationship between the average absorption coefficient and the natural logarithm of mass concentration. For metaldehyde, there exists a simpler linear relationship between the average absorption coefficient and the mass concentration. Because of the characteristics of THz absorption of paraformaldehyde and metaldehyde, the THz-TDS can be applied to the qualitative and quantitative detection of the two aldehydes to reduce the unpredictable hazards due to these substances.

CuInGaSe{sub 2} nanoparticles by pulsed laser ablation in liquid medium

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

Mendivil, M.I.; García, L.V.; Krishnan, B.

2015-12-15

Highlights: • CIGS nanocolloids were synthesized using PLAL technique. • Characterized their morphology, structure, composition and optical properties. • Morphologies were dependent on ablation wavelength and liquid medium. • Optical absorption and bandgap of these nanocolloids were tunable. - Abstract: Pulsed laser ablation in liquid medium (PLALM) is a nanofabrication technique to produce complex nanostructures. CuInGaSe{sub 2} (CIGS) is an alloy with applications in photovoltaic industry. In this work, we studied the effects of laser ablation wavelength, energy fluence and liquid medium on the properties of the CIGS nanoparticles synthesized by PLALM. The nanoparticles obtained were analyzed by transmission electronmore » microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), selected area electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS) and UV–vis absorption spectroscopy. XPS results confirmed the chemical states and composition of the ablated products. TEM analysis showed different morphologies for the nanomaterials obtained in different liquid media and ablation wavelengths. The optical properties for these CIGS nanocolloids were analyzed using UV–vis absorption spectroscopy. The results demonstrated the use of PLALM as a useful synthesis technique for nanoparticles of quaternary photovoltaic materials.« less

Group 6 metal pentacarbonyl complexes of air-stable primary, secondary, and tertiary ferrocenylethylphosphines.

PubMed

Rabiee Kenaree, Amir; Sauvé, Ethan R; Ragogna, Paul J; Gilroy, Joe B

2016-02-21

The synthesis and characterization of a series of Group 6 metal pentacarbonyl complexes of air stable primary, secondary, and tertiary phosphines containing ferrocenylethyl substituents are reported [M(CO)5L: M = Cr, Mo, W; L = PH2(CH2CH2Fc), PH(CH2CH2Fc)2, P(CH2CH2Fc)3]. The structure and composition of the complexes were confirmed by multinuclear NMR spectroscopy, IR and UV-Vis absorption spectroscopy, mass spectrometry, X-ray crystallography, and elemental analysis. The solid-state structural data reported revealed trends in M-C and M-P bond lengths that mirrored those of the atomic radii of the Group 6 metals involved. UV-Vis absorption spectroscopy and cyclic voltammetry highlighted characteristics consistent with electronically isolated ferrocene units including wavelengths of maximum absorption between 435 and 441 nm and reversible one-electron (per ferrocene unit) oxidation waves between 10 and -5 mV relative to the ferrocene/ferrocenium redox couple. IR spectroscopy confirmed that the σ donating ability of the phosphines increased as ferrocenylethyl substituents were introduced and that the tertiary phosphine ligand described is a stronger σ donor than PPh3 and a weaker σ donor than PEt3, respectively.

Novel Semi-Parametric Algorithm for Interference-Immune Tunable Absorption Spectroscopy Gas Sensing

PubMed Central

Michelucci, Umberto; Venturini, Francesca

2017-01-01

One of the most common limits to gas sensor performance is the presence of unwanted interference fringes arising, for example, from multiple reflections between surfaces in the optical path. Additionally, since the amplitude and the frequency of these interferences depend on the distance and alignment of the optical elements, they are affected by temperature changes and mechanical disturbances, giving rise to a drift of the signal. In this work, we present a novel semi-parametric algorithm that allows the extraction of a signal, like the spectroscopic absorption line of a gas molecule, from a background containing arbitrary disturbances, without having to make any assumption on the functional form of these disturbances. The algorithm is applied first to simulated data and then to oxygen absorption measurements in the presence of strong fringes.To the best of the authors’ knowledge, the algorithm enables an unprecedented accuracy particularly if the fringes have a free spectral range and amplitude comparable to those of the signal to be detected. The described method presents the advantage of being based purely on post processing, and to be of extremely straightforward implementation if the functional form of the Fourier transform of the signal is known. Therefore, it has the potential to enable interference-immune absorption spectroscopy. Finally, its relevance goes beyond absorption spectroscopy for gas sensing, since it can be applied to any kind of spectroscopic data. PMID:28991161

Mid-infrared absorption spectroscopy using quantum cascade lasers

NASA Astrophysics Data System (ADS)

Haibach, Fred; Erlich, Adam; Deutsch, Erik

2011-06-01

Block Engineering has developed an absorption spectroscopy system based on widely tunable Quantum Cascade Lasers (QCL). The QCL spectrometer rapidly cycles through a user-selected range in the mid-infrared spectrum, between 6 to 12 μm (1667 to 833 cm-1), to detect and identify substances on surfaces based on their absorption characteristics from a standoff distance of up to 2 feet with an eye-safe laser. It can also analyze vapors and liquids in a single device. For military applications, the QCL spectrometer has demonstrated trace explosive, chemical warfare agent (CWA), and toxic industrial chemical (TIC) detection and analysis. The QCL's higher power density enables measurements from diffuse and highly absorbing materials and substrates. Other advantages over Fourier Transform Infrared (FTIR) spectroscopy include portability, ruggedness, rapid analysis, and the ability to function from a distance through free space or a fiber optic probe. This paper will discuss the basic technology behind the system and the empirical data on various safety and security applications.

A new on-axis micro-spectrophotometer for combining Raman, fluorescence and UV/Vis absorption spectroscopy with macromolecular crystallography at the Swiss Light Source

PubMed Central

Pompidor, Guillaume; Dworkowski, Florian S. N.; Thominet, Vincent; Schulze-Briese, Clemens; Fuchs, Martin R.

2013-01-01

The combination of X-ray diffraction experiments with optical methods such as Raman, UV/Vis absorption and fluorescence spectroscopy greatly enhances and complements the specificity of the obtained information. The upgraded version of the in situ on-axis micro-spectrophotometer, MS2, at the macromolecular crystallography beamline X10SA of the Swiss Light Source is presented. The instrument newly supports Raman and resonance Raman spectroscopy, in addition to the previously available UV/Vis absorption and fluorescence modes. With the recent upgrades of the spectral bandwidth, instrument stability, detection efficiency and control software, the application range of the instrument and its ease of operation were greatly improved. Its on-axis geometry with collinear X-ray and optical axes to ensure optimal control of the overlap of sample volumes probed by each technique is still unique amongst comparable facilities worldwide and the instrument has now been in general user operation for over two years. PMID:23955041

Multiphoton-gated cycloreversion reaction of a fluorescent diarylethene derivative as revealed by transient absorption spectroscopy.

PubMed

Nagasaka, Tatsuhiro; Kunishi, Tomohiro; Sotome, Hikaru; Koga, Masafumi; Morimoto, Masakazu; Irie, Masahiro; Miyasaka, Hiroshi

2018-06-07

The one- and two-photon cycloreversion reactions of a fluorescent diarylethene derivative with oxidized benzothiophene moieties were investigated by means of ultrafast laser spectroscopy. Femtosecond transient absorption spectroscopy under the one-photon excitation condition revealed that the excited closed-ring isomer is simply deactivated into the initial ground state with a time constant of 2.6 ns without remarkable cycloreversion, the results of which are consistent with the very low cycloreversion reaction yield (<10-5) under steady-state light irradiation. On the other hand, an efficient cycloreversion reaction was observed under irradiation with a picosecond laser pulse at 532 nm. The excitation intensity dependence of the cycloreversion reaction indicates that a highly excited state attained by the stepwise two-photon absorption is responsible for the marked increase of the cycloreversion reaction, and the quantum yield at the highly excited state was estimated to be 0.018 from quantitative analysis, indicating that the reaction is enhanced by a factor of >1800.

Fringes in FTIR spectroscopy revisited: understanding and modelling fringes in infrared spectroscopy of thin films.

PubMed

Konevskikh, Tatiana; Ponossov, Arkadi; Blümel, Reinhold; Lukacs, Rozalia; Kohler, Achim

2015-06-21

The appearance of fringes in the infrared spectroscopy of thin films seriously hinders the interpretation of chemical bands because fringes change the relative peak heights of chemical spectral bands. Thus, for the correct interpretation of chemical absorption bands, physical properties need to be separated from chemical characteristics. In the paper at hand we revisit the theory of the scattering of infrared radiation at thin absorbing films. Although, in general, scattering and absorption are connected by a complex refractive index, we show that for the scattering of infrared radiation at thin biological films, fringes and chemical absorbance can in good approximation be treated as additive. We further introduce a model-based pre-processing technique for separating fringes from chemical absorbance by extended multiplicative signal correction (EMSC). The technique is validated by simulated and experimental FTIR spectra. It is further shown that EMSC, as opposed to other suggested filtering methods for the removal of fringes, does not remove information related to chemical absorption.

Cobalt Oxide Nanoclusters on Rutile Titania as Bifunctional Units for Water Oxidation Catalysis and Visible Light Absorption: Understanding the Structure-Activity Relationship.

PubMed

Maeda, Kazuhiko; Ishimaki, Koki; Okazaki, Megumi; Kanazawa, Tomoki; Lu, Daling; Nozawa, Shunsuke; Kato, Hideki; Kakihana, Masato

2017-02-22

The structure of cobalt oxide (CoO x ) nanoparticles dispersed on rutile TiO 2 (R-TiO 2 ) was characterized by X-ray diffraction, UV-vis-NIR diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray absorption fine-structure spectroscopy, and X-ray photoelectron spectroscopy. The CoO x nanoparticles were loaded onto R-TiO 2 by an impregnation method from an aqueous solution containing Co(NO 3 ) 2 ·6H 2 O followed by heating in air. Modification of the R-TiO 2 with 2.0 wt % Co followed by heating at 423 K for 1 h resulted in the highest photocatalytic activity with good reproducibility. Structural analyses revealed that the activity of this photocatalyst depended strongly on the generation of Co 3 O 4 nanoclusters with an optimal distribution. These nanoclusters are thought to interact with the R-TiO 2 surface, resulting in visible light absorption and active sites for water oxidation.

A new on-axis micro-spectrophotometer for combining Raman, fluorescence and UV/Vis absorption spectroscopy with macromolecular crystallography at the Swiss Light Source.

PubMed

Pompidor, Guillaume; Dworkowski, Florian S N; Thominet, Vincent; Schulze-Briese, Clemens; Fuchs, Martin R

2013-09-01

The combination of X-ray diffraction experiments with optical methods such as Raman, UV/Vis absorption and fluorescence spectroscopy greatly enhances and complements the specificity of the obtained information. The upgraded version of the in situ on-axis micro-spectrophotometer, MS2, at the macromolecular crystallography beamline X10SA of the Swiss Light Source is presented. The instrument newly supports Raman and resonance Raman spectroscopy, in addition to the previously available UV/Vis absorption and fluorescence modes. With the recent upgrades of the spectral bandwidth, instrument stability, detection efficiency and control software, the application range of the instrument and its ease of operation were greatly improved. Its on-axis geometry with collinear X-ray and optical axes to ensure optimal control of the overlap of sample volumes probed by each technique is still unique amongst comparable facilities worldwide and the instrument has now been in general user operation for over two years.

Chirped-Pulse Fourier Transform Microwave Spectroscopy Coupled with a Flash Pyrolysis Microreactor: Structural Determination of the Reactive Intermediate Cyclopentadienone.

PubMed

Kidwell, Nathanael M; Vaquero-Vara, Vanesa; Ormond, Thomas K; Buckingham, Grant T; Zhang, Di; Mehta-Hurt, Deepali N; McCaslin, Laura; Nimlos, Mark R; Daily, John W; Dian, Brian C; Stanton, John F; Ellison, G Barney; Zwier, Timothy S

2014-07-03

Chirped-pulse Fourier transform microwave spectroscopy (CP-FTMW) is combined with a flash pyrolysis (hyperthermal) microreactor as a novel method to investigate the molecular structure of cyclopentadienone (C5H4═O), a key reactive intermediate in biomass decomposition and aromatic oxidation. Samples of C5H4═O were generated cleanly from the pyrolysis of o-phenylene sulfite and cooled in a supersonic expansion. The (13)C isotopic species were observed in natural abundance in both C5H4═O and in C5D4═O samples, allowing precise measurement of the heavy atom positions in C5H4═O. The eight isotopomers include: C5H4═O, C5D4═O, and the singly (13)C isotopomers with (13)C substitution at the C1, C2, and C3 positions. Microwave spectra were interpreted by CCSD(T) ab initio electronic structure calculations and an re molecular structure for C5H4═O was found. Comparisons of the structure of this "anti-aromatic" molecule are made with those of comparable organic molecules, and it is concluded that the disfavoring of the "anti-aromatic" zwitterionic resonance structure is consistent with a more pronounced C═C/C-C bond alternation.

Saving Your Students' Skin. Undergraduate Experiments That Probe UV Protection by Sunscreens and Sunglasses.

ERIC Educational Resources Information Center

Abney, James R.; Scalettar, Bethe A.

1998-01-01

Describes absorption spectroscopy experiments that allow students to explore the mechanisms by which sunscreens and sunglasses provide protection from ultraviolet radiation. Exposes students to absorption phenomena in an engaging way. (DDR)

Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

NASA Astrophysics Data System (ADS)

Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th; Heimann, P. A.; Dorchies, F.

2014-04-01

The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called ``molecular movie'' within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.

Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

PubMed Central

Gaudin, J.; Fourment, C.; Cho, B. I.; Engelhorn, K.; Galtier, E.; Harmand, M.; Leguay, P. M.; Lee, H. J.; Nagler, B.; Nakatsutsumi, M.; Ozkan, C.; Störmer, M.; Toleikis, S.; Tschentscher, Th; Heimann, P. A.; Dorchies, F.

2014-01-01

The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called “molecular movie” within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level of the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes. PMID:24740172

[Study on transient absorption spectrum of tungsten nanoparticle with HepG2 tumor cell].

PubMed

Cao, Lin; Shu, Xiao-Ning; Liang, Dong; Wang, Cong

2014-07-01

Significance of this study lies in tungsten nano materials can be used as a preliminary innovative medicines applied basic research. This paper investigated the inhibition of tungsten nanoparticles which effected on human hepatoma HepG2 cells by MTT. The authors use transient absorption spectroscopy (TAS) technology absorption and emission spectra characterization of charge transfer between nanoparticles and tumor cell. The authors discussed the role of the tungsten nanoparticles in the tumor early detection of the disease and its anti-tumor properties. In the HepG2 experiments system, 100-150 microg x mL(-1) is the best drug concentration of anti-tumor activity which recact violently within 6 hours and basically completed in 24 hours. The results showed that transient absorption spectroscopy can be used as tumor detection methods and characterization of charge transfer between nano-biosensors and tumor cells. Tungsten nanoparticles have potential applications as anticancer drugs.

Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

DOE PAGES

Sneeden, Eileen Y.; Hackett, Mark J.; Cotelesage, Julien J. H.; ...

2017-07-27

Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s → 3p transition tomore » the singly occupied molecular orbital of the free radical. In conclusion, our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.« less

Local Structure Determination of Carbon/Nickel Ferrite Composite Nanofibers Probed by X-ray Absorption Spectroscopy.

PubMed

Nilmoung, Sukunya; Kidkhunthod, Pinit; Maensiri, Santi

2015-11-01

Carbon/NiFe2O4 composite nanofibers have been successfully prepared by electrospinning method using a various concentration solution of Ni and Fe nitrates dispersed into polyacrylonitride (PAN) solution in N,N' dimethylformamide. The phase and mophology of PAN/NiFe2O4 composite samples were characterized and investigated by X-ray diffraction and scanning electron microscopy. The magnetic properties of the prepared samples were measured at ambient temperature by a vibrating sample magnetometer. It is found that all composite samples exhibit ferromagnetism. This could be local-structurally explained by the existed oxidation states of Ni2+ and Fe3+ in the samples. Moreover, local environments around Ni and Fe ions could be revealed by X-ray absorption spectroscopy (XAS) measurement including X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS).

Laser diode absorption spectroscopy for accurate CO(2) line parameters at 2 microm: consequences for space-based DIAL measurements and potential biases.

PubMed

Joly, Lilian; Marnas, Fabien; Gibert, Fabien; Bruneau, Didier; Grouiez, Bruno; Flamant, Pierre H; Durry, Georges; Dumelie, Nicolas; Parvitte, Bertrand; Zéninari, Virginie

2009-10-10

Space-based active sensing of CO(2) concentration is a very promising technique for the derivation of CO(2) surface fluxes. There is a need for accurate spectroscopic parameters to enable accurate space-based measurements to address global climatic issues. New spectroscopic measurements using laser diode absorption spectroscopy are presented for the preselected R30 CO(2) absorption line ((20(0)1)(III)<--(000) band) and four others. The line strength, air-broadening halfwidth, and its temperature dependence have been investigated. The results exhibit significant improvement for the R30 CO(2) absorption line: 0.4% on the line strength, 0.15% on the air-broadening coefficient, and 0.45% on its temperature dependence. Analysis of potential biases of space-based DIAL CO(2) mixing ratio measurements associated to spectroscopic parameter uncertainties are presented.

Towards simultaneous measurements of electronic and structural properties in ultra-fast x-ray free electron laser absorption spectroscopy experiments

DOE PAGES

Gaudin, J.; Fourment, C.; Cho, B. I.; ...

2014-04-17

The rapidly growing ultrafast science with X-ray lasers unveils atomic scale processes with unprecedented time resolution bringing the so called “molecular movie” within reach. X-ray absorption spectroscopy is one of the most powerful x-ray techniques providing both local atomic order and electronic structure when coupled with ad-hoc theory. Collecting absorption spectra within few x-ray pulses is possible only in a dispersive setup. We demonstrate ultrafast time-resolved measurements of the LIII-edge x-ray absorption near-edge spectra of irreversibly laser excited Molybdenum using an average of only few x-ray pulses with a signal to noise ratio limited only by the saturation level ofmore » the detector. The simplicity of the experimental set-up makes this technique versatile and applicable for a wide range of pump-probe experiments, particularly in the case of non-reversible processes.« less

High sensitivity detection of NO2 employing off-axis integrated cavity output spectroscopy coupled with multiple line integrated spectroscopy

NASA Astrophysics Data System (ADS)

Rao, Gottipaty N.; Karpf, Andreas

2011-05-01

We report on the development of a new sensor for NO2 with ultrahigh sensitivity of detection. This has been accomplished by combining off-axis integrated cavity output spectroscopy (OA-ICOS) (which can provide large path lengths of the order of several km in a small volume cell) with multiple line integrated absorption spectroscopy (MLIAS) (where we integrate the absorption spectra over a large number of rotational-vibrational transitions of the molecular species to further improve the sensitivity). Employing an external cavity tunable quantum cascade laser operating in the 1601 - 1670 cm-1 range and a high-finesse optical cavity, the absorption spectra of NO2 over 100 transitions in the R-band have been recorded. From the observed linear relationship between the integrated absorption vs. concentration of NO2, we report an effective sensitivity of detection of 10 ppt for NO2. To the best of our knowledge, this is among the most sensitive levels of detection of NO2 to date. A sensitive sensor for the detection of NO2 will be helpful to monitor the ambient air quality, combustion emissions from the automobiles, power plants, aircraft and for the detection of nitrate based explosives (which are commonly used in improvised explosives (IEDs)). Additionally such a sensor would be valuable for the study of complex chemical reactions that undergo in the atmosphere resulting in the formation of photochemical smog, tropospheric ozone and acid rain.

VCSEL-based oxygen spectroscopy for structural analysis of pharmaceutical solids

NASA Astrophysics Data System (ADS)

Svensson, T.; Andersson, M.; Rippe, L.; Svanberg, S.; Andersson-Engels, S.; Johansson, J.; Folestad, S.

2008-02-01

We present a minimalistic and flexible single-beam instrumentation based on sensitive tunable diode laser absorption spectroscopy (TDLAS) and its use in structural analysis of highly scattering pharmaceutical solids. By utilising a vertical cavity surface emitting laser (VCSEL) for sensing of molecular oxygen dispersed in tablets, we address structural properties such as porosity. Experiments involve working with unknown path lengths, severe backscattering and diffuse light. These unusual experimental conditions has led to the use of the term gas in scattering media absorption spectroscopy (GASMAS). By employing fully digital wavelength modulation spectroscopy and coherent sampling, system sensitivity in ambient air experiments reaches the 10-7 range. Oxygen absorption exhibited by our tablets, being influenced by both sample porosity and scattering, was in the range 8×10-5 to 2×10-3, and corresponds to 2-50 mm of path length through ambient air (Leq). The day-to-day reproducibility was on average 1.8% (0.3 mm Leq), being limited by mechanical positioning. This is the first time sub-millimetre sensitivity is reached in GASMAS. We also demonstrate measurements on gas transport on a 1-s time scale. By employing pulsed illumination and time-correlated single-photon counting, we reveal that GASMAS exhibits excellent correlation with time-domain photon migration. In addition, we introduce an optical measure of porosity by relating oxygen absorption to average photon time-of-flight. Finally, the simplicity, robustness and low cost of this novel TDLAS instrumentation provide industrial potential.

First calibration measurements of an FTIR absorption spectroscopy system for liquid hydrogen isotopologues for the isotope separation system of fusion power plants

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

Groessle, R.; Beck, A.; Bornschein, B.

2015-03-15

Fusion facilities like ITER and DEMO will circulate huge amounts of deuterium and tritium in their fuel cycle with an estimated throughput of kg per hour. One important capability of these fuel cycles is to separate the hydrogen isotopologues (H{sub 2}, D{sub 2}, T{sub 2}, HD, HT, DT). For this purpose the Isotope Separation System (ISS), using cryogenic distillation, as part of the Tritium Enrichment Test Assembly (TRENTA) is under development at Tritium Laboratory Karlsruhe. Fourier transform infrared absorption spectroscopy (FTIR) has been selected to prove its capability for online monitoring of the tritium concentration in the liquid phase atmore » the bottom of the distillation column of the ISS. The actual research-development work is focusing on the calibration of such a system. Two major issues are the identification of appropriate absorption lines and their dependence on the isotopic concentrations and composition. For this purpose the Tritium Absorption IR spectroscopy experiment has been set up as an extension of TRENTA. For calibration a Raman spectroscopy system is used. First measurements, with equilibrated mixtures of H{sub 2}, D{sub 2} and HD demonstrate that FTIR can be used for quantitative analysis of liquid hydro-gen isotopologues and reveal a nonlinear dependence of the integrated absorbance from the D{sub 2} concentration in the second vibrational branch of D{sub 2} FTIR spectra. (authors)« less

Nonlinear Spectroscopy of Rubidium: An Undergraduate Experiment

ERIC Educational Resources Information Center

Jacques, V.; Hingant, B.; Allafort, A.; Pigeard, M.; Roch, J. F.

2009-01-01

In this paper, we describe two complementary nonlinear spectroscopy methods which both allow one to achieve Doppler-free spectra of atomic gases. First, saturated absorption spectroscopy is used to investigate the structure of the 5S[subscript 1/2] [right arrow] 5P[subscript 3/2] transition in rubidium. Using a slightly modified experimental…

High power, widely tunable, mode-hop free, continuous wave external cavity quantum cascade laser for multi-species trace gas detection

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

Centeno, R.; Marchenko, D.; Mandon, J.

We present a high power, widely tunable, continuous wave external cavity quantum cascade laser designed for infrared vibrational spectroscopy of molecules exhibiting broadband and single line absorption features. The laser source exhibits single mode operation with a tunability up to 303 cm{sup −1} (∼24% of the center wavelength) at 8 μm, with a maximum optical output power of 200 mW. In combination with off-axis integrated output spectroscopy, trace-gas detection of broadband absorption gases such as acetone was performed and a noise equivalent absorption sensitivity of 3.7 × 10{sup −8 }cm{sup −1 }Hz{sup −1/2} was obtained.

Saturated absorption in a rotational molecular transition at 2.5 THz using a quantum cascade laser

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

Consolino, L., E-mail: luigi.consolino@ino.it; Campa, A.; Ravaro, M.

2015-01-12

We report on the evidence of saturation effects in a rotational transition of CH{sub 3}OH around 2.5 THz, induced by a free-running continuous-wave quantum cascade laser (QCL). The QCL emission is used for direct-absorption spectroscopy experiments, allowing to study the dependence of the absorption coefficient on gas pressure and laser intensity. A saturation intensity of 25 μW/mm{sup 2}, for a gas pressure of 17 μbar, is measured. This result represents the initial step towards the implementation of a QCL-based high-resolution sub-Doppler THz spectroscopy, which is expected to improve by orders of magnitude the precision of THz spectrometers.

Effects of alkyl spacer group length on Vis-NIR absorption behavior in FTC-like guest-host EO polymers

NASA Astrophysics Data System (ADS)

Barto, Richard R., Jr.; Bedworth, Peter V.; Epstein, Joseph A.; Ermer, Susan P.; Taylor, Rebecca E.; Frank, Curtis W.

2003-07-01

Spectral absorption behavior of a series of FTC-like dyes of varying shape incorporated into amorphous polycarbonate (APC) is characterized by photothermal deflection spectroscopy. Previous Monte Carlo calculations by Dalton and Robinson predict a strong dependence of the macroscopic nonlinear optical susceptibility on the chromophore waist:length aspect ratio in electric field-poled films. This dependence arises from London interactions between chromophores, which are expected to influence the absorption characteristics of the composite both by changing the local polarity of the medium and through dipole interactions. It is expected that these interactions will play a role in the absorption characteristics of unpoled films as well. Of particular interest are the spectral characteristics of the red edge of the main dye electronic absorption peak, and the fine structure in the near-IR, dominated by overtones of fundamental C-H stretching and bending modes. The spectral structure in these key regions can be influenced by inter- and intramolecular interactions and conformational changes in the dye. The near-IR structure, in turn, will dictate absorption loss in optical devices prepared from these materials at key transmission wavelengths (1.3 and 1.55 um). In this study, a homologous series of spacer lengths, ranging from ethyl to hexyl, attached to an FTC-like NLO chromophore, LMCO-46M, is characterized by a combination of photothermal deflection spectroscopy (PDS) and UV-Vis spectroscopy to examine the effects of the molecular environment on near-IR loss at 1090 nm, 1300 nm and 1550 nm.

Gas-phase broadband spectroscopy using active sources: progress, status, and applications

PubMed Central

Cossel, Kevin C.; Waxman, Eleanor M.; Finneran, Ian A.; Blake, Geoffrey A.; Ye, Jun; Newbury, Nathan R.

2017-01-01

Broadband spectroscopy is an invaluable tool for measuring multiple gas-phase species simultaneously. In this work we review basic techniques, implementations, and current applications for broadband spectroscopy. We discuss components of broad-band spectroscopy including light sources, absorption cells, and detection methods and then discuss specific combinations of these components in commonly-used techniques. We finish this review by discussing potential future advances in techniques and applications of broad-band spectroscopy. PMID:28630530

X-ray absorption spectroscopy: EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge Structure)

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

Alp, E.E.; Mini, S.M.; Ramanathan, M.

1990-04-01

The x-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. It has also played an important role in the discovery and systematization of rare-earth elements. The discovery of synchrotron radiation in 1952, and later the availability of broadly tunable synchrotron based x-ray sources have revitalized this technique since the 1970's. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge by Sayers et. al. has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-raymore » Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. An excellent description of the principles and data analysis techniques of EXAFS is given by Teo. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, we will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and samples limitations.« less

HREELS to identify electronic structures of organic thin films.

PubMed

Oeter, D; Ziegler, C; Göpel, W

1995-10-01

The electronic structure of alpha-oligothiophene (alphanT) thin films has been investigated for increasing chain lengths of n= 4-8 thiophene units with high resolution electron energy loss spectroscopy (HREELS) in the specular reflection geometry at a primary energy of 15 eV. The great advantage of this technique in contrast to UV/VIS absorption spectroscopy results from the fact, that the impact scattering mechanism of HREELS makes it possible to also detect optically forbidden electronic transitions. On the other hand, the electrons used as probes in HREELS have a wavelength which is two orders of magnitudes smaller if compared to those of photons used in UV/VIS absorption spectroscopy. Therefore individual molecules are excited by HREELS independent from each other and hence the excitation of collective excitons is not possible. As a result, information about the orientation of the molecules cannot be achieved with HREELS, which, however, is possible in polarization-dependent UV/VIS spectroscopy.

X-ray absorption fine structure (XAFS) spectroscopy using synchrotron radiation

NASA Astrophysics Data System (ADS)

Shrivastava, B. D.

2012-05-01

The X-ray absorption fine structure (XAFS) spectra are best recorded when a highly intense beam of X-rays from a synchrotron is used along with a good resolution double crystal or curved crystal spectrometer and detectors like ionization chambers, scintillation counters, solid state detectors etc. Several synchrotrons around the world have X-ray beamlines dedicated specifically to XAFS spectroscopy. Fortunately, the Indian synchrotron (Indus-2) at Raja Ramanna Centre for Advanced Technology (RRCAT) at Indore has started operation. A dispersive type EXAFS beamline called BL-8 has been commissioned at this synchrotron and another beamline having double crystal monochromator (DCM) is going to be commissioned shortly. In Indian context, in order that more research workers use these beamlines, the study of XAFS spectroscopy using synchrotron radiation becomes important. In the present work some of the works done by our group on XAFS spectroscopy using synchrotron radiation have been described.

Cavity-Enhanced Absorption Spectroscopy and Photoacoustic Spectroscopy for Human Breath Analysis

NASA Astrophysics Data System (ADS)

Wojtas, J.; Tittel, F. K.; Stacewicz, T.; Bielecki, Z.; Lewicki, R.; Mikolajczyk, J.; Nowakowski, M.; Szabra, D.; Stefanski, P.; Tarka, J.

2014-12-01

This paper describes two different optoelectronic detection techniques: cavity-enhanced absorption spectroscopy and photoacoustic spectroscopy. These techniques are designed to perform a sensitive analysis of trace gas species in exhaled human breath for medical applications. With such systems, the detection of pathogenic changes at the molecular level can be achieved. The presence of certain gases (biomarkers), at increased concentration levels, indicates numerous human diseases. Diagnosis of a disease in its early stage would significantly increase chances for effective therapy. Non-invasive, real-time measurements, and high sensitivity and selectivity, capable of minimum discomfort for patients, are the main advantages of human breath analysis. At present, monitoring of volatile biomarkers in breath is commonly useful for diagnostic screening, treatment for specific conditions, therapy monitoring, control of exogenous gases (such as bacterial and poisonous emissions), as well as for analysis of metabolic gases.

Frontiers in Chemical Physics

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

Bowlan, Pamela Renee

2016-05-02

These are slides dealing with frontiers in chemical physics. The following topics are covered: Time resolving chemistry with ultrashort pulses in the 0.1-40 THz spectral range; Example: Mid-infrared absorption spectrum of the intermediate state CH 2OO; Tracking reaction dynamics through changes in the spectra; Single-shot measurement of the mid-IR absorption dynamics; Applying 2D coherent mid-IR spectroscopy to learn more about transition states; Time resolving chemical reactions at a catalysis using mid-IR and THz pulses; Studying topological insulators requires a surface sensitive probe; Nonlinear phonon dynamics in Bi 2Se 3; THz-pump, SHG-probe as a surface sensitive coherent 2D spectroscopy; Nanometer andmore » femtosecond spatiotemporal resolution mid-IR spectroscopy; Coherent two-dimensional THz/mid-IR spectroscopy with 10nm spatial resolution; Pervoskite oxides as catalysts; Functionalized graphene for catalysis; Single-shot spatiotemporal measurements; Spatiotemporal pulse measurement; Intense, broad-band THz/mid-IR generation with organic crystals.« less

Coordination of Fe, Ga and Ge in high pressure glasses by Moessbauer, Raman and X-ray absorption spectroscopy, and geological implications

NASA Technical Reports Server (NTRS)

Fleet, M. E.; Henderson, G. S.; Herzberg, C. T.; Crozier, E. D.; Osborne, M. D.; Scarfe, C. M.

1984-01-01

For some time, it has been recognized that the structure of silicate liquids has a great bearing on such magma properties as viscosity, diffusivity, and thermal expansion and on the extrapolation of thermodynamic quantities outside of the experimentally measurable range. In this connection it is vital to know if pressure imposes changes in melt structure similar to the pressure-induced reconstructive transformations in crystals. In the present study on 1 bar and high pressure glasses, an investigation is conducted regarding the coordination of Fe(3+) in Fe silicate glasses by Moessbauer spectroscopy. Raman spectroscopy is employed to explore the coordinations of Ge(4+) in GeO2 glasses and of Ga(3+) in NaGa silicate glasses, while the coordination of Ga(3+) in NaGaSiO4 glasses is studied with the aid of methods of X-ray absorption spectroscopy.

Coordination of Fe, Ga and Ge in high pressure glasses by Moessbauer, Raman and X-ray absorption spectroscopy, and geological implications

NASA Astrophysics Data System (ADS)

Fleet, M. E.; Herzberg, C. T.; Henderson, G. S.; Crozier, E. D.; Osborne, M. D.; Scarfe, C. M.

1984-07-01

For some time, it has been recognized that the structure of silicate liquids has a great bearing on such magma properties as viscosity, diffusivity, and thermal expansion and on the extrapolation of thermodynamic quantities outside of the experimentally measurable range. In this connection it is vital to know if pressure imposes changes in melt structure similar to the pressure-induced reconstructive transformations in crystals. In the present study on 1 bar and high pressure glasses, an investigation is conducted regarding the coordination of Fe(3+) in Fe silicate glasses by Moessbauer spectroscopy. Raman spectroscopy is employed to explore the coordinations of Ge(4+) in GeO2 glasses and of Ga(3+) in NaGa silicate glasses, while the coordination of Ga(3+) in NaGaSiO4 glasses is studied with the aid of methods of X-ray absorption spectroscopy.

Laser optogalvanic spectroscopy of molecules

NASA Technical Reports Server (NTRS)

Webster, C. R.; Rettner, C. T.

1983-01-01

In laser optogalvanic (LOG) spectroscopy, a tunable laser is used to probe the spectral characteristics of atomic or molecular species within an electrical discharge in a low pressure gas. Optogalvanic signals arise when the impedance of the discharge changes in response to the absorption of laser radiation. The technique may, therefore, be referred to as impedance spectroscopy. This change in impedance may be monitored as a change in the voltage across the discharge tube. LOG spectra are recorded by scanning the wavelength of a chopped CW dye laser while monitoring the discharge voltage with a lock-in amplifier. LOG signals are obtained if the laser wavelength matches a transition in a species present in the discharge (or flame), and if the absorption of energy in the laser beam alters the impedance of the discharge. Infrared LOG spectroscopy of molecules has been demonstrated and may prove to be the most productive application in the field of optogalvanic techniques.

Biological X-ray absorption spectroscopy (BioXAS): a valuable tool for the study of trace elements in the life sciences.

PubMed

Strange, Richard W; Feiters, Martin C

2008-10-01

Using X-ray absorption spectroscopy (XAS) the binding modes (type and number of ligands, distances and geometry) and oxidation states of metals and other trace elements in crystalline as well as non-crystalline samples can be revealed. The method may be applied to biological systems as a 'stand-alone' technique, but it is particularly powerful when used alongside other X-ray and spectroscopic techniques and computational approaches. In this review, we highlight how biological XAS is being used in concert with crystallography, spectroscopy and computational chemistry to study metalloproteins in crystals, and report recent applications on relatively rare trace elements utilised by living organisms and metals involved in neurodegenerative diseases.

A high-temperature furnace for in situ synchrotron X-ray spectroscopy under controlled atmospheric conditions.

PubMed

Eeckhout, Sigrid Griet; Gorges, Bernard; Barthe, Laurent; Pelosi, Orietta; Safonova, Olga; Giuli, Gabriele

2008-09-01

A high-temperature furnace with an induction heater coil has been designed and constructed for in situ X-ray spectroscopic experiments under controlled atmospheric conditions and temperatures up to 3275 K. The multi-purpose chamber design allows working in backscattering and normal fluorescence mode for synchrotron X-ray absorption and emission spectroscopy. The use of the furnace is demonstrated in a study of the in situ formation of Cr oxide between 1823 K and 2023 K at logPO(2) values between -10.0 and -11.3 using X-ray absorption near-edge spectroscopy. The set-up is of particular interest for studying liquid metals, alloys and other electrically conductive materials under extreme conditions.

Quantification of DNA in simple eukaryotic cells using Fourier transform infrared spectroscopy.

PubMed

Whelan, Donna R; Bambery, Keith R; Puskar, Ljiljana; McNaughton, Don; Wood, Bayden R

2013-10-01

A technique capable of detecting and monitoring nucleic acid concentration offers potential in diagnosing cancer and further developing an understanding of the biochemistry of disease. The application of Fourier transform infrared (FTIR) spectroscopy has previously been hindered by the supposed non-Beer-Lambert absorption behavior of DNA in intact cells making elucidation of the DNA bands difficult. We use known composition DNA/hemoglobin standards to successfully estimate the DNA content in avian erythrocyte nuclei (44.2%) and intact erythrocytes (12.8%). Furthermore we demonstrate that the absorption of cellular DNA does follow the Beer-Lambert Law and highlights the role of conformation and hydration in FTIR spectroscopy of biological samples. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen-Mediated Electron Doping of Gold Clusters As Revealed by In Situ X-ray and UV-vis Absorption Spectroscopy.

PubMed

Ishida, Ryo; Hayashi, Shun; Yamazoe, Seiji; Kato, Kazuo; Tsukuda, Tatsuya

2017-06-01

We previously reported that small (∼1.2 nm) gold clusters stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) exhibited a localized surface plasmon resonance (LSPR) band at ∼520 nm in the presence of NaBH 4 . To reveal the mechanism of this phenomenon, the electronic structure of Au:PVP during the reaction with NaBH 4 in air was examined by means of in situ X-ray absorption spectroscopy at Au L 3 -edge and UV-vis spectroscopy. These measurements indicated that the appearance of the LSPR band is not associated with the growth in size but is ascribed to electron doping to the Au sp band by the adsorbed H atoms.

Development of vacuum ultraviolet absorption spectroscopy system for wide measurement range of number density using a dual-tube inductively coupled plasma light source

NASA Astrophysics Data System (ADS)

Kuwahara, Akira; Matsui, Makoto; Yamagiwa, Yoshiki

2012-12-01

A vacuum ultraviolet absorption spectroscopy system for a wide measurement range of atomic number densities is developed. Dual-tube inductively coupled plasma was used as a light source. The probe beam profile was optimized for the target number density range by changing the mass flow rate of the inner and outer tubes. This system was verified using cold xenon gas. As a result, the measurement number density range was extended from the conventional two orders to five orders of magnitude.

Optical Diagnostics in the Gaseous Electronics Conference Reference Cell

PubMed Central

Hebner, G. A.; Greenberg, K. E.

1995-01-01

A number of laser-induced fluorescence and absorption spectroscopy studies have been conducted using Gaseous Electronics Conference Reference Cells. Laser-induced fluorescence has been used to measure hydrogen atom densities, to measure argon metastable spatial profiles, to determine the sheath electric field, and to infer the electron density and temperature. Absorption spectroscopy, using lamp sources and diode lasers, has been used to measure metastable atom densities in helium and argon discharges and fluorocarbon densities in silicon etching discharges. The experimental techniques and sample results of these investigations are reviewed. PMID:29151748

An electrochemical and photophysical study of a covalently linked inorganic-organic dyad.

PubMed

Kahnt, Axel; Heiniger, Leo-Philipp; Liu, Shi-Xia; Tu, Xiaoyan; Zheng, Zhiping; Hauser, Andreas; Decurtins, Silvio; Guldi, Dirk M

2010-02-22

A molecular donor-acceptor dyad comprising a hexarhenium cluster core, [Re(6)(mu(3)-Se)(8)](2+), and a fullerene moiety which are covalently linked through a pyridine ligand was synthesized and fully characterized. The electrochemical and photophysical properties are reported. The detailed study includes cyclic voltammetry, steady-state absorption and fluorescence spectroscopy, radiation chemistry and transient absorption spectroscopy. A light-induced electron transfer between the inorganic cluster moiety and the fullerene can be excluded. However, a light-induced energy transfer from the rhenium cluster to the fullerene is proposed.

Absorption spectroscopy and multi-angle scattering measurements in the visible spectral range for the geographic classification of Italian exravirgin olive oils

NASA Astrophysics Data System (ADS)

Mignani, Anna G.; Ciaccheri, Leonardo; Cimato, Antonio; Sani, Graziano; Smith, Peter R.

2004-03-01

Absorption spectroscopy and multi-angle scattering measurements in the visible spectral range are innovately used to analyze samples of extra virgin olive oils coming from selected areas of Tuscany, a famous Italian region for the production of extra virgin olive oil. The measured spectra are processed by means of the Principal Component Analysis method, so as to create a 3D map capable of clustering the Tuscan oils within the wider area of Italian extra virgin olive oils.

Total Absorption Study of Beta Decays Relevant for Nuclear Applications and Nuclear Structure

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

Algora, A.; Valencia, E.; Tain, J. L.

2014-06-01

We present an overview of our activities related to the study of the beta decay of neutron rich nuclei relevant for nuclear applications. Recent results of the study of the beta decay of Br using a new segmented total absorption spectrometer are presented. Our measurements were performed at the IGISOL facility using trap-assisted total absorption spectroscopy.

An environmentally friendly method for the fabrication of reduced graphene oxide foam with a super oil absorption capacity.

PubMed

He, Yongqiang; Liu, Yue; Wu, Tao; Ma, Junkui; Wang, Xingrui; Gong, Qiaojuan; Kong, Weina; Xing, Fubao; Liu, Yu; Gao, Jianping

2013-09-15

Three kinds of graphene oxide (GO) foams were fabricated using different freezing methods (unidirectional freezing drying (UDF), non-directional freezing drying, and air freezing drying), and the corresponding reduced graphene oxide (RGO) foams were prepared by their thermal reduction of those GO foams. These RGO foams were characterized by Fourier transform infrared spectroscopy, thermal gravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The absorption process and the factors that influence the absorption capacity were investigated. The RGO foams are hydrophobic and showed extremely high absorbing abilities for organic liquids. The absorption capacity of the RGO foams made by UDF was higher than 100 g g(-1) for all the oils tested (gasoline, diesel oil, pump oil, lubricating oil and olive oil) and had the highest value of about 122 g g(-1) for olive oil. The oil absorption capacity of the GO foams was lower than that of the RGO foams, but for olive oil, the absorption capacity was still high than 70 g g(-1), which is higher than that of most oil absorbents. Copyright © 2013 Elsevier B.V. All rights reserved.

Cavity ring-down spectroscopy in the liquid phase

NASA Astrophysics Data System (ADS)

Xu, Shucheng; Sha, Guohe; Xie, Jinchun

2002-02-01

A new application for cavity ring-down spectroscopic (CRDS) technique using a pulsed polarized light source has been developed in the absorption measurement of liquids for "colorless" organic compounds using both a single sample cell and double sample cells inserted in an optical cavity at Brewster angle. At present an experimental capability of measuring absorption coefficients as small as 2-5×10-7 cm-1 has been demonstrated by measurement of the absorption baselines. The first spectra for CRDS in the liquid phase, the C-H stretching fifth vibrational overtones of benzene in the pure liquid and hexane solution are obtained. The optical absorption length for liquids in both a single sample cell and double sample cells of 1 cm length is up to 900 cm due to multipass of light within an optical cavity. Compared to the thermal lens and optoacoustic spectroscopic techniques, the sensitivity for CRDS mainly depends on the optical absorption path of the sample (single passing path of the sample times multipass times), is not determined by the laser power and the length of the sample cell. The absolute absorption coefficient and band intensity for the sample are determined directly by the spectroscopy.

Measurements of gas parameters in plasma-assisted supersonic combustion processes using diode laser spectroscopy

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

Bolshov, Mikhail A; Kuritsyn, Yu A; Liger, V V

2009-09-30

We report a procedure for temperature and water vapour concentration measurements in an unsteady-state combustion zone using diode laser absorption spectroscopy. The procedure involves measurements of the absorption spectrum of water molecules around 1.39 {mu}m. It has been used to determine hydrogen combustion parameters in M = 2 gas flows in the test section of a supersonic wind tunnel. The relatively high intensities of the absorption lines used have enabled direct absorption measurements. We describe a differential technique for measurements of transient absorption spectra, the procedure we used for primary data processing and approaches for determining the gas temperature andmore » H{sub 2}O concentration in the probed zone. The measured absorption spectra are fitted with spectra simulated using parameters from spectroscopic databases. The combustion-time-averaged ({approx}50 ms) gas temperature and water vapour partial pressure in the hot wake region are determined to be 1050 K and 21 Torr, respectively. The large signal-to-noise ratio in our measurements allowed us to assess the temporal behaviour of these parameters. The accuracy in our temperature measurements in the probed zone is {approx}40 K. (laser applications and other topics in quantum electronics)« less

Frequency-agile, rapid scanning spectroscopy: absorption sensitivity of 2 × 10-12 cm-1 Hz-1/2 with a tunable diode laser

NASA Astrophysics Data System (ADS)

Long, D. A.; Truong, G.-W.; van Zee, R. D.; Plusquellic, D. F.; Hodges, J. T.

2014-03-01

We present ultrasensitive measurements of molecular absorption using frequency-agile rapid scanning, cavity ring-down spectroscopy with an external-cavity diode laser. A microwave source that drives an electro-optic phase modulator with a bandwidth of 20 GHz generates pairs of sidebands on the probe laser. The optical cavity provides for high sensitivity and filters the carrier and all but a single, selected sideband. Absorption spectra were acquired by stepping the tunable sideband from mode-to-mode of the ring-down cavity at a rate that was limited only by the cavity decay time. This approach allows for scanning rates of 8 kHz per cavity resonance, a minimum detectable absorption coefficient of 1.7 × 10-11 cm-1 after only 20 ms of averaging, and a noise-equivalent absorption coefficient of 1.7 × 10-12 cm-1 Hz-1/2. By comparison with cavity-enhanced laser absorption spectrometers reported in the literature, the present system is, to the best of our knowledge, among the most sensitive and has by far the highest spectrum scanning rate.

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Measurements of gas parameters in plasma-assisted supersonic combustion processes using diode laser spectroscopy

NASA Astrophysics Data System (ADS)

Bolshov, Mikhail A.; Kuritsyn, Yu A.; Liger, V. V.; Mironenko, V. R.; Leonov, S. B.; Yarantsev, D. A.

2009-09-01

We report a procedure for temperature and water vapour concentration measurements in an unsteady-state combustion zone using diode laser absorption spectroscopy. The procedure involves measurements of the absorption spectrum of water molecules around 1.39 μm. It has been used to determine hydrogen combustion parameters in M = 2 gas flows in the test section of a supersonic wind tunnel. The relatively high intensities of the absorption lines used have enabled direct absorption measurements. We describe a differential technique for measurements of transient absorption spectra, the procedure we used for primary data processing and approaches for determining the gas temperature and H2O concentration in the probed zone. The measured absorption spectra are fitted with spectra simulated using parameters from spectroscopic databases. The combustion-time-averaged (~50 ms) gas temperature and water vapour partial pressure in the hot wake region are determined to be 1050 K and 21 Torr, respectively. The large signal-to-noise ratio in our measurements allowed us to assess the temporal behaviour of these parameters. The accuracy in our temperature measurements in the probed zone is ~40 K.

Surface degradation of uranium tetrafluoride

DOE PAGES

Tobin, J. G.; Duffin, A. M.; Yu, S. -W.; ...

2017-05-01

A detailed analysis of a single crystal of uranium tetrafluoride has been carried out. The techniques include x-ray absorption spectroscopy, as well as x-ray photoelectron spectroscopy and x-ray emission spectroscopy. Evidence will be presented for the presence of a uranyl species, possibly UO 2F 2, as a product of, or participant in the surface degradation.

Frequency-domain optical absorption spectroscopy of finite tissue volumes using diffusion theory.

PubMed

Pogue, B W; Patterson, M S

1994-07-01

The goal of frequency-domain optical absorption spectroscopy is the non-invasive determination of the absorption coefficient of a specific tissue volume. Since this allows the concentration of endogenous and exogenous chromophores to be calculated, there is considerable potential for clinical application. The technique relies on the measurement of the phase and modulation of light, which is diffusely reflected or transmitted by the tissue when it is illuminated by an intensity-modulated source. A model of light propagation must then be used to deduce the absorption coefficient. For simplicity, it is usual to assume the tissue is either infinite in extent (for transmission measurements) or semi-infinite (for reflectance measurements). The goal of this paper is to examine the errors introduced by these assumptions when measurements are actually performed on finite volumes. Diffusion-theory calculations and experimental measurements were performed for slabs, cylinders and spheres with optical properties characteristic of soft tissues in the near infrared. The error in absorption coefficient is presented as a function of object size as a guideline to when the simple models may be used. For transmission measurements, the error is almost independent of the true absorption coefficient, which allows absolute changes in absorption to be measured accurately. The implications of these errors in absorption coefficient for two clinical problems--quantitation of an exogenous photosensitizer and measurement of haemoglobin oxygenation--are presented and discussed.

Optical spectroscopy of nanoscale and heterostructured oxides

NASA Astrophysics Data System (ADS)

Senty, Tess R.

Through careful analysis of a material's properties, devices are continually getting smaller, faster and more efficient each day. Without a complete scientific understanding of material properties, devices cannot continue to improve. This dissertation uses optical spectroscopy techniques to understand light-matter interactions in several oxide materials with promising uses mainly in light harvesting applications. Linear absorption, photoluminescence and transient absorption spectroscopy are primarily used on europium doped yttrium vanadate nanoparticles, copper gallium oxide delafossites doped with iron, and cadmium selenide quantum dots attached to titanium dioxide nanoparticles. Europium doped yttrium vanadate nanoparticles have promising applications for linking to biomolecules. Using Fourier-transform infrared spectroscopy, it was shown that organic ligands (benzoic acid, 3-nitro 4-chloro-benzoic acid and 3,4-dihydroxybenzoic acid) can be attached to the surface of these molecules using metal-carboxylate coordination. Photoluminescence spectroscopy display little difference in the position of the dominant photoluminescence peaks between samples with different organic ligands although there is a strong decrease in their intensity when 3,4-dihydroxybenzoic acid is attached. It is shown that this strong quenching is due to the presence of high-frequency hydroxide vibrational modes within the organic linker. Ultraviolet/visible linear absorption measurements on delafossites display that by doping copper gallium oxide with iron allows for the previously forbidden fundamental gap transition to be accessed. Using tauc plots, it is shown that doping with iron lowers the bandgap from 2.8 eV for pure copper gallium oxide, to 1.7 eV for samples with 1 -- 5% iron doping. Using terahertz transient absorption spectroscopy measurements, it was also determined that doping with iron reduces the charge mobility of the pure delafossite samples. A comparison of cadmium selenide quantum dots, both with and without capping ligands, attached to titanium dioxide nanoparticles is performed using a new transient absorption analysis technique. Multiple exponential fit models were applied to the system and compared with the new inversion analysis technique. It is shown how the new inversion analysis can map out the charge carrier dynamics, providing carrier recombination rates and lifetimes as a function of carrier concentration, where the multiple exponential fit technique is not dependent on the carrier concentration. With the inversion analysis technique it is shown that capping ligands allow for increased charge transfer due to traps being passivated on the quantum dot surface.

Polarization-controlled optimal scatter suppression in transient absorption spectroscopy

PubMed Central

Malý, Pavel; Ravensbergen, Janneke; Kennis, John T. M.; van Grondelle, Rienk; Croce, Roberta; Mančal, Tomáš; van Oort, Bart

2017-01-01

Ultrafast transient absorption spectroscopy is a powerful technique to study fast photo-induced processes, such as electron, proton and energy transfer, isomerization and molecular dynamics, in a diverse range of samples, including solid state materials and proteins. Many such experiments suffer from signal distortion by scattered excitation light, in particular close to the excitation (pump) frequency. Scattered light can be effectively suppressed by a polarizer oriented perpendicular to the excitation polarization and positioned behind the sample in the optical path of the probe beam. However, this introduces anisotropic polarization contributions into the recorded signal. We present an approach based on setting specific polarizations of the pump and probe pulses, combined with a polarizer behind the sample. Together, this controls the signal-to-scatter ratio (SSR), while maintaining isotropic signal. We present SSR for the full range of polarizations and analytically derive the optimal configuration at angles of 40.5° between probe and pump and of 66.9° between polarizer and pump polarizations. This improves SSR by (or compared to polarizer parallel to probe). The calculations are validated by transient absorption experiments on the common fluorescent dye Rhodamine B. This approach provides a simple method to considerably improve the SSR in transient absorption spectroscopy. PMID:28262765

Direct absorption spectroscopy sensor for temperature and H2O concentration of flat flame burner

NASA Astrophysics Data System (ADS)

Duan, Jin-hu; Jin, Xing; Wang, Guang-yu; Qu, Dong-sheng

2016-01-01

A tunable diode laser absorption sensor, based on direct absorption spectroscopy and time division multiplexing scheme, was developed to measure H2O concentration and temperature of flat flame burner. At the height of 15mm from the furnace surface, temperature and concentration were measured at different equivalence ratios. Then the distance between the laser and the furnace surface was changed while the equivalence ratio was fixed at 1 and experiments were performed to measure temperature and H2O concentration at every height. At last flame temperatures and H2O concentrations were obtained by simulation and computational analysis and these combustion parameters were compared with the reference. The results showed that the experimental results were in accordance with the reference values. Temperature errors were less than 4% and H2O component concentration errors were less than 5%and both of them reached their maximum when the equivalent ratio was set at 1. The temperature and H2O concentration increased with the height from furnace surface to laser when it varied from 3mm to 9mm and it decreased when it varied from 9mm to 30mm and they reached their maximum at the height of 9mm. Keywords: tunable diode laser, direct absorption spectroscopy

The water vapour self-continuum absorption in the infrared atmospheric windows: new laser measurements near 3.3 and 2.0 µm

NASA Astrophysics Data System (ADS)

Lechevallier, Loic; Vasilchenko, Semen; Grilli, Roberto; Mondelain, Didier; Romanini, Daniele; Campargue, Alain

2018-04-01

The amplitude, the temperature dependence, and the physical origin of the water vapour absorption continuum are a long-standing issue in molecular spectroscopy with direct impact in atmospheric and planetary sciences. In recent years, we have determined the self-continuum absorption of water vapour at different spectral points of the atmospheric windows at 4.0, 2.1, 1.6, and 1.25 µm, by highly sensitive cavity-enhanced laser techniques. These accurate experimental constraints have been used to adjust the last version (3.2) of the semi-empirical MT_CKD model (Mlawer-Tobin_Clough-Kneizys-Davies), which is widely incorporated in atmospheric radiative-transfer codes. In the present work, the self-continuum cross-sections, CS, are newly determined at 3.3 µm (3007 cm-1) and 2.0 µm (5000 cm-1) by optical-feedback-cavity enhanced absorption spectroscopy (OFCEAS) and cavity ring-down spectroscopy (CRDS), respectively. These new data allow extending the spectral coverage of the 4.0 and 2.1 µm windows, respectively, and testing the recently released 3.2 version of the MT_CKD continuum. By considering high temperature literature data together with our data, the temperature dependence of the self-continuum is also obtained.

High-performance dispersive Raman and absorption spectroscopy as tools for drug identification

NASA Astrophysics Data System (ADS)

Pawluczyk, Olga; Andrey, Sam; Nogas, Paul; Roy, Andrew; Pawluczyk, Romuald

2009-02-01

Due to increasing availability of pharmaceuticals from many sources, a need is growing to quickly and efficiently analyze substances in terms of the consistency and accuracy of their chemical composition. Differences in chemical composition occur at very low concentrations, so that highly sensitive analytical methods become crucial. Recent progress in dispersive spectroscopy with the use of 2-dimensional detector arrays, permits for signal integration along a long (up to 12 mm long) entrance slit of a spectrometer, thereby increasing signal to noise ratio and improving the ability to detect small concentration changes. This is achieved with a non-scanning, non-destructive system. Two different methods using P&P Optica high performance spectrometers were used. High performance optical dispersion Raman and high performance optical absorption spectroscopy were employed to differentiate various acetaminophen-containing drugs, such as Tylenol and other generic brands, which differ in their ingredients. A 785 nm excitation wavelength was used in Raman measurements and strong Raman signals were observed in the spectral range 300-1800 cm-1. Measurements with the absorption spectrometer were performed in the wavelength range 620-1020 nm. Both Raman and absorption techniques used transmission light spectrometers with volume phase holographic gratings and provided sufficient spectral differences, often structural, allowing for drug differentiation.

Detection of hydrogen peroxide based on long-path absorption spectroscopy using a CW EC-QCL

NASA Astrophysics Data System (ADS)

Sanchez, N. P.; Yu, Y.; Dong, L.; Griffin, R.; Tittel, F. K.

2016-02-01

A sensor system based on a CW EC-QCL (mode-hop-free range 1225-1285 cm-1) coupled with long-path absorption spectroscopy was developed for the monitoring of gas-phase hydrogen peroxide (H2O2) using an interference-free absorption line located at 1234.055 cm-1. Wavelength modulation spectroscopy (WMS) with second harmonic detection was implemented for data processing. Optimum levels of pressure and modulation amplitude of the sensor system led to a minimum detection limit (MDL) of 25 ppb using an integration time of 280 sec. The selected absorption line for H2O2, which exhibits no interference from H2O, makes this sensor system suitable for sensitive and selective monitoring of H2O2 levels in decontamination and sterilization processes based on Vapor Phase Hydrogen Peroxide (VPHP) units, in which a mixture of H2O and H2O2 is generated. Furthermore, continuous realtime monitoring of H2O2 concentrations in industrial facilities employing this species can be achieved with this sensing system in order to evaluate average permissible exposure levels (PELs) and potential exceedances of guidelines established by the US Occupational Safety and Health Administration for H2O2.

Effect of reduction time on third order optical nonlinearity of reduced graphene oxide

NASA Astrophysics Data System (ADS)

Sreeja, V. G.; Vinitha, G.; Reshmi, R.; Anila, E. I.; Jayaraj, M. K.

2017-04-01

We report the influence of reduction time on structural, linear and nonlinear optical properties of reduced graphene oxide (rGO) thin films synthesized by spin coating method. We observed that the structural, linear and nonlinear optical properties can be tuned with reduction time in GO is due to the increased structural ordering because of the restoration of sp2 carbon atoms with the time of reduction. The nonlinear absorption studies by open aperture Z-scan technique exhibited a saturable absorption. The nonlinear refraction studies showed the self de focusing nature of rGO by closed aperture Z scan technique. The nonlinear absorption coefficient and saturation intensity varies with the time for reduction of GO which is attributed to the depletion of valence band and the conduction band filling effect. Our results emphasize duration for reduction of GO dependent optical nonlinearity of rGO thin films to a great extent and explore its applications Q switched mode locking laser systems for generating ultra short laser pulses and in optical sensors. The rGO coated films were characterized by X-Ray diffraction method (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, UV-Vis absorption spectroscopy (UV-Vis), Photoluminescence (PL) and Scanning electron microscope (SEM) measurements.

[Signal analysis and spectrum distortion correction for tunable diode laser absorption spectroscopy system].

PubMed

Bao, Wei-Yi; Zhu, Yong; Chen, Jun; Chen, Jun-Qing; Liang, Bo

2011-04-01

In the present paper, the signal of a tunable diode laser absorption spectroscopy (TDLAS) trace gas sensing system, which has a wavelength modulation with a wide range of modulation amplitudes, is studied based on Fourier analysis method. Theory explanation of spectrum distortion induced by laser intensity amplitude modulation is given. In order to rectify the spectrum distortion, a method of synchronous amplitude modulation suppression by a variable optical attenuator is proposed. To validate the method, an experimental setup is designed. Absorption spectrum measurement experiments on CO2 gas were carried out. The results show that the residual laser intensity modulation amplitude of the experimental system is reduced to -0.1% of its original value and the spectrum distortion improvement is 92% with the synchronous amplitude modulation suppression. The modulation amplitude of laser intensity can be effectively reduced and the spectrum distortion can be well corrected by using the given correction method and system. By using a variable optical attenuator in the TDLAS (tunable diode laser absorption spectroscopy) system, the dynamic range requirements of photoelectric detector, digital to analog converter, filters and other aspects of the TDLAS system are reduced. This spectrum distortion correction method can be used for online trace gas analyzing in process industry.

Pathlength Determination for Gas in Scattering Media Absorption Spectroscopy

PubMed Central

Mei, Liang; Somesfalean, Gabriel; Svanberg, Sune

2014-01-01

Gas in scattering media absorption spectroscopy (GASMAS) has been extensively studied and applied during recent years in, e.g., food packaging, human sinus monitoring, gas diffusion studies, and pharmaceutical tablet characterization. The focus has been on the evaluation of the gas absorption pathlength in porous media, which a priori is unknown due to heavy light scattering. In this paper, three different approaches are summarized. One possibility is to simultaneously monitor another gas with known concentration (e.g., water vapor), the pathlength of which can then be obtained and used for the target gas (e.g., oxygen) to retrieve its concentration. The second approach is to measure the mean optical pathlength or physical pathlength with other methods, including time-of-flight spectroscopy, frequency-modulated light scattering interferometry and the frequency domain photon migration method. By utilizing these methods, an average concentration can be obtained and the porosities of the material are studied. The last method retrieves the gas concentration without knowing its pathlength by analyzing the gas absorption line shape, which depends upon the concentration of buffer gases due to intermolecular collisions. The pathlength enhancement effect due to multiple scattering enables also the use of porous media as multipass gas cells for trace gas monitoring. All these efforts open up a multitude of different applications for the GASMAS technique. PMID:24573311

Method for calibration-free scanned-wavelength modulation spectroscopy for gas sensing

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

Hanson, Ronald K.; Jeffries, Jay B.; Sun, Kai

A method of calibration-free scanned-wavelength modulation spectroscopy (WMS) absorption sensing is provided by obtaining absorption lineshape measurements of a gas sample on a sensor using 1f-normalized WMS-2f where an injection current to an injection current-tunable diode laser (TDL) is modulated at a frequency f, where a wavelength modulation and an intensity modulation of the TDL are simultaneously generated, extracting using a numerical lock-in program and a low-pass filter appropriate band-width WMS-nf (n=1, 2, . . . ) signals, where the WMS-nf signals are harmonics of the f, determining a physical property of the gas sample according to ratios of themore » WMS-nf signals, determining the zero-absorption background using scanned-wavelength WMS, and determining non-absorption losses using at least two of the harmonics, where a need for a non-absorption baseline measurement is removed from measurements in environments where collision broadening has blended transition linewidths, where calibration free WMS measurements without knowledge of the transition linewidth is enabled.« less

[Study of high temperature water vapor concentration measurement method based on absorption spectroscopy].

PubMed

Chen, Jiu-ying; Liu, Jian-guo; He, Jun-feng; He, Ya-bai; Zhang, Guang-le; Xu, Zhen-yu; Gang, Qiang; Wang, Liao; Yao, Lu; Yuan, Song; Ruan, Jun; Dai, Yun-hai; Kan, Rui-feng

2014-12-01

Tunable diode laser absorption spectroscopy (TDLAS) has been developed to realize the real-time and dynamic measurement of the combustion temperature, gas component concentration, velocity and other flow parameters, owing to its high sensitivity, fast time response, non-invasive character and robust nature. In order to obtain accurate water vapor concentration at high temperature, several absorption spectra of water vapor near 1.39 μm from 773 to 1273 K under ordinary pressure were recorded in a high temperature experiment setup using a narrow band diode laser. The absorbance of high temperature absorption spectra was calculated by combined multi-line nonlinear least squares fitting method. Two water vapor absorption lines near 7154.35 and 7157.73 cm(-1) were selected for measurement of water vapor at high temperature. A model method for high temperature water vapor concentration was first proposed. Water vapor concentration from the model method at high temperature is in accordance with theoretical reasoning, concentration measurement standard error is less than 0.2%, and the relative error is less than 6%. The feasibility of this measuring method is verified by experiment.

[Using 2-DCOS to identify the molecular spectrum peaks for the isomer in the multi-component mixture gases Fourier transform infrared analysis].

PubMed

Zhao, An-Xin; Tang, Xiao-Jun; Zhang, Zhong-Hua; Liu, Jun-Hua

2014-10-01

The generalized two-dimensional correlation spectroscopy and Fourier transform infrared were used to identify hydrocarbon isomers in the mixed gases for absorption spectra resolution enhancement. The Fourier transform infrared spectrum of n-butane and iso-butane and the two-dimensional correlation infrared spectrum of concentration perturbation were used for analysis as an example. The all band and the main absorption peak wavelengths of Fourier transform infrared spectrum for single component gas showed that the spectra are similar, and if they were mixed together, absorption peaks overlap and peak is difficult to identify. The synchronous and asynchronous spectrum of two-dimensional correlation spectrum can clearly identify the iso-butane and normal butane and their respective characteristic absorption peak intensity. Iso-butane has strong absorption characteristics spectrum lines at 2,893, 2,954 and 2,893 cm(-1), and n-butane at 2,895 and 2,965 cm(-1). The analysis result in this paper preliminary verified that the two-dimensional infrared correlation spectroscopy can be used for resolution enhancement in Fourier transform infrared spectrum quantitative analysis.

Light Source Effects on Aerosol Photoacoustic Spectroscopy Measurements

PubMed Central

Radney, James G.; Zangmeister, Christopher D.

2016-01-01

Photoacoustic spectroscopy measurements of flame-generated soot aerosol coated with small amounts of water yielded absorption enhancements that were dependent on the laser used: quasi-continuous wave (Q-CW, ≈ 650 ps pulse duration and 78 MHz repetition rate) versus continuous wave (CW). Water coating thickness was controlled by exposing the aerosol to a set relative humidity (RH). At ≈ 85 % RH, the mass of the soot particles increased by an amount comparable to a monolayer of water being deposited and enhanced the measured absorption by 36 % and 15 % for the Q-CW and CW lasers, respectively. Extinction measurements were also performed using a cavity ring-down spectrometer (extinction equals the sum of absorption and scattering) with a CW laser and negligible enhancement was observed at all RH. These findings demonstrate that source choice can impact measurements of aerosols with volatile coatings and that the absorption enhancements at high RH previously measured by Radney and Zangmeister (2015) [1] are the result of laser source used (Q-CW) and not from an increase in the particle absorption cross section. PMID:28066027

Bandgap Inhomogeneity of a PbSe Quantum Dot Ensemble from Two-Dimensional Spectroscopy and Comparison to Size Inhomogeneity from Electron Microscopy

DOE PAGES

Park, Samuel D.; Baranov, Dmitry; Ryu, Jisu; ...

2017-01-03

Femtosecond two-dimensional Fourier transform spectroscopy is used to determine the static bandgap inhomogeneity of a colloidal quantum dot ensemble. The excited states of quantum dots absorb light, so their absorptive two-dimensional (2D) spectra will typically have positive and negative peaks. We show that the absorption bandgap inhomogeneity is robustly determined by the slope of the nodal line separating positive and negative peaks in the 2D spectrum around the bandgap transition; this nodal line slope is independent of excited state parameters not known from the absorption and emission spectra. The absorption bandgap inhomogeneity is compared to a size and shape distributionmore » determined by electron microscopy. The electron microscopy images are analyzed using new 2D histograms that correlate major and minor image projections to reveal elongated nanocrystals, a conclusion supported by grazing incidence small-angle X-ray scattering and high-resolution transmission electron microscopy. Lastly, the absorption bandgap inhomogeneity quantitatively agrees with the bandgap variations calculated from the size and shape distribution, placing upper bounds on any surface contributions.« less

Resonant Absorption in GaAs-Based Nanowires by Means of Photo-Acoustic Spectroscopy

NASA Astrophysics Data System (ADS)

Petronijevic, E.; Leahu, G.; Belardini, A.; Centini, M.; Li Voti, R.; Hakkarainen, T.; Koivusalo, E.; Guina, M.; Sibilia, C.

2018-03-01

Semiconductor nanowires made of high refractive index materials can couple the incoming light to specific waveguide modes that offer resonant absorption enhancement under the bandgap wavelength, essential for light harvesting, lasing and detection applications. Moreover, the non-trivial ellipticity of such modes can offer near field interactions with chiral molecules, governed by near chiral field. These modes are therefore very important to detect. Here, we present the photo-acoustic spectroscopy as a low-cost, reliable, sensitive and scattering-free tool to measure the spectral position and absorption efficiency of these modes. The investigated samples are hexagonal nanowires with GaAs core; the fabrication by means of lithography-free molecular beam epitaxy provides controllable and uniform dimensions that allow for the excitation of the fundamental resonant mode around 800 nm. We show that the modulation frequency increase leads to the discrimination of the resonant mode absorption from the overall absorption of the substrate. As the experimental data are in great agreement with numerical simulations, the design can be optimized and followed by photo-acoustic characterization for a specific application.

Tomographic multiaxis-differential optical absorption spectroscopy observations of Sun-illuminated targets: a technique providing well-defined absorption paths in the boundary layer

NASA Astrophysics Data System (ADS)

Frins, Erna; Bobrowski, Nicole; Platt, Ulrich; Wagner, Thomas

2006-08-01

A novel experimental procedure to measure the near-surface distribution of atmospheric trace gases by using passive multiaxis differential absorption optical spectroscopy (MAX-DOAS) is proposed. The procedure consists of pointing the receiving telescope of the spectrometer to nonreflecting surfaces or to bright targets placed at known distances from the measuring device, which are illuminated by sunlight. We show that the partial trace gas absorptions between the top of the atmosphere and the target can be easily removed from the measured total absorption. Thus it is possible to derive the average concentration of trace gases such as NO2, HCHO, SO2, H2O, Glyoxal, BrO, and others along the line of sight between the instrument and the target similar to the well-known long-path DOAS observations (but with much less expense). If tomographic arrangements are used, even two- or three-dimensional trace gas distributions can be retrieved. The basic assumptions of the proposed method are confirmed by test measurements taken across the city of Heidelberg.

Remote laser evaporative molecular absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hughes, Gary B.; Lubin, Philip; Cohen, Alexander; Madajian, Jonathan; Kulkarni, Neeraj; Zhang, Qicheng; Griswold, Janelle; Brashears, Travis

2016-09-01

We describe a novel method for probing bulk molecular and atomic composition of solid targets from a distant vantage. A laser is used to melt and vaporize a spot on the target. With sufficient flux, the spot temperature rises rapidly, and evaporation of surface materials occurs. The melted spot creates a high-temperature blackbody source, and ejected material creates a plume of surface materials in front of the spot. Molecular and atomic absorption occurs as the blackbody radiation passes through the ejected plume. Bulk molecular and atomic composition of the surface material is investigated by using a spectrometer to view the heated spot through the ejected plume. The proposed method is distinct from current stand-off approaches to composition analysis, such as Laser-Induced Breakdown Spectroscopy (LIBS), which atomizes and ionizes target material and observes emission spectra to determine bulk atomic composition. Initial simulations of absorption profiles with laser heating show great promise for Remote Laser-Evaporative Molecular Absorption (R-LEMA) spectroscopy. The method is well-suited for exploration of cold solar system targets—asteroids, comets, planets, moons—such as from a spacecraft orbiting the target. Spatial composition maps could be created by scanning the surface. Applying the beam to a single spot continuously produces a borehole or trench, and shallow subsurface composition profiling is possible. This paper describes system concepts for implementing the proposed method to probe the bulk molecular composition of an asteroid from an orbiting spacecraft, including laser array, photovoltaic power, heating and ablation, plume characteristics, absorption, spectrometry and data management.

Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

DOE PAGES

Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; ...

2015-03-02

We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~10 6 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10 7 laser pulses, wemore » also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.« less

Tetra- and Heptametallic Ru(II),Rh(III) Supramolecular Hydrogen Production Photocatalysts

DOE PAGES

Manbeck, Gerald F.; Fujita, Etsuko; Brewer, Karen J.

2017-06-01

Supramolecular mixed metal complexes combining the trimetallic chromophore [{(bpy) 2Ru(dpp)} 2Ru(dpp)] 6+ (Ru 3) with [Rh(bpy)Cl 2] + or [RhCl 2] + catalytic fragments to form [{(bpy) 2Ru(dpp)} 2Ru(dpp)RhCl 2(bpy)](PF 6) 7 (Ru 3Rh) or [{(bpy) 2Ru(dpp)} 2Ru(dpp)] 2RhCl 2(PF 6) 13 (Ru 3RhRu 3) (bpy = 2,2'-bipyridine and dpp = 2,3-bis(2-pyridyl)pyrazine) catalyze the photochemical reduction of protons to H 2. This first example of a heptametallic Ru,Rh photocatalyst produces over 300 turnovers of H 2 upon photolysis of a solution of acetonitrile, water, triflic acid, and N,N-dimethylaniline as an electron donor. Conversely, the tetrametallic Ru 3Rh produces only 40more » turnovers of H 2 due to differences in the excited state properties and nature of the catalysts upon reduction as ascertained from electrochemical data, transient absorption spectroscopy, and flash-quench experiments. And while the lowest unoccupied molecular orbital of Ru 3Rh is localized on a bridging ligand, it is Rh-centered in Ru 3RhRu 3 facilitating electron collection at Rh in the excited state and reductively quenched state. The Ru → Rh charge separated state of Ru 3RhRu 3 is endergonic with respect to the emissive Ru → dpp 3MLCT excited and cannot be formed by static electron transfer quenching of the 3MLCT state. Instead, a mechanism of subnanosecond charge separation from high lying states is proposed. Multiple reductions of Ru 3 and Ru 3Rh using sodium amalgam were carried out to compare UV–vis absorption spectra of reduced species and to evaluate the stability of highly reduced complexes. Furthermore, the Ru 3 and Ru 3Rh can be reduced by 10 and 13 electrons, respectively, to final states with all bridging ligands doubly reduced and all bpy ligands singly reduced.« less

Ultrafast Transient Absorption Spectroscopy Investigation of Photoinduced Dynamics in Novel Donor-Acceptor Core-Shell Nanostructures for Organic Photovoltaics

NASA Astrophysics Data System (ADS)

Strain, Jacob; Jamhawi, Abdelqader; Abeywickrama, Thulitha M.; Loomis, Wendy; Rathnayake, Hemali; Liu, Jinjun

2016-06-01

Novel donor-acceptor nanostructures were synthesized via covalent synthesis and/or UV cross-linking method. Their photoinduced dynamics were investigated with ultrafast transient absorption (TA) spectroscopy. These new nanostructures are made with the strategy in mind to reduce manufacturing steps in the process of fabricating an organic photovoltaic cell. By imitating the heterojunction interface within a fixed particle domain, several fabrication steps can be bypassed reducing cost and giving more applicability to other film deposition methods. Such applications include aerosol deposition and ink-jet printing. The systems that were studied by TA spectroscopy include PDIB core, PDIB-P3HT core-shell, and PDIB-PANT core-shell which range in size from 60 to 130 nm. Within the experimentally accessible spectra range there resides a region of ground state bleaching, stimulated emission, and excited-state absorption of both neutrals and anions. Control experiments have been carried out to assign these features. At high pump fluences the TA spectra of PDIB core alone also indicate an intramolecular charge separation. The TA spectroscopy results thus far suggest that the core-shells resemble the photoinduced dynamics of a standard film although the particles are dispersed in solution, which indicates the desired outcome of the work.

Infrared absorption spectroscopy and sensing of protein monolayers using high performance enhancing substrates and a mobile phone (Conference Presentation)

NASA Astrophysics Data System (ADS)

Dana, Aykutlu; Ayas, Sencer; Bakan, Gokhan; Ozgur, Erol; Guner, Hasan; Celebi, Kemal

2016-09-01

Infrared absorption spectroscopy has greatly benefited from the electromagnetic field enhancement offered by plasmonic surfaces. However, because of the localized nature of plasmonic fields, such field enhancements are limited to nm-scale volumes. Here, we demonstrate that a relatively small, but spatially-uniform field enhancement can yield a superior infrared detection performance compared to the plasmonic field enhancement exhibited by optimized infrared nanoantennas. A specifically designed CaF2/Al thin film surface is shown to enable observation of stronger vibrational signals from the probe material, with wider bandwidth and a deeper spatial extent of the field enhancement as compared to optimized plasmonic surfaces. It is demonstrated that the surface structure presented here can enable chemically specific and label-free detection of organic monolayers using surface enhanced infrared spectroscopy. Also, a low cost hand held infrared absorption measurement setup is demonstrated using a miniature bolometric sensor and a mobile phone. A specifically designed grating in combination with an IR light source yields an IR spectrometer covering 7-12 um range, with about 100 cm-1 resolution. Combining the enhancing substrates with the spectroscopy setup, low cost, high sensitivity mobile infrared sensing is enabled. The results have implications in homeland security and environmental monitoring as well as chemical analysis.

Synthesis and characterization of TiO₂ and TiO₂/Ag for use in photodegradation of methylviologen, with kinetic study by laser flash photolysis.

PubMed

Ramos, Dayana Doffinger; Bezerra, Paula C S; Quina, Frank H; Dantas, Renato F; Casagrande, Gleison A; Oliveira, Silvio C; Oliveira, Márcio R S; Oliveira, Lincoln C S; Ferreira, Valdir S; Oliveira, Samuel L; Machulek, Amilcar

2015-01-01

This paper reports the synthesis, characterization, and application of TiO2 and TiO2/Ag nanoparticles for use in photocatalysis, employing the herbicide methylviologen (MV) as a substrate for photocatalytic activity testing. At suitable metal to oxide ratios, increases in silver surface coating on TiO2 enhanced the efficiency of heterogeneous photocatalysis by increasing the electron transfer constant. The sol-gel method was used for TiO2 synthesis. P25 TiO2 was the control material. Both oxides were subjected to the same silver incorporation process. The materials were characterized by conventional spectroscopy, SEM micrography, X-ray diffraction, calculation of surface area per mass of catalyst, and thermogravimetry. Also, electron transfers between TiO2 or TiO2/Ag and MV in the absence and presence of sodium formate were investigated using laser flash photolysis. Oxides synthesized with 2.0 % silver exhibited superior photocatalytic activity for MV degradation.

High performance SONOS flash memory with in-situ silicon nanocrystals embedded in silicon nitride charge trapping layer

NASA Astrophysics Data System (ADS)

Lim, Jae-Gab; Yang, Seung-Dong; Yun, Ho-Jin; Jung, Jun-Kyo; Park, Jung-Hyun; Lim, Chan; Cho, Gyu-seok; Park, Seong-gye; Huh, Chul; Lee, Hi-Deok; Lee, Ga-Won

2018-02-01

In this paper, SONOS-type flash memory device with highly improved charge-trapping efficiency is suggested by using silicon nanocrystals (Si-NCs) embedded in silicon nitride (SiNX) charge trapping layer. The Si-NCs were in-situ grown by PECVD without additional post annealing process. The fabricated device shows high program/erase speed and retention property which is suitable for multi-level cell (MLC) application. Excellent performance and reliability for MLC are demonstrated with large memory window of ∼8.5 V and superior retention characteristics of 7% charge loss for 10 years. High resolution transmission electron microscopy image confirms the Si-NC formation and the size is around 1-2 nm which can be verified again in X-ray photoelectron spectroscopy (XPS) where pure Si bonds increase. Besides, XPS analysis implies that more nitrogen atoms make stable bonds at the regular lattice point. Photoluminescence spectra results also illustrate that Si-NCs formation in SiNx is an effective method to form deep trap states.

Structural characterization and physicochemical properties of protein extracted from soybean meal assisted by steam flash-explosion with dilute acid soaking.

PubMed

Zhang, Yanpeng; Yang, Ruijin; Zhang, Weinong; Hu, Zhixiong; Zhao, Wei

2017-03-15

The aim of this work was to analyze the influence of steam flash-explosion (SFE) with dilute acid soaking pretreatment on the structural characteristics and physiochemical properties of protein from soybean meal (SBM). The pretreatment led to depolymerisation of soy protein isolate (SPI) and formation of new protein aggregation through non-disulfide covalent bonds, which resulted in broader MW distribution of SPI. The analysis of CD spectroscopy showed that the SFE treatment induced minor changes in secondary structure, however, the intrinsic tryptophan fluorescence revealed that acid soaking and SFE treatment pronouncedly altered the tertiary structure of SPI. The protein zeta potential was shown to be increased after SFE treatment attributed to the changes in protein structure and the covalent coupling between carbohydrate and protein. These results contribute to clarifying the mechanisms of the effect of pretreatment on SPI structure, thus moving further toward implementing SFE in the processing chain of SPI. Copyright © 2016 Elsevier Ltd. All rights reserved.

Observations of the peculiar object MWC 560 in outburst

NASA Technical Reports Server (NTRS)

Michalitsianos, A. G.; Maran, S. P.; Oliversen, R. J.; Bopp, B.; Kontizas, E.

1991-01-01

The results of ultraviolet spectroscopy, photoelectric photometry, and supplemental high-resolution H(alpha) spectroscopy of a photometric outburst of MWC 560 are discussed. Ultraviolet spectra are shown to be consistent with the ejection of an optically thick shell that produced strong absorption blends of Fe II and Cr II. The velocities reported exceed by far those previously found in symbiotic stars or recurrent novas. In addition to the variable high-velocity system of broad absorption features, a relatively stable system of Mg II, Mg I, Fe II, Cr II, and other ionic absorptions is observed. It is pointed out that the spectroscopic phenomena in MWC 560 resemble those found in XX Ophiuchi, but the velocities in the MWC 560 are an order of magnitude higher than those found in XX Oph.

The determination of vanadium in brines by atomic absorption spectroscopy

USGS Publications Warehouse

Crump-Wiesner, Hans J.; Feltz, H.R.; Purdy, W.C.

1971-01-01

A standard addition method is described for the determination of vanadium in brines by atomic absorption spectroscopy with a nitrous oxide-acetylene flame. Sample pH is adjusted to 1.0 with concentrated hydrochloric acid and the vanadium is directly extracted with 5% cupferron in methyl isobutyl ketone (MIBK). The ketone layer is then aspirated into the flame and the recorded absorption values are plotted as a function of the concentration of the added metal. As little as 2.5 ??g l-1 of vanadium can be detected under the conditions of the procedure. Tungsten and tin interfere when present in excess of 5 and 10 ??g ml-1, respectively. The concentrations of the two interfering ions normally found in brines are well below interference levels. ?? 1971.

Space Launch System Base Heating Test: Tunable Diode Laser Absorption Spectroscopy

NASA Technical Reports Server (NTRS)

Parker, Ron; Carr, Zak; MacLean, Matthew; Dufrene, Aaron; Mehta, Manish

2016-01-01

This paper describes the Tunable Diode Laser Absorption Spectroscopy (TDLAS) measurement of several water transitions that were interrogated during a hot-fire testing of the Space Launch Systems (SLS) sub-scale vehicle installed in LENS II. The temperature of the recirculating gas flow over the base plate was found to increase with altitude and is consistent with CFD results. It was also observed that the gas above the base plate has significant velocity along the optical path of the sensor at the higher altitudes. The line-by-line analysis of the H2O absorption features must include the effects of the Doppler shift phenomena particularly at high altitude. The TDLAS experimental measurements and the analysis procedure which incorporates the velocity dependent flow will be described.

Terahertz spectroscopy of brain tissue from a mouse model of Alzheimer's disease

NASA Astrophysics Data System (ADS)

Shi, Lingyan; Shumyatsky, Pavel; Rodríguez-Contreras, Adrián; Alfano, Robert

2016-01-01

The terahertz (THz) absorption and index of refraction of brain tissues from a mouse model of Alzheimer's disease (AD) and a control wild-type (normal) mouse were compared using THz time-domain spectroscopy (THz-TDS). Three dominating absorption peaks associated to torsional-vibrational modes were observed in AD tissue, at about 1.44, 1.8, and 2.114 THz, closer to the peaks of free tryptophan molecules than in normal tissue. A possible reason is that there is more free tryptophan in AD brain tissue, while in normal brain tissue more tryptophan is attached to other molecules. Our study suggests that THz-absorption modes may be used as an AD biomarker fingerprint in brain, and that THz-TDS is a promising technique for early diagnosis of AD.

IDENTIFICATION OF IRON PHASES IN BIOSOLIDS VIA MOSSBAUER SPECTROSCOPY

EPA Science Inventory

Continuous debate regarding inorganic and organic phases in biosolids as prominent sorbents of metals has yielded limited definitive data. We have demonstrated with X-ray absorption and X-ray fluorescence spectroscopies that metals in biosolids have a significant association with...

Method for studying gas composition in the human mastoid cavity by use of laser spectroscopy.

PubMed

Lindberg, Sven; Lewander, Märta; Svensson, Tomas; Siemund, Roger; Svanberg, Katarina; Svanberg, Sune

2012-04-01

We evaluated a method for gas monitoring in the mastoid cavity using tunable diode laser spectroscopy by comparing it to simultaneously obtained computed tomographic (CT) scans. The presented optical technique measures free gases, oxygen (O2), and water vapor (H2O) within human tissue by use of low-power diode lasers. Laser light was sent into the tip of the mastoid process, and the emerging light at the level of the antrum was captured with a detector placed on the skin. The absorption of H2O was used to monitor the probed gas volume of the mastoid cavity, and it was compared to the CT scan-measured volume. The ratio between O2 absorption and H2O absorption estimated the O2 content in the mastoid cavity and thus the ventilation. The parameters were compared to the grading of mastoid cavities based on the CT scans (n = 31). The reproducibility of the technique was investigated by measuring each mastoid cavity 4 times. Both O2 and H2O were detected with good reproducibility. The H2O absorption and the CT volume correlated (r = 0.69). The average ratio between the normalized O2 absorption and the H2O absorption signals was 0.7, indicating a lower O2 content than in surrounding air (expected ratio, 1.0), which is consistent with previous findings made by invasive techniques. All mastoid cavities with radiologic signs of disease were detected. Laser spectroscopy monitoring appears to be a usable tool for noninvasive investigations of gas composition in the mastoid cavity, providing important clinical information regarding size and ventilation.

Development of integrated platform based on chalcogenides for sensing applications in the mid-infrared

NASA Astrophysics Data System (ADS)

Gutierrez-Arroyo, Aldo; Bodiou, Loïc.; Lemaitre, Jonathan; Baudet, Emeline; Baillieul, Marion; Hardy, Isabelle; Caillaud, Celine; Colas, Florent; Boukerma, Kada; Rinnert, Emmanuel; Michel, Karine; Bureau, Bruno; Nazabal, Virginie; Charrier, Joël.

2018-03-01

Mid-Infrared (mid-IR) spectral range, spanning from 2 μm to 20 μm, is ideal for chemical sensing using spectroscopy thanks to the presence of vibrational absorption bands of many liquid and gas substances in this wavelength range. Indeed, mid-IR spectroscopy allows simultaneous qualitative and quantitative analysis by, respectively, identifying molecules from their spectral signature and relating the concentrations of different chemical agents to their absorption coefficient according to Beer-Lambert law. In the last years, photonic integrated sensors based on mid-IR spectroscopy have emerged as a cheap, accurate, and compact solution that would enable continuous real-time on-site diagnostics and monitoring of molecular species without the need to collect samples for off-site measurements. Here, we report the design, processing and characterization of a photonic integrated transducer based on selenide ridge waveguides. Evanescent wave detection of chemical substances in liquid phase (isopropyl alcohol, C3H8O, and acetic acid, C2H4O2, both dissolved in cyclohexane) is presented using their absorption at a wavelength of 7.7 μm.

UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

PubMed

Ochmann, Miguel; Hussain, Abid; von Ahnen, Inga; Cordones, Amy A; Hong, Kiryong; Lee, Jae Hyuk; Ma, Rory; Adamczyk, Katrin; Kim, Tae Kyu; Schoenlein, Robert W; Vendrell, Oriol; Huse, Nils

2018-05-30

We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH 2 S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

Atomically designed precursors in optical fiber amplifiers: The thermal stability of the heterobimetallic ErAl3(OPri)12 in a solution-coated silica soot

NASA Astrophysics Data System (ADS)

Engholm, M.; Lashgari, K.; Edvardsson, S.; Westin, G.; Norin, L.

2005-06-01

The thermal stability of the bimetallic alkoxide ErAl3(OPri)12 doped in an unsintered silica (soot) has been investigated. Samples have been heated to different temperatures (up to 1500°C and analyzed by using ultraviolet-visible-near infrared absorption spectroscopy, infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal gravimetric analysis, and powder x-ray diffraction. It is seen that the doped samples heated up to 1000°C show broad glasslike absorption spectra, indicating an amorphous structure, while the high-temperature sample shows an ordered crystallinelike structure with sharp characteristic absorption peaks. X-ray diffraction measurements indicate the formation of an ordered structure at temperatures of 1500°C, revealing a crystal phase of silica and phases of erbium and aluminosilicate. A comparison is also made with a sample doped with aqueous ErCl3 and Al(NO3)3. It is concluded that the local structure of the ErAl3 precursor is not preserved at temperatures above 1000°C. Alternative doping procedures are discussed.

The effect of water absorption on the dielectric properties of polyethylene hexagonal boron nitride nanocomposites

NASA Astrophysics Data System (ADS)

Ayoob, Raed; Alhabill, Fuad N.; Andritsch, Thomas; Vaughan, Alun S.

2018-02-01

The effect of water absorption on the dielectric response of polyethylene/hexagonal boron nitride nanocomposites has been studied by dielectric spectroscopy. The nanocomposites have been prepared with hBN concentrations ranging from 2 wt% to 30 wt%. Fourier transform infrared spectroscopy and thermogravimetric analysis revealed a very small amount of hydroxyl groups on the surface of hBN. Mass loss measurements showed that the nanocomposites did not absorb any water under ambient and dry conditions while there was some water absorption under wet conditions. The dielectric spectroscopy results showed a broad relaxation peak, indicative of different states of water with water shells of different thickness, which moved to higher frequencies with increasing water content. However, the dielectric losses were significantly lower than the losses reported in the literature of nanocomposites under wet conditions. In addition, all the absorbed water was successfully removed under vacuum conditions which demonstrated that the interactions between the water and the nanocomposites were very weak, due to the hydrophobic nature of the hBN surface. This is a highly useful property, when considering these materials for applications in electrical insulation.

Fusion of Ultraviolet-Visible and Infrared Transient Absorption Spectroscopy Data to Model Ultrafast Photoisomerization.

PubMed

Debus, Bruno; Orio, Maylis; Rehault, Julien; Burdzinski, Gotard; Ruckebusch, Cyril; Sliwa, Michel

2017-08-03

Ultrafast photoisomerization reactions generally start at a higher excited state with excess of internal vibrational energy and occur via conical intersections. This leads to ultrafast dynamics which are difficult to investigate with a single transient absorption spectroscopy technique, be it in the ultraviolet-visible (UV-vis) or infrared (IR) domain. On one hand, the information available in the UV-vis domain is limited as only slight spectral changes are observed for different isomers. On the other hand, the interpretation of vibrational spectra is strongly hindered by intramolecular relaxation and vibrational cooling. These limitations can be circumvented by fusing UV-vis and IR transient absorption spectroscopy data in a multiset multivariate curve resolution analysis. We apply this approach to describe the spectrodynamics of the ultrafast cis-trans photoisomerization around the C-N double bond observed for aromatic Schiff bases. Twisted intermediate states could be elucidated, and isomerization was shown to occur through a continuous complete rotation. More broadly, data fusion can be used to rationalize a vast range of ultrafast photoisomerization processes of interest in photochemistry.

Spectroscopic Studies of Carotenoid-to-Bacteriochlorophyll Energy Transfer in LHRC Photosynthetic Complex from Roseiflexus castenholzii

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

Niedzwiedzki, Dariusz; Collins, Aaron M.; LaFountain, Amy M.

Carotenoids present in the photosynthetic light-harvesting reaction center (LHRC) complex from chlorosome lacking filamentous anoxygenic phototroph, Roseiflexus castenholzii were purified and characterized for their photochemical properties. The LHRC from anaerobically grown cells contains five different carotenoids, methoxy-keto-myxocoxanthin, γ-carotene, and its three derivatives, whereas the LHRC from aerobically grown cells contains only three carotenoid pigments with methoxy-keto-myxocoxanthin being the dominant one. The spectroscopic properties and dynamics of excited singlet states of the carotenoids were studied by steady-state absorption, fluorescence and ultrafast time-resolved optical spectroscopy in organic solvent and in the intact LHRC complex. Time-resolved transient absorption spectroscopy performed in the near-infraredmore » (NIR) on purified carotenoids combined with steady-state absorption spectroscopy led to the precise determination of values of the energies of the S 1(2 1A g -) excited state. Global and single wavelength fitting of the ultrafast spectral and temporal data sets of the carotenoids in solvents and in the LHRC revealed the pathways of de-excitation of the carotenoid excited states.« less

[Identification of different Citrus sinensis (L.) Osbeck trees varieties using Fourier transform infrared spectroscopy and hierarchical cluster analysis].

PubMed

Yi, Shi-Lai; Deng, Lie; He, Shao-Lan; Shi, You-Ming; Zheng, Yong-Qiang; Lu, Qiang; Xie, Rang-Jin; Wei, Xian-Guoi; Li, Song-Wei; Jian, Shui-Xian

2012-11-01

Researched on diversity of the spring leaf samples of seven different Citrus sinensis (L.) Osbeck varieties by Fourier transform infrared (FTIR) spectroscopy technology, the results showed that the Fourier transform infrared spectra of seven varieties leaves was composited by the absorption band of cellulose and polysaccharide mainly, the wave number of characteristics absorption peaks were similar at their FTIR spectra. However, there were some differences in shape of peaks and relatively absorption intensity. The conspicuous difference was presented at the region between 1 500 and 700 cm(-1) by second derivative spectra. Through the hierarchical cluster analysis (HCA) of second derivative spectra between 1 500 and 700 cm(-1), the results showed that the clustering of the different varieties of Citrus sinensis (L.) Osbeck varieties was classification according to genetic relationship. The results showed that FTIR spectroscopy combined with hierarchical cluster analysis could be used to identify and classify of citrus varieties rapidly, it was an extension method to study on early leaves of varieties orange seedlings.

Investigating the local structure of B-site cations in (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 using X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Blanchard, Peter E. R.; Grosvenor, Andrew P.

2018-05-01

The structural properties of (1-x)BaTiO3-xBiScO3 and (1-x)PbTiO3-xBiScO3 were investigated using powder X-ray diffraction and X-ray absorption spectroscopy. Diffraction measurements confirmed that substituting small amounts of BiScO3 into BaTiO3 initially stabilizes a cubic phase at x = 0.2 before impurity phases begin to form at x = 0.5. BiScO3 substitution also resulted in noticeable changes in the local coordination environment of Ti4+. X-ray absorption near-edge spectroscopy (XANES) analysis showed that replacing Ti4+ with Sc3+ results in an increase in the off-centre displacement of Ti4+ cations. Surprisingly, BiScO3 substitution has no effect on the displacement of the Ti4+ cation in the (1-x)PbTiO3-xBiScO3 solid solution.

Arsenic Re-Mobilization in Water Treatment Adsorbents Under Reducing Conditions: Part II, XAS and Modeling Study

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

Liu,S.; Jing, C.; Meng, X.

2008-01-01

The mechanism of arsenic re-mobilization in spent adsorbents under reducing conditions was studied using X-ray absorption spectroscopy and surface complexation model calculations. X-ray absorption near edge structure (XANES) spectroscopy demonstrated that As(V) was partially reduced to As(III) in spent granular ferric hydroxide (GFH), titanium dioxide (TiO2), activated alumina (AA) and modified activated alumina (MAA) adsorbents after 2 years of anaerobic incubation. As(V) was completely reduced to As(III) in spent granular ferric oxide (GFO) under 2-year incubation. The extended X-ray absorption fine structure (EXAFS) spectroscopy analysis showed that As(III) formed bidentate binuclear surface complexes on GFO as evidenced by an averagemore » As(III)-O bond distance of 1.78 Angstroms and As(III)-Fe distance of 3.34 Angstroms . The release of As from the spent GFO and TiO2 was simulated using the charge distribution multi-site complexation (CD-MUSIC) model. The observed redox ranges for As release and sulfate mobility were described by model calculations.« less

Combined characterization of bovine polyhemoglobin microcapsules by UV-Vis absorption spectroscopy and cyclic voltammetry.

PubMed

Knirsch, Marcos Camargo; Dell'Anno, Filippo; Salerno, Marco; Larosa, Claudio; Polakiewicz, Bronislaw; Eggenhöffner, Roberto; Converti, Attilio

2017-03-01

Polyhemoglobin produced from pure bovine hemoglobin by reaction with PEG bis(N-succynimidil succinate) as a cross-linking agent was encapsulated in gelatin and dehydrated by freeze-drying. Free carboxyhemoglobin and polyhemoglobin microcapsules were characterized by UV-Vis spectroscopy in the absorption range 450-650 nm and cyclic voltammetry in the voltage range from -0.8 to 0.6 mV to evaluate the ability to break the bond with carbon monoxide and to study the carrier's affinity for oxygen, respectively. SEM used to observe the shape of cross-linked gelatin-polyhemoglobin microparticles showed a regular distribution of globular shapes, with mean size of ~750 nm, which was ascribed to gelatin. Atomic absorption spectroscopy was also performed to detect iron presence in microparticles. Cyclic voltammetry using an Ag-AgCl electrode highlighted characteristic peaks at around -0.6 mV that were attributed to reversible oxygen bonding with iron in oxy-polyhemoglobin structure. These results suggest this technique as a powerful, direct and alternative method to evaluate the extent of hemoglobin oxygenation.

Balmer Absorption Lines in FeLoBALs

NASA Astrophysics Data System (ADS)

Aoki, K.; Iwata, I.; Ohta, K.; Tamura, N.; Ando, M.; Akiyama, M.; Kiuchi, G.; Nakanishi, K.

2007-10-01

We discovered non-stellar Balmer absorption lines in two many-narrow-trough FeLoBALs (mntBALs) by the near-infrared spectroscopy with Subaru/CISCO. Presence of the non-stellar Balmer absorption lines is known to date only in the Seyfert galaxy NGC 4151; thus our discovery is the first cases for quasars. Since all known active galactic nuclei with Balmer absorption lines share similar characteristics, it is suggested that there is a population of BAL quasars which have unique structures at their nuclei or unique evolutionary phase.

Application of terahertz spectroscopy for characterization of biologically active organic molecules in natural environment

NASA Astrophysics Data System (ADS)

Karaliūnas, Mindaugas; Jakštas, Vytautas; Nasser, Kinan E.; Venckevičius, Rimvydas; Urbanowicz, Andrzej; Kašalynas, Irmantas; Valušis, Gintaras

2016-09-01

In this work, a comparative research of biologically active organic molecules in its natural environment using the terahertz (THz) time domain spectroscopy (TDS) and Fourier transform spectroscopy (FTS) systems is carried out. Absorption coefficient and refractive index of Nicotiana tabacum L. leaves containing nicotine, Cannabis sativa L. leaves containing tetrahydrocannabinol, and Humulu lupulus L. leaves containing α-acids, active organic molecules that obtain in natural environment, were measured in broad frequency range from 0.1 to 13 THz at room temperature. In the spectra of absorption coefficient the features were found to be unique for N. tabacum, C. sativa and H. lupulus. Moreover, those features can be exploited for identification of C. sativa sex and N. tabacum origin. The refractive index can be also used to characterize different species.

Tunable lasers and their application in analytical chemistry

NASA Technical Reports Server (NTRS)

Steinfeld, J. I.

1975-01-01

The impact that laser techniques might have in chemical analysis is examined. Absorption, scattering, and heterodyne detection is considered. Particular emphasis is placed on the advantages of using frequency-tunable sources, and dye solution lasers are regarded as the outstanding example of this type of laser. Types of spectroscopy that can be carried out with lasers are discussed along with the ultimate sensitivity or minimum detectable concentration of molecules that can be achieved with each method. Analytical applications include laser microprobe analysis, remote sensing and instrumental methods such as laser-Raman spectroscopy, atomic absorption/fluorescence spectrometry, fluorescence assay techniques, optoacoustic spectroscopy, and polarization measurements. The application of lasers to spectroscopic methods of analysis would seem to be a rewarding field both for research in analytical chemistry and for investments in instrument manufacturing.

Terahertz Absorption and Circular Dichroism Spectroscopy of Solvated Biopolymers

NASA Astrophysics Data System (ADS)

Xu, Jing; Plaxco, Kevin; Allen, S. James

2006-03-01

Biopolymers are expected to exhibit broad spectral features in the terahertz frequency range, corresponding to their functionally relevant, global and sub-global collective vibrational modes with ˜ picosecond timescale. Recent advances in terahertz technology have stimulated researchers to employ terahertz absorption spectroscopy to directly probe these postulated collective modes. However, these pioneering studies have been limited to dry and, at best, moist samples. Successful isolation of low frequency vibrational activities of solvated biopolymers in their natural water environment has remained elusive, due to the overwhelming attenuation of the terahertz radiation by water. Here we have developed a terahertz absorption and circular dichroism spectrometer suitable for studying biopolymers in biologically relevant water solutions. We have precisely isolated, for the first time, the terahertz absorption of solvated prototypical proteins, Bovine Serum Albumin and Lysozyme, and made important direct comparison to the existing molecular dynamic simulations and normal mode calculations. We have also successfully demonstrated the magnetic circular dichroism in semiconductors, and placed upper bounds on the terahertz circular dichroism signatures of prototypical proteins in water solution.

Near-edge x-ray absorption fine structure spectroscopy at atmospheric pressure with a table-top laser-induced soft x-ray source

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

Kühl, Frank-Christian, E-mail: Frank-christian.kuehl@mail.de; Müller, Matthias, E-mail: matthias.mueller@llg-ev.de; Schellhorn, Meike

2016-07-15

The authors present a table-top soft x-ray absorption spectrometer, accomplishing investigations of the near-edge x-ray absorption fine structure (NEXAFS) in a laboratory environment. The system is based on a low debris plasma ignited by a picosecond laser in a pulsed krypton gas jet, emitting soft x-ray radiation in the range from 1 to 5 nm. For absorption spectroscopy in and around the “water window” (2.3–4.4 nm), a compact helium purged sample compartment for experiments at atmospheric pressure has been constructed and tested. NEXAFS measurements on CaCl{sub 2} and KMnO{sub 4} samples were conducted at the calcium and manganese L-edges, as well asmore » at the oxygen K-edge in air, atmospheric helium, and under vacuum, respectively. The results indicate the importance of atmospheric conditions for an investigation of sample hydration processes.« less

Enhancing the sensitivity of mid-IR quantum cascade laser-based cavity-enhanced absorption spectroscopy using RF current perturbation.

PubMed

Manfred, Katherine M; Kirkbride, James M R; Ciaffoni, Luca; Peverall, Robert; Ritchie, Grant A D

2014-12-15

The sensitivity of mid-IR quantum cascade laser (QCL) off-axis cavity-enhanced absorption spectroscopy (CEAS), often limited by cavity mode structure and diffraction losses, was enhanced by applying a broadband RF noise to the laser current. A pump-probe measurement demonstrated that the addition of bandwidth-limited white noise effectively increased the laser linewidth, thereby reducing mode structure associated with CEAS. The broadband noise source offers a more sensitive, more robust alternative to applying single-frequency noise to the laser. Analysis of CEAS measurements of a CO(2) absorption feature at 1890  cm(-1) averaged over 100 ms yielded a minimum detectable absorption of 5.5×10(-3)  Hz(-1/2) in the presence of broadband RF perturbation, nearly a tenfold improvement over the unperturbed regime. The short acquisition time makes this technique suitable for breath applications requiring breath-by-breath gas concentration information.

Nanoparticle Filtration in a RTM Processed Epoxy/Carbon Fiber Composite

NASA Technical Reports Server (NTRS)

Miller, Sandi G.; Micham, Logan; Copa, Christine C.; Criss, James M., Jr.; Mintz, Eric A.

2011-01-01

Several epoxy matrix composite panels were fabricated by resin transfer molding (RTM) E862/W resin onto a triaxially braided carbon fiber pre-form. Nanoparticles including carbon nanofiber, synthetic clay, and functionalized graphite were dispersed in the E862 matrix, and the extent of particle filtration during processing was characterized. Nanoparticle dispersion in the resin flashing on both the inlet and outlet edges of the panel was compared by TEM. Variation in physical properties such as Tg and moisture absorption throughout the panel were also characterized. All nanoparticle filled panels showed a decrease in Tg along the resin flow path across the panel, indicating nanoparticle filtration, however there was little change in moisture absorption. This works illustrates the need to obtain good nano-particle dispersion in the matrix resin to prevent particle agglomeration and hence particle filtration in the resultant polymer matrix composites (PMC).

Shock-tube studies of silicon-compound vapors

NASA Technical Reports Server (NTRS)

Park, C.; Fujiwara, T.

1977-01-01

Test gas mixtures containing SiO, SiO2, Si2, and SiH were produced in a shock tube by processing shock waves through a mixture of SiCl4 + N2O + Ar, SiH4 + Ar, or SiH4 + O2 + Ar. Absorption spectra of the test gases were studied photographically in the reflected shock region using a xenon flash lamp as the light source in the range of wavelengths between 250 and 600 nm. SiO was found to be a dominant species in the vapors produced by the SiCl4 + N2O and SiH4 + O2 mixtures. Spontaneous combustion was observed in the SiH4 + O2 + Ar mixture prior to the shock arrival, and the resulting solid SiO2 particles evaporated behind the shock wave. Spectral absorption characteristics of SiO, SiO2, Si2, and SiH were determined by studying the test gases.

Photochemical primary process of photo-Fries rearrangement reaction of 1-naphthyl acetate as studied by MFE probe.

PubMed

Gohdo, Masao; Takamasu, Tadashi; Wakasa, Masanobu

2011-01-14

Photo-Fries rearrangement reactions of 1-naphthyl acetate (NA) in n-hexane and in cyclohexane were studied by the magnetic field effect probe (MFE probe) under magnetic fields (B) of 0 to 7 T. Transient absorptions of the 1-naphthoxyl radical, T-T absorption of NA, and a short-lifetime intermediate (τ = 24 ns) were observed by a nanosecond laser flash photolysis technique. In n-hexane, the yield of escaped 1-naphthoxyl radicals dropped dramatically upon application of a 3 mT field, but then the yield increased with increasing B for 3 mT < B≤ 7 T. These observed MFEs can be explained by the hyperfine coupling and the Δg mechanisms through the singlet radical pair. The fact that MFEs were observed for the present photo-Fries rearrangement reaction indicates the presence of a singlet radical pair intermediate with a lifetime as long as several tens of nanoseconds.

Consequences of realistic embedding for the L 2,3 edge XAS of α-Fe 2 O 3

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

Bagus, Paul S.; Nelin, Connie J.; Sassi, Michel

Cluster models of condensed systems are often used to simulate the core-level spectra obtained with X-ray Photoelectron Spectroscopy, XPS, or with X-ray Absorption Spectroscopy, XAS, especially for near edge features.

Multi-photon ionization of atoms in intense short-wavelength radiation fields

NASA Astrophysics Data System (ADS)

Meyer, Michael

2015-05-01

The unprecedented characteristics of XUV and X-ray Free Electron Lasers (FELs) have stimulated numerous investigations focusing on the detailed understanding of fundamental photon-matter interactions in atoms and molecules. In particular, the high intensities (up to 106 W/cm2) giving rise to non-linear phenomena in the short wavelength regime. The basic phenomenology involves the production of highly charged ions via electron emission to which both sequential and direct multi-photon absorption processes contribute. The detailed investigation of the role and relative weight of these processes under different conditions (wavelength, pulse duration, intensity) is the key element for a comprehensive understanding of the ionization dynamics. Here the results of recent investigations are presented, performed at the FELs in Hamburg (FLASH) and Trieste (FERMI) on atomic systems with electronic structures of increasing complexity (Ar, Ne and Xe). Mainly, electron spectroscopy is used to obtain quantitative information about the relevance of various multi-photon ionization processes. For the case of Ar, a variety of processes including above threshold ionization (ATI) from 3p and 3s valence shells, direct 2p two-photon ionization and resonant 2p-4p two-photon excitations were observed and their role was quantitatively determined comparing the experimental ionization yields to ab-initio calculations of the cross sections for the multi-photon processes. Using Ar as a benchmark to prove the reliability of the combined experimental and theoretical approach, the more complex and intriguing case of Xe was studied. Especially, the analysis of the two-photon ATI from the Xe 4d shell reveals new insight into the character of the 4d giant resonance, which was unresolved in the linear one-photon regime. Finally, the influence of intense XUV radiation to the relaxation dynamics of the Ne 2s-3p resonance was investigated by angle-resolved electron spectroscopy, especially be observing the intensity dependent variation of the angular distribution patterns for the sequential ionization process.

Spectroscopic Analysis of Desiccation-Induced Alterations of the Chlorophyllide Transformation Pathway in Etiolated Barley Leaves1

PubMed Central

Le Lay, Pascaline; Böddi, Béla; Kovacevic, Dragan; Juneau, Philippe; Dewez, David; Popovic, Radovan

2001-01-01

Effects of water deficit on the chlorophyllide (Chlide) transformation pathway were studied in etiolated barley (Hordeum vulgare) leaves by analyzing absorption spectra and 77-K fluorescence spectra deconvoluted in components. Chlide transformations were examined in dehydrated leaves exposed to a 35-ms saturating flash triggering protochlorophyllide (Pchlide) and Chlide transformation processes. During the 90 min following the flash, we found that dehydration induced modifications of Chlide transformations, but no effect on Pchlide phototransformation into Chlide was observed. During this time, content of NADPH-Pchlide oxydoreductase in leaves did not change. Chlide transformation process in dehydrated leaves was characterized by the alteration of the Shibata shift process, by the appearance of a new Chlide species emitting at 692 nm, and by the favored formation of Chl(ide) A668F676. The formation of Chl(ide) A668F676, so-called “free Chlide,” was probably induced by disaggregation of highly aggregated Chlide complexes. Here, we offer evidence for the alteration of photoactive Pchlide regeneration process, which may be caused by the desiccation-induced inhibition of Pchlide synthesis. PMID:11553748

Visible light emission measurements from a dense electrothermal launcher plasma

NASA Astrophysics Data System (ADS)

Hankins, O. E.; Bourham, M. A.; Earnhart, J.; Gilligan, J. G.

1993-01-01

Measurements of the visible light emission from dense, weakly non-ideal plasmas have been performed on the experimental electrothermal launcher device 'SIRENS'. The plasma is created by the ablation or a Lexan insulator in the source, which then flows through a cylindrical barrel which serves as the material sample. Visible light emission spectra have been observed both in-bore and from the muzzle flash or the barrel, and from the flash or the source. Due to high plasma opacity (the plasma emits as a near blackbody) and absorption by the molecular components of the vapor shield, the hotter core or the arc has been difficult to observe. Recent measurements along the axis or the device indicate time-averaged plasma temperatures in the barrel or about 1 eV for lower energy shots, which agree with experimental measurements of the average heat flux and plasma conductivity along the barrel. Measurements or visible emission from the source indicate time averaged temperatures of 1 to 2 eV which agree with the theoretical estimates derived from ablated mass measurements and calculated estimates derived from plasma conductivity measurements.

Quantum-enhanced spectroscopy with entangled multiphoton states

NASA Astrophysics Data System (ADS)

Dinani, Hossein T.; Gupta, Manish K.; Dowling, Jonathan P.; Berry, Dominic W.

2016-06-01

Traditionally, spectroscopy is performed by examining the position of absorption lines. However, at frequencies near the transition frequency, additional information can be obtained from the phase shift. In this work we consider the information about the transition frequency obtained from both the absorption and the phase shift, as quantified by the Fisher information in an interferometric measurement. We examine the use of multiple single-photon states, NOON states, and numerically optimized states that are entangled and have multiple photons. We find the optimized states that improve over the standard quantum limit set by independent single photons for some atom number densities.

Quantum Cascade Laser Absorption Spectroscopy as a Plasma Diagnostic Tool: An Overview

PubMed Central

Welzel, Stefan; Hempel, Frank; Hübner, Marko; Lang, Norbert; Davies, Paul B.; Röpcke, Jürgen

2010-01-01

The recent availability of thermoelectrically cooled pulsed and continuous wave quantum and inter-band cascade lasers in the mid-infrared spectral region has led to significant improvements and new developments in chemical sensing techniques using in-situ laser absorption spectroscopy for plasma diagnostic purposes. The aim of this article is therefore two-fold: (i) to summarize the challenges which arise in the application of quantum cascade lasers in such environments, and, (ii) to provide an overview of recent spectroscopic results (encompassing cavity enhanced methods) obtained in different kinds of plasma used in both research and industry. PMID:22163581

Structure of Co-Doped Alq3 thin films investigated by grazing incidence X-ray absorption fine structure and Fourier transform infrared spectroscopy.

PubMed

Lin, Liang; Pang, Zhiyong; Fang, Shaojie; Wang, Fenggong; Song, Shumei; Huang, Yuying; Wei, Xiangjun; Yu, Haisheng; Han, Shenghao

2011-02-10

The structural properties of Co-doped tris(8-hydroxyquinoline)aluminum (Alq(3)) have been studied by grazing incidence X-ray absorption fine structure (GIXAFS) and Fourier transform infrared spectroscopy (FTIR). GIXAFS analysis suggests that there are multivalent Co-Alq(3) complexes and the doped Co atoms tend to locate at the attraction center with respect to N and O atoms and bond with them. The FTIR spectra indicate that the Co atoms interact with the meridional (mer) isomer of Alq(3) rather than forming inorganic compounds.

Wavelength modulation spectroscopy--digital detection of gas absorption harmonics based on Fourier analysis.

PubMed

Mei, Liang; Svanberg, Sune

2015-03-20

This work presents a detailed study of the theoretical aspects of the Fourier analysis method, which has been utilized for gas absorption harmonic detection in wavelength modulation spectroscopy (WMS). The lock-in detection of the harmonic signal is accomplished by studying the phase term of the inverse Fourier transform of the Fourier spectrum that corresponds to the harmonic signal. The mathematics and the corresponding simulation results are given for each procedure when applying the Fourier analysis method. The present work provides a detailed view of the WMS technique when applying the Fourier analysis method.

Microwave-induced direct spin-flip transitions in mesoscopic Pd/Co heterojunctions

NASA Astrophysics Data System (ADS)

Pietsch, Torsten; Egle, Stefan; Keller, Martin; Fridtjof-Pernau, Hans; Strigl, Florian; Scheer, Elke

2016-09-01

We experimentally investigate the effect of resonant microwave absorption on the magneto-conductance of tunable Co/Pd point contacts. At the interface a non-equilibrium spin accumulation is created via microwave absorption and can be probed via point contact spectroscopy. We interpret the results as a signature of direct spin-flip excitations in Zeeman-split spin-subbands within the Pd normal metal part of the junction. The inverse effect, which is associated with the emission of a microwave photon in a ferromagnet/normal metal point contact, can also be detected via its unique signature in transport spectroscopy.

Formation of TiO2 nanorings due to rapid thermal annealing of swift heavy ion irradiated films.

PubMed

Thakurdesai, Madhavi; Sulania, I; Narsale, A M; Kanjilal, D; Bhattacharyya, Varsha

2008-09-01

Amorphous thin films of TiO2 deposited by Pulsed Laser Deposition (PLD) method are irradiated by Swift Heavy Ion (SHI) beam. The irradiated films are subsequently annealed by Rapid Thermal Annealing (RTA) method. Atomic Force Microscopy (AFM) study reveals formation of nano-rings on the surface after RTA processing. Phase change is identified by Glancing Angle X-ray Diffraction (GAXRD) and Raman spectroscopy. Optical characterisation is carried out by UV-VIS absorption spectroscopy. Though no shift of absorption edge is observed after irradiation, RTA processing does show redshift.

Quantum cascade laser absorption spectroscopy as a plasma diagnostic tool: an overview.

PubMed

Welzel, Stefan; Hempel, Frank; Hübner, Marko; Lang, Norbert; Davies, Paul B; Röpcke, Jürgen

2010-01-01

The recent availability of thermoelectrically cooled pulsed and continuous wave quantum and inter-band cascade lasers in the mid-infrared spectral region has led to significant improvements and new developments in chemical sensing techniques using in-situ laser absorption spectroscopy for plasma diagnostic purposes. The aim of this article is therefore two-fold: (i) to summarize the challenges which arise in the application of quantum cascade lasers in such environments, and, (ii) to provide an overview of recent spectroscopic results (encompassing cavity enhanced methods) obtained in different kinds of plasma used in both research and industry.

[Gas pipeline leak detection based on tunable diode laser absorption spectroscopy].

PubMed

Zhang, Qi-Xing; Wang, Jin-Jun; Liu, Bing-Hai; Cai, Ting-Li; Qiao, Li-Feng; Zhang, Yong-Ming

2009-08-01

The principle of tunable diode laser absorption spectroscopy and harmonic detection technique was introduced. An experimental device was developed by point sampling through small multi-reflection gas cell. A specific line near 1 653. 7 nm was targeted for methane measurement using a distributed feedback diode laser as tunable light source. The linearity between the intensity of second harmonic signal and the concentration of methane was determined. The background content of methane in air was measured. The results show that gas sensors using tunable diode lasers provide a high sensitivity and high selectivity method for city gas pipeline leak detection.

QCL spectroscopy combined with the least squares method for substance analysis

NASA Astrophysics Data System (ADS)

Samsonov, D. A.; Tabalina, A. S.; Fufurin, I. L.

2017-11-01

The article briefly describes distinctive features of quantum cascade lasers (QCL). It also describes an experimental set-up for acquiring mid-infrared absorption spectra using QCL. The paper demonstrates experimental results in the form of normed spectra. We tested the application of the least squares method for spectrum analysis. We used this method for substance identification and extraction of concentration data. We compare the results with more common methods of absorption spectroscopy. Eventually, we prove the feasibility of using this simple method for quantitative and qualitative analysis of experimental data acquired with QCL.

An x-ray absorption spectroscopy study of Cd binding onto a halophilic archaeon

NASA Astrophysics Data System (ADS)

Showalter, Allison R.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Bunker, Bruce A.

2016-05-01

X-ray absorption spectroscopy (XAS) and cadmium (Cd) isotherm experiments determine how Cd adsorbs to the surface of halophilic archaeon Halobacterium noricense. This archaeon, isolated from the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico could be involved with the transport of toxic metals stored in the transuranic waste in the salt mine. The isotherm experiments show that adsorption is relatively constant across the tolerable pH range for H. noricense. The XAS results indicate that Cd adsorption occurs predominately via a sulfur site, most likely sulfhydryl, with the same site dominating all measured pH values.

Plasmon-Exciton Coupling Interaction for Surface Catalytic Reactions.

PubMed

Wang, Jingang; Lin, Weihua; Xu, Xuefeng; Ma, Fengcai; Sun, Mengtao

2018-05-01

In this review, we firstly reveal the physical principle of plasmon-exciton coupling interaction with steady absorption spectroscopy, and ultrafast transition absorption spectroscopy, based on the pump-prop technology. Secondly, we introduce the fabrication of electro-optical device of two-dimensional semiconductor-nanostructure noble metals hybrid, based on the plasmon-exciton coupling interactions. Thirdly, we introduce the applications of plasmon-exciton coupling interaction in the field of surface catalytic reactions. Lastly, the perspective of plasmon-exciton coupling interaction and applications closed this review. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Static magnetic Faraday rotation spectroscopy combined with a differential scheme for OH detection

NASA Astrophysics Data System (ADS)

Zhao, Weixiong; Deng, Lunhua; Qian, Xiaodong; Fang, Bo; Gai, Yanbo; Chen, Weidong; Gao, Xiaoming; Zhang, Weijun

2015-04-01

The hydroxyl (OH) radical plays a critical role in atmospheric chemistry due to its high reactivity with volatile organic compounds (VOCs) and other trace gaseous species. Because of its very short life time and very low concentration in the atmosphere, interference-free high sensitivity in-situ OH monitoring by laser spectroscopy represents a real challenge. Faraday rotation spectroscopy (FRS) relies on the particular magneto-optic effect observed for paramagnetic species, which makes it capable of enhancing the detection sensitivity and mitigation of spectral interferences from diamagnetic species in the atmosphere. When an AC magnetic field is used, the Zeeman splitting of the molecular absorption line (and thus the magnetic circular birefringence) is modulated. This provides an 'internal modulation' of the sample, which permits to suppress the external noise like interference fringes. An alternative FRS detection scheme is to use a static magnetic field (DC-field) associated with laser wavelength modulation to effectively modulate the Zeeman splitting of the absorption lines. In the DC field case, wavelength modulation of the laser frequency can provide excellent performance compared to most of the sensing systems based on direct absorption and wavelength modulation spectroscopy. The dimension of the DC solenoid is not limited by the resonant frequency of the RLC circuit, which makes large dimension solenoid coil achievable and the absorption base length could be further increased. By employing a combination of the environmental photochemical reactor or smog chamber with multipass absorption cell, one can lower the minimum detection limit for high accuracy atmospheric chemistry studies. In this paper, we report on the development of a DC field based FRS in conjunction with a balanced detection scheme for OH radical detection at 2.8 μm and the construction of OH chemistry research platform which combined a large dimension superconducting magnetic coil with the multipass cell and photochemical reactor chamber for real time in-situ measurement of OH radical concentration in the chamber.

Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer† †Electronic supplementary information (ESI) available: Syntheses, structure characterization data, and UV/vis absorption and emission spectra. See DOI: 10.1039/c4sc03865g

PubMed Central

Guo, Song; Xu, Liang; Xu, Kejing; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-01-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C60 was used as the complementary hydrogen bonding module (C-1), in which the C60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C60 module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C60 module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion. PMID:29218142

[Experimental research of turbidity influence on water quality monitoring of COD in UV-visible spectroscopy].

PubMed

Tang, Bin; Wei, Biao; Wu, De-Cao; Mi, De-Ling; Zhao, Jing-Xiao; Feng, Peng; Jiang, Shang-Hai; Mao, Ben-Jiang

2014-11-01

Eliminating turbidity is a direct effect spectroscopy detection of COD key technical problems. This stems from the UV-visible spectroscopy detected key quality parameters depend on an accurate and effective analysis of water quality parameters analytical model, and turbidity is an important parameter that affects the modeling. In this paper, we selected formazine turbidity solution and standard solution of potassium hydrogen phthalate to study the turbidity affect of UV--visible absorption spectroscopy detection of COD, at the characteristics wavelength of 245, 300, 360 and 560 nm wavelength point several characteristics with the turbidity change in absorbance method of least squares curve fitting, thus analyzes the variation of absorbance with turbidity. The results show, In the ultraviolet range of 240 to 380 nm, as the turbidity caused by particle produces compounds to the organics, it is relatively complicated to test the turbidity affections on the water Ultraviolet spectra; in the visible region of 380 to 780 nm, the turbidity of the spectrum weakens with wavelength increases. Based on this, this paper we study the multiplicative scatter correction method affected by the turbidity of the water sample spectra calibration test, this method can correct water samples spectral affected by turbidity. After treatment, by comparing the spectra before, the results showed that the turbidity caused by wavelength baseline shift points have been effectively corrected, and features in the ultraviolet region has not diminished. Then we make multiplicative scatter correction for the three selected UV liquid-visible absorption spectroscopy, experimental results shows that on the premise of saving the characteristic of the Ultraviolet-Visible absorption spectrum of water samples, which not only improve the quality of COD spectroscopy detection SNR, but also for providing an efficient data conditioning regimen for establishing an accurate of the chemical measurement methods.

Two-dimensional molybdenum disulphide nanosheet-covered metal nanoparticle array as a floating gate in multi-functional flash memories

NASA Astrophysics Data System (ADS)

Han, Su-Ting; Zhou, Ye; Chen, Bo; Zhou, Li; Yan, Yan; Zhang, Hua; Roy, V. A. L.

2015-10-01

Semiconducting two-dimensional materials appear to be excellent candidates for non-volatile memory applications. However, the limited controllability of charge trapping behaviors and the lack of multi-bit storage studies in two-dimensional based memory devices require further improvement for realistic applications. Here, we report a flash memory consisting of metal NPs-molybdenum disulphide (MoS2) as a floating gate by introducing a metal nanoparticle (NP) (Ag, Au, Pt) monolayer underneath the MoS2 nanosheets. Controlled charge trapping and long data retention have been achieved in a metal (Ag, Au, Pt) NPs-MoS2 floating gate flash memory. This controlled charge trapping is hypothesized to be attributed to band bending and a built-in electric field ξbi between the interface of the metal NPs and MoS2. The metal NPs-MoS2 floating gate flash memories were further proven to be multi-bit memory storage devices possessing a 3-bit storage capability and a good retention capability up to 104 s. We anticipate that these findings would provide scientific insight for the development of novel memory devices utilizing an atomically thin two-dimensional lattice structure.Semiconducting two-dimensional materials appear to be excellent candidates for non-volatile memory applications. However, the limited controllability of charge trapping behaviors and the lack of multi-bit storage studies in two-dimensional based memory devices require further improvement for realistic applications. Here, we report a flash memory consisting of metal NPs-molybdenum disulphide (MoS2) as a floating gate by introducing a metal nanoparticle (NP) (Ag, Au, Pt) monolayer underneath the MoS2 nanosheets. Controlled charge trapping and long data retention have been achieved in a metal (Ag, Au, Pt) NPs-MoS2 floating gate flash memory. This controlled charge trapping is hypothesized to be attributed to band bending and a built-in electric field ξbi between the interface of the metal NPs and MoS2. The metal NPs-MoS2 floating gate flash memories were further proven to be multi-bit memory storage devices possessing a 3-bit storage capability and a good retention capability up to 104 s. We anticipate that these findings would provide scientific insight for the development of novel memory devices utilizing an atomically thin two-dimensional lattice structure. Electronic supplementary information (ESI) available: Energy-dispersive X-ray spectroscopy (EDS) spectra of the metal NPs, SEM image of MoS2 on Au NPs, erasing operations of the metal NPs-MoS2 memory device, transfer characteristics of the standard FET devices and Ag NP devices under programming operation, tapping-mode AFM height image of the fabricated MoS2 film for pristine MoS2 flash memory, gate signals used for programming the Au NPs-MoS2 and Pt NPs-MoS2 flash memories, and data levels recorded for 100 sequential cycles. See DOI: 10.1039/c5nr05054e

Ultrafast X-Ray Absorption Spectroscopy of Isochorically Heated Warm Dense Matter

NASA Astrophysics Data System (ADS)

Engelhorn, Kyle Craig

This dissertation will present a series of new tools, together with new techniques, focused on the understanding of warm and dense matter. We report on the development of a high time resolution and high detection efficiency x-ray camera. The camera is integrated with a short pulse laser and an x-ray beamline at the Advanced Light Source synchrotron. This provides an instrument for single shot, broadband x-ray absorption spectroscopy of warm and dense matter with 2 picosecond time resolution. Warm and dense matter is created by isochorically heating samples of known density with an ultrafast optical laser pulse, and X-ray absorption spectroscopy probes the unoccupied electronic density of states before the onset of hydrodynamic expansion and electron-ion equilibrium is reached. Measured spectra from a variety of materials are compared with first principle molecular dynamics and density functional theory calculations. In heated silicon dioxide spectra, two novel pre-edge features are observed, a peak below the band gap and absorption within the band gap, while a reduction was observed in the features above the edge. From consideration of the calculated spectra, the peak below the gap is attributed to valence electrons that have been promoted to the conduction band, the absorption within the gap is attributed to broken Si-O bonds, and the reduction above the edge is attributed to an elevated ionic temperature. In heated copper spectra, a time-dependent shift and broadening of the absorption edge are observed, consistent with and elevated electron temperature. The temporal evolution of the electronic temperature is accurately determined by fitting the measured spectra with calculated spectra. The electron-ion equilibration is studied with a two-temperature model. In heated nickel spectra, a shift of the absorption edge is observed. This shift is found to be inconsistent with calculated spectra and independent of incident laser fluence. A shift of the chemical potential is applied to the calculated spectra to obtain satisfactory agreement with measured spectra.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

NASA Astrophysics Data System (ADS)

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; Hartig, K. C.; Phillips, M. C.

2018-06-01

Rapid, in-field, and non-contact isotopic analysis of solid materials is extremely important to a large number of applications, such as nuclear nonproliferation monitoring and forensics, geochemistry, archaeology, and biochemistry. Presently, isotopic measurements for these and many other fields are performed in laboratory settings. Rapid, in-field, and non-contact isotopic analysis of solid material is possible with optical spectroscopy tools when combined with laser ablation. Laser ablation generates a transient vapor of any solid material when a powerful laser interacts with a sample of interest. Analysis of atoms, ions, and molecules in a laser-produced plasma using optical spectroscopy tools can provide isotopic information with the advantages of real-time analysis, standoff capability, and no sample preparation requirement. Both emission and absorption spectroscopy methods can be used for isotopic analysis of solid materials. However, applying optical spectroscopy to the measurement of isotope ratios from solid materials presents numerous challenges. Isotope shifts arise primarily due to variation in nuclear charge distribution caused by different numbers of neutrons, but the small proportional nuclear mass differences between nuclei of various isotopes lead to correspondingly small differences in optical transition wavelengths. Along with this, various line broadening mechanisms in laser-produced plasmas and instrumental broadening generated by the detection system are technical challenges frequently encountered with emission-based optical diagnostics. These challenges can be overcome by measuring the isotope shifts associated with the vibronic emission bands from molecules or by using the techniques of laser-based absorption/fluorescence spectroscopy to marginalize the effect of instrumental broadening. Absorption and fluorescence spectroscopy probe the ground state atoms existing in the plasma when it is cooler, which inherently provides narrower lineshapes, as opposed to emission spectroscopy which requires higher plasma temperatures to be able to detect thermally excited emission. Improvements in laser and detection systems and spectroscopic techniques have allowed for isotopic measurements to be carried out at standoff distances under ambient atmospheric conditions, which have expanded the applicability of optical spectroscopy-based isotopic measurements to a variety of scientific fields. These technological advances offer an in-situ measurement capability that was previously not available. This review will focus on isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing knowledge/technological gaps identified from the current literature and suggestions for the future work.

Infrared absorption and admittance spectroscopy of Ge quantum dots on a strained SiGe layer

NASA Astrophysics Data System (ADS)

Yakimov, A. I.; Nikiforov, A. I.; Timofeev, V. A.; Dvurechenskii, A. V.

2011-12-01

A combined infrared absorption and admittance spectroscopy is carried out in examining the energy level structure and the hole emission process in self-assembled Ge quantum dots (QDs) placed on a strained Si0.65Ge0.35 quantum well (QW), which, in turn, is incorporated in a Si matrix. In the midinfrared spectral range, the dots exhibit three dominant absorption bands peaked at 130, 250 and 390 meV. By a comparison between absorption measurements and six-band {\\bf k}\\;{\\bm \\cdot}\\;{\\bf p} calculations, the long-wave (~130 meV) resonance is attributed to a transition from the QD hole ground state to the two-dimensional heavy-hole states confined in the Si0.65Ge0.35 layer. The mid-wave absorption band around 390 meV is ascribed to a transition from the QD hole ground state to the three-dimensional continuum states of the Si matrix. An equivalent absorption cross section for these two types of transitions is determined to be 1.2 × 10-15 cm2 and 1.2 × 10-16 cm2, respectively. The origin of the transmission minimum around 250 meV is more ambiguous. We tentatively propose that it can be due to transition either from the highest heavy-hole subband of the Si0.65Ge0.35 QW to continuum states above the Si barrier or from the dot states to the light-hole and split-off subbands of the Si0.65Ge0.35 layer. The photoinduced bleaching of the near-infrared absorption is detected under interband optical excitation of undoped samples. This finding is explained by blocking the interband transitions inside the dots due to the state filling effect. By using the admittance spectroscopy, the mechanism of hole escape from QDs in the presence of an ac vertical electric field is identified. A thermally activated emission from the QD ground state into the two-dimensional states of the Si0.65Ge0.35 well is observed. From the temperature- and frequency-dependent measurements the QD hole ground state is determined to be located ~160 meV below the heavy-hole subband of the Si0.65Ge0.35 layer in good agreement with the results obtained by infrared absorption spectroscopy and six-band {\\bf k}\\;{\\bm \\cdot}\\;{\\bf p} theory. The information acquired from our experimental observations is valuable for feasible device applications.

Examination of Arsenic Speciation in Sulfidic Solutions Using X-ray Absorption Spectroscopy

EPA Science Inventory

The chemical speciation of arsenic in sulfidic waters is complicated by the existence of thioarsenic species. The purpose of this research was to use advanced spectroscopy techniques along with speciation modeling and chromatography to elucidate the chemical speciation of As in ...

Terahertz Time Domain Spectroscopy of Phonon-Depopulation Based Quantum Cascade Lasers

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

Rungsawang, R.; Dhillon, S. S.; Jukam, N.

2011-12-23

A 3.1 THz phonon depopulation-based quantum-cascade-laser is investigated using terahertz time domain spectroscopy. A gain of 25 cm{sup -1} and absorption features due to the lower laser level being populated from a parasitic electronic channel are highlighted.

APPLYING OPEN-PATH OPTICAL SPECTROSCOPY TO HEAVY-DUTY DIESEL EMISSIONS

EPA Science Inventory

Non-dispersive infrared absorption has been used to measure gaseous emissions for both stationary and mobile sources. Fourier transform infrared spectroscopy has been used for stationary sources as both extractive and open-path methods. We have applied the open-path method for bo...

MEASUREMENT OF AMMONIA EMISSIONS FROM MECHANICALLY VENTILATED POULTRY HOUSES USING MULTIPATH TUNABLE DIODE LASER SPECTROSCOPY

EPA Science Inventory

Ammonia emissions from mechanically ventilated poultry operations are an important environmental concern. Open Path Tunable Diode Laser Absorption Spectroscopy has emerged as a robust real-time method for gas phase measurement of ammonia concentrations in agricultural settings. ...

Terahertz time-domain spectroscopy of submonolayer water adsorption in hydrophilic silica aerogel.

PubMed

Zhang, Jiangquan; Grischkowsky, Daniel

2004-05-01

We report a terahertz time-domain spectroscopy study of the adsorption of water in hydrophilic silica aerogel. The adsorbed water is in submonolayer form and shows properties of index of refraction similar to those of bulk water but different absorption properties.

Ghost Spectroscopy with Classical Thermal Light Emitted by a Superluminescent Diode

NASA Astrophysics Data System (ADS)

Janassek, Patrick; Blumenstein, Sébastien; Elsäßer, Wolfgang

2018-02-01

We propose and realize the first classical ghost-imaging (GI) experiment in the frequency or wavelength domain, thus performing ghost spectroscopy using thermal light exhibiting photon bunching. The required wavelength correlations are provided by light emitted by spectrally broadband near-infrared amplified spontaneous emission of a semiconductor-based superluminescent diode. They are characterized by wavelength-resolved intensity cross-correlation measurements utilizing two-photon-absorption interferometry. Finally, a real-world spectroscopic application of this ghost spectroscopy with a classical light scheme is demonstrated in which an absorption band of trichloromethane (chloroform) at 1214 nm is reconstructed with a spectral resolution of 10 nm as a proof-of-principle experiment. This ghost-spectroscopy work fills the gap of a hitherto missing analogy between the spatial and the spectral domain in classical GI modalities, with the expectation of contributing towards a broader dissemination of correlated photon ghost modalities, hence paving the way towards more applications which exploit the favorable advantages.

Probing interfacial characteristics of rubrene/pentacene and pentacene/rubrene bilayers with soft X-ray spectroscopy.

PubMed

Seo, J H; Pedersen, T M; Chang, G S; Moewes, A; Yoo, K-H; Cho, S J; Whang, C N

2007-08-16

The electronic structure of rubrene/pentacene and pentacene/rubrene bilayers has been investigated using soft X-ray absorption spectroscopy, resonant X-ray emission spectroscopy, and density-functional theory calculations. X-ray absorption and emission measurements reveal that it has been possible to alter the lowest unoccupied and the highest occupied molecular orbital states of rubrene in rubrene/pentacene bilayer. In the reverse case, one gets p* molecular orbital states originating from the pentacene layer. Resonant X-ray emission spectra suggest a reduction in the hole-transition probabilities for the pentacene/rubrene bilayer in comparison to reference pentacene layer. For the rubrenepentacene structure, the hole-transition probability shows an increase in comparison to the rubrene reference. We also determined the energy level alignment of the pentacene-rubrene interface by using X-ray and ultraviolet photoelectron spectroscopy. From these comparisons, it is found that the electronic structure of the pentacene-rubrene interface has a strong dependence on interface characteristics which depends on the order of the layers used.

Hazardous Gas Detection Sensor Using Broadband Light-Emitting Diode-Based Absorption Spectroscopy for Space Applications

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

Terracciano, Anthony; Thurmond, Kyle; Villar, Michael

As space travel matures and extended duration voyages become increasingly common, it will be necessary to include arrays of early fire detection systems aboard spacefaring vessels, space habitats, and in spacesuits. As gasses that are relevant to combustion and pyrolysis have absorption features in the midinfrared range, it is possible to utilize absorption spectroscopy as a means of detecting and quantifying the concentration of these hazardous compounds. Within this work, a sensor for detecting carbon dioxide has been designed and tested autonomously on a high-altitude balloon flight. The sensor utilizes a 4.2-mm lightemitting diode source, amplitude modulation to characterize speciesmore » concentrations, and frequency modulation to characterize ambient temperature. Future work will include expanding the sensor design to detect other gases, and demonstrating suborbital flight capability.« less

Overtone spectroscopy of N2H+ molecular ions—application of cavity ring-down spectroscopy

NASA Astrophysics Data System (ADS)

Kálosi, Á.; Dohnal, P.; Shapko, D.; Roučka, Š.; Plašil, R.; Johnsen, R.; Glosík, J.

2017-10-01

A stationary afterglow apparatus in conjunction with a laser absorption cavity ring-down spectrometer has been employed to observe absorption lines in the P- and R-branches of the (200) <-- (000) and (2110) <-- (0110) vibrational bands of the N2H+ molecular ion as a part of an ongoing study of the electron-ion recombination of N2H+ in afterglow plasmas. The probed absorption lines lie in the near-infrared spectral region around 1580 nm. The observed transition wavenumbers were fitted to experimental accuracy and improved molecular constants for the (200) vibrational state were obtained. The employed experimental technique enables probing of the translational, rotational and vibrational temperature of the studied ions as well as the determination of the number densities of different quantum states of the ion in discharge and afterglow plasma.

Applications of “Tender” Energy (1-5 keV) X-ray Absorption Spectroscopy in Life Sciences

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

Northrup, Paul; Leri, Alessandra; Tappero, Ryan

The “tender” energy range of 1 to 5 keV, between the energy ranges of most “hard” (>5 keV) and “soft” (<1 keV) synchrotron X-ray facilities, offers some unique opportunities for synchrotron-based X-ray absorption fine structure spectroscopy in life sciences. In particular the K absorption edges of Na through Ca offer opportunities to study local structure, speciation, and chemistry of many important biological compounds, structures and processes. This is an area of largely untapped science, in part due to a scarcity of optimized facilities. Such measurements also entail unique experimental challenges. Lastly, this brief review describes the technique, its experimental challenges,more » recent progress in development of microbeam measurement capabilities, and several highlights illustrating applications in life sciences.« less

Optofluidic-Tunable Color Filters And Spectroscopy Based On Liquid-Crystal Microflows

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

Cuennet, J. G.; Vasdekis, Andreas E.; Psaltis, D.

The integration of color filters with microfluidics has attracted substantial attention in recent years, for on-chip absorption, fluorescence, or Raman analysis. We describe such tunable filters based on the micro-flow of liquid crystals. The filter operation is based on the wavelength dependent liquid crystal birefringence that can be tuned by modifying the flow velocity field in the microchannel. The latter is possible both temporally and spatially by varying the inlet pressure and the channel geometry respectively. We explored the use of these optofluidic filters for on-chip absorption spectroscopy; by integrating the distance dependent color filter with a dye-filled micro-channel, themore » absorption spectrum of a dye could be measured. Liquid crystal microflows simplify substantially the optofluidic integration, actuation and tuning of color filters for lab-on-a-chip spectroscopic applications.« less

Hazardous Gas Detection Sensor Using Broadband Light-Emitting Diode-Based Absorption Spectroscopy for Space Applications

DOE PAGES

Terracciano, Anthony; Thurmond, Kyle; Villar, Michael; ...

2018-03-12

As space travel matures and extended duration voyages become increasingly common, it will be necessary to include arrays of early fire detection systems aboard spacefaring vessels, space habitats, and in spacesuits. As gasses that are relevant to combustion and pyrolysis have absorption features in the midinfrared range, it is possible to utilize absorption spectroscopy as a means of detecting and quantifying the concentration of these hazardous compounds. Within this work, a sensor for detecting carbon dioxide has been designed and tested autonomously on a high-altitude balloon flight. The sensor utilizes a 4.2-mm lightemitting diode source, amplitude modulation to characterize speciesmore » concentrations, and frequency modulation to characterize ambient temperature. Future work will include expanding the sensor design to detect other gases, and demonstrating suborbital flight capability.« less

Site partitioning of Cr3+ in the trichroic alexandrite BeAl2O4:Cr3+ crystal: contribution from x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Bordage, Amélie; Rossano, Stéphanie; Horn, Adolf Heinrich; Fuchs, Yves

2012-06-01

X-ray absorption spectroscopy measurements at the Cr K-edge of a trichroic crystal of alexandrite BeAl2O4:Cr3+ for different orientations of the crystal with respect to the polarization and direction of the x-ray incident beam have been performed. Analysis of the experimental spectra with the help of first-principles calculations of x-ray absorption spectra allowed us to estimate the proportion of chromium Cr3+ cations among the two different octahedral sites of the alexandrite structure (70% in the Cs site-30% in the Ci site). The methodology presented in this work opens up new possibilities in the field of mineralogy for the study of complex minerals containing several sites potentially occupied by several transition elements or for solid solutions.

Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries

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

Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke

2016-03-07

Here, we evaluate the utilities of fluorescence-yield (FY) modes in soft X-ray absorption spectroscopy (XAS) of several cathodematerials for Li-ion batteries. In the case of total-FY (TFY) XAS for LiNi 0.5Mn 1.5O 4, the line shape of the Mn L 3-edge XAS was largely distorted by the self-absorption and saturation effects, while the distortions were less pronounced at the Ni L 3 edge. The distortions were suppressed for the inverse-partial-FY (IPFY) spectra. We found that, in the cathodematerials, the IPFY XAS is highly effective for the Cr, Mn, and Fe L edges and the TFY and PFY modes are usefulmore » enough for the Ni L edge which is far from the O K edge.« less

Specimen charging in X-ray absorption spectroscopy: correction of total electron yield data from stabilized zirconia in the energy range 250-915 eV.

PubMed

Vlachos, Dimitrios; Craven, Alan J; McComb, David W

2005-03-01

The effects of specimen charging on X-ray absorption spectroscopy using total electron yield have been investigated using powder samples of zirconia stabilized by a range of oxides. The stabilized zirconia powder was mixed with graphite to minimize the charging but significant modifications of the intensities of features in the X-ray absorption near-edge fine structure (XANES) still occurred. The time dependence of the charging was measured experimentally using a time scan, and an algorithm was developed to use this measured time dependence to correct the effects of the charging. The algorithm assumes that the system approaches the equilibrium state by an exponential decay. The corrected XANES show improved agreement with the electron energy-loss near-edge fine structure obtained from the same samples.

Applications of “Tender” Energy (1-5 keV) X-ray Absorption Spectroscopy in Life Sciences

DOE PAGES

Northrup, Paul; Leri, Alessandra; Tappero, Ryan

2016-02-15

The “tender” energy range of 1 to 5 keV, between the energy ranges of most “hard” (>5 keV) and “soft” (<1 keV) synchrotron X-ray facilities, offers some unique opportunities for synchrotron-based X-ray absorption fine structure spectroscopy in life sciences. In particular the K absorption edges of Na through Ca offer opportunities to study local structure, speciation, and chemistry of many important biological compounds, structures and processes. This is an area of largely untapped science, in part due to a scarcity of optimized facilities. Such measurements also entail unique experimental challenges. Lastly, this brief review describes the technique, its experimental challenges,more » recent progress in development of microbeam measurement capabilities, and several highlights illustrating applications in life sciences.« less

Dynamical Study of Femtosecond-Laser-Ablated Liquid-Aluminum Nanoparticles Using Spatiotemporally Resolved X-Ray-Absorption Fine-Structure Spectroscopy

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

Oguri, Katsuya; Okano, Yasuaki; Nishikawa, Tadashi

2007-10-19

We study the temperature evolution of aluminum nanoparticles generated by femtosecond laser ablation with spatiotemporally resolved x-ray-absorption fine-structure spectroscopy. We successfully identify the nanoparticles based on the L-edge absorption fine structure of the ablation plume in combination with the dependence of the edge structure on the irradiation intensity and the expansion velocity of the plume. In particular, we show that the lattice temperature of the nanoparticles is estimated from the L-edge slope, and that its spatial dependence reflects the cooling of the nanoparticles during plume expansion. The results reveal that the emitted nanoparticles travel in a vacuum as a condensedmore » liquid phase with a lattice temperature of about 2500 to 4200 K in the early stage of plume expansion.« less

Measurements of the rate constant of HOsub2 + NOsub2 + Nsub2 --> HOsub2NOsub2 + Nsub2 using near-infrared wavelength-modulation spectroscopy and UV-visible absorption spectroscopy

NASA Technical Reports Server (NTRS)

Christensen, L. E.; Okumura, M.; Sander, S. P.; Friedl, R. R.; Miller, C. E.; Sloan, J. J.

2004-01-01

Rate coefficients for the reaction HO(sub 2)+ NO(sub 2) + N(sub 2) --> HO(sub 2)NO(sub 2) + N(sub 2) (reaction 1) were measured using simultaneous near-IR and UV spectroscopy from 220 to 298 K and from 45 to 200 Torr.

Application of Cavity Enhanced Absorption Spectroscopy to the Detection of Nitric Oxide, Carbonyl Sulphide, and Ethane—Breath Biomarkers of Serious Diseases

PubMed Central

Wojtas, Jacek

2015-01-01

The paper presents one of the laser absorption spectroscopy techniques as an effective tool for sensitive analysis of trace gas species in human breath. Characterization of nitric oxide, carbonyl sulphide and ethane, and the selection of their absorption lines are described. Experiments with some biomarkers showed that detection of pathogenic changes at the molecular level is possible using this technique. Thanks to cavity enhanced spectroscopy application, detection limits at the ppb-level and short measurements time (<3 s) were achieved. Absorption lines of reference samples of the selected volatile biomarkers were probed using a distributed feedback quantum cascade laser and a tunable laser system consisting of an optical parametric oscillator and difference frequency generator. Setup using the first source provided a detection limit of 30 ppb for nitric oxide and 250 ppb for carbonyl sulphide. During experiments employing a second laser, detection limits of 0.9 ppb and 0.3 ppb were obtained for carbonyl sulphide and ethane, respectively. The conducted experiments show that this type of diagnosis would significantly increase chances for effective therapy of some diseases. Additionally, it offers non-invasive and real time measurements, high sensitivity and selectivity as well as minimizing discomfort for patients. For that reason, such sensors can be used in screening for early detection of serious diseases. PMID:26091398

Synthesis and binding properties of arylethyne-linked porphyrin-zinc complexes for organic electronics applications.

PubMed

Reainthippayasakul, W; Paosawatyanyong, B; Bhanthumnavin, W

2013-05-01

Conjugated meso-alkynyl 5,15-dimesitylporphyrin metal complexes have been synthesized by Sonogashira coupling reaction in good yields. Alkynyl groups were chosen as a link at the meso positions in order to extend the pi-conjugated length of porphyrin rings. These synthesized porphyrin derivatives were characterized by 1H NMR spectroscopy and MALDI-TOF mass spectrometry. Moreover, UV-visible spectroscopy and fluorescence spectroscopy were also used to investigate their photophysical properties. It has been demonstrated that central metal ions as well as meso substituents on porphyrin rings affected the electronic absorption and emission spectra of the compounds. Spectroscopic results revealed that alkyne-linked porphyrin metal complexes showed higher pi-conjugation compared with porphyrin building blocks resulting in red shifts in both absorption and emission spectra. Coordination properties of synthesized porphyrins were preliminarily investigated by UV-visible absorption and fluorescence emission spectroscopic titration with pyridine as axial ligand. The formation of porphyrin-pyridine complexes resulted in significant red shifts in absorption spectra and decrease of fluorescence intensity in emission spectra. Moreover, the 1H NMR titration experiments suggested that central metal ions play an important role to coordinate with pyridine and the coordination of porphyrin zinc(II) complex with pyridine occur in a 1:1 ratio. From these spectroscopic results, alkyne-linked porphyrin metal complexes offer potential applications as materials for optical organic nanosensors.

Application of Cavity Enhanced Absorption Spectroscopy to the Detection of Nitric Oxide, Carbonyl Sulphide, and Ethane--Breath Biomarkers of Serious Diseases.

PubMed

Wojtas, Jacek

2015-06-17

The paper presents one of the laser absorption spectroscopy techniques as an effective tool for sensitive analysis of trace gas species in human breath. Characterization of nitric oxide, carbonyl sulphide and ethane, and the selection of their absorption lines are described. Experiments with some biomarkers showed that detection of pathogenic changes at the molecular level is possible using this technique. Thanks to cavity enhanced spectroscopy application, detection limits at the ppb-level and short measurements time (<3 s) were achieved. Absorption lines of reference samples of the selected volatile biomarkers were probed using a distributed feedback quantum cascade laser and a tunable laser system consisting of an optical parametric oscillator and difference frequency generator. Setup using the first source provided a detection limit of 30 ppb for nitric oxide and 250 ppb for carbonyl sulphide. During experiments employing a second laser, detection limits of 0.9 ppb and 0.3 ppb were obtained for carbonyl sulphide and ethane, respectively. The conducted experiments show that this type of diagnosis would significantly increase chances for effective therapy of some diseases. Additionally, it offers non-invasive and real time measurements, high sensitivity and selectivity as well as minimizing discomfort for patients. For that reason, such sensors can be used in screening for early detection of serious diseases.

Capturing the radical ion-pair intermediate in DNA guanine oxidation

PubMed Central

Jie, Jialong; Liu, Kunhui; Wu, Lidan; Zhao, Hongmei; Song, Di; Su, Hongmei

2017-01-01

Although the radical ion pair has been frequently invoked as a key intermediate in DNA oxidative damage reactions and photoinduced electron transfer processes, the unambiguous detection and characterization of this species remain formidable and unresolved due to its extremely unstable nature and low concentration. We use the strategy that, at cryogenic temperatures, the transient species could be sufficiently stabilized to be detectable spectroscopically. By coupling the two techniques (the cryogenic stabilization and the time-resolved laser flash photolysis spectroscopy) together, we are able to capture the ion-pair transient G+•⋯Cl− in the chlorine radical–initiated DNA guanine (G) oxidation reaction, and provide direct evidence to ascertain the intricate type of addition/charge separation mechanism underlying guanine oxidation. The unique spectral signature of the radical ion-pair G+•⋯Cl− is identified, revealing a markedly intense absorption feature peaking at 570 nm that is distinctive from G+• alone. Moreover, the ion-pair spectrum is found to be highly sensitive to the protonation equilibria within guanine-cytosine base pair (G:C), which splits into two resolved bands at 480 and 610 nm as the acidic proton transfers along the central hydrogen bond from G+• to C. We thus use this exquisite sensitivity to track the intrabase-pair proton transfer dynamics in the double-stranded DNA oligonucleotides, which is of critical importance for the description of the proton-coupled charge transfer mechanisms in DNA. PMID:28630924

Why Flash Type Matters: A Statistical Analysis

NASA Astrophysics Data System (ADS)

Mecikalski, Retha M.; Bitzer, Phillip M.; Carey, Lawrence D.

2017-09-01

While the majority of research only differentiates between intracloud (IC) and cloud-to-ground (CG) flashes, there exists a third flash type, known as hybrid flashes. These flashes have extensive IC components as well as return strokes to ground but are misclassified as CG flashes in current flash type analyses due to the presence of a return stroke. In an effort to show that IC, CG, and hybrid flashes should be separately classified, the two-sample Kolmogorov-Smirnov (KS) test was applied to the flash sizes, flash initiation, and flash propagation altitudes for each of the three flash types. The KS test statistically showed that IC, CG, and hybrid flashes do not have the same parent distributions and thus should be separately classified. Separate classification of hybrid flashes will lead to improved lightning-related research, because unambiguously classified hybrid flashes occur on the same order of magnitude as CG flashes for multicellular storms.

Bodipy-C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer.

PubMed

Guo, Song; Xu, Liang; Xu, Kejing; Zhao, Jianzhang; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-07-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives ( B-1 , B-2 and B-3 , which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C 60 was used as the complementary hydrogen bonding module ( C-1 ), in which the C 60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references ( B-1-Me , B-2-Me and B-3-Me ), which are unable to form strong H-bonds with C-1 . Triple H-bonds are formed between each Bodipy antenna ( B-1 , B-2 and B-3 ) and the C 60 module ( C-1 ). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C 60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C 60 module (for assembly B-1·C-1 ), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1 ). Intra-assembly forward-backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet-triplet annihilation upconversion.

Etude de la dynamique des porteurs dans des nanofils de silicium par spectroscopie terahertz

NASA Astrophysics Data System (ADS)

Beaudoin, Alexandre

Ce memoire presente une etude des proprietes de conduction electrique et de la dynamique temporelle des porteurs de charges dans des nanofils de silicium sondes par rayonnement terahertz. Les cas de nanofils de silicium non intentionnellement dopes et dopes type n sont compares pour differentes configurations du montage experimental. Les mesures de spectroscopie terahertz en transmission montre qu'il est possible de detecter la presence de dopants dans les nanofils via leur absorption du rayonnement terahertz (˜ 1--12 meV). Les difficultes de modelisation de la transmission d'une impulsion electromagnetique dans un systeme de nanofils sont egalement discutees. La detection differentielle, une modification au systeme de spectroscopie terahertz, est testee et ses performances sont comparees au montage de caracterisation standard. Les instructions et des recommendations pour la mise en place de ce type de mesure sont incluses. Les resultats d'une experience de pompe optique-sonde terahertz sont egalement presentes. Dans cette experience, les porteurs de charge temporairement crees suite a l'absorption de la pompe optique (lambda ˜ 800 nm) dans les nanofils (les photoporteurs) s'ajoutent aux porteurs initialement presents et augmentent done l'absorption du rayonnement terahertz. Premierement, l'anisotropie de l'absorption terahertz et de la pompe optique par les nanofils est demontree. Deuxiemement, le temps de recombinaison des photoporteurs est etudie en fonction du nombre de photoporteurs injectes. Une hypothese expliquant les comportements observes pour les nanofils non-dopes et dopes-n est presentee. Troisiemement, la photoconductivite est extraite pour les nanofils non-dopes et dopes-n sur une plage de 0.5 a 2 THz. Un lissage sur la photoconductivite permet d'estimer le nombre de dopants dans les nanofils dopes-n. Mots-cles: nanofil, silicium, terahertz, conductivite, spectroscopie, photoconductivite.

Thermal denaturation of protein studied by terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Fu, Xiuhua; Li, Xiangjun; Liu, Jianjun; Du, Yong; Hong, Zhi

2012-12-01

In this study, the absorption spectra of native or thermal protein were measured in 0.2-1.4THz using terahertz time-domain spectroscopy (THz-TDS) system at room temperature, their absorption spectra and the refractive spectra were obtained. Experimental results indicate that protein both has strong absorption but their characteristics were not distinct in the THz region, and the absorption decreased during thermal denatured state. In order to prove protein had been denatured, we used Differential scanning calorimeter (DSC) measured their denatured temperature, from their DSC heating traces, collagen Td=101℃, Bovine serum albumin Td=97℃. While we also combined the Fourier transform infrared spectrometer (FTIR) to investigate their secondary and tertiary structure before and after denatuation, but the results did not have the distinct changes. We turned the absorption spectra and the refractive spectra to the dielectric spectra, and used the one-stage Debye model simulated the terahertz dielectric spectra of protein before and after denaturation. This research proved that the terahertz spectrum technology is feasible in testing protein that were affected by temperature or other factors which can provide theoretical foundation in the further study about the THz spectrum of protein and peptide temperature stability.

Detection of Ozone and Nitric Oxide in Decomposition Products of Air-Insulated Switchgear Using Ultraviolet Differential Optical Absorption Spectroscopy (UV-DOAS).

PubMed

Li, Yalong; Zhang, Xiaoxing; Li, Xin; Cui, Zhaolun; Xiao, Hai

2018-01-01

Air-insulated switchgear cabinets play a role in the protection and control of the modern power grid, and partial discharge (PD) switchgear is a long-term process in the non-normal operation of one of the situations; thus, condition monitoring of the switchgear is important. The air-insulated switchgear during PD enables the decomposition of air components, namely, O 3 and NO. A set of experimental platforms was designed on the basis of the principle of ultraviolet differential optical absorption spectroscopy (UV-DOAS) to detect O 3 and NO concentrations in air-insulated switchgear. Differential absorption algorithm and wavelet transform were used to extract effective absorption spectra; a linear relationship between O 3 and NO concentrations and absorption spectrum data were established. O 3 detection linearity was up to 0.9992 and the detection limit was at 3.76 ppm. NO detection linearity was up to 0.9990 and the detection limit was at 0.64 ppm. Results indicate that detection platform is suitable for detecting trace O 3 and NO gases produced by PD of the air-insulated switchgear.

Tunable Diode Laser Atomic Absorption Spectroscopy for Detection of Potassium under Optically Thick Conditions.

PubMed

Qu, Zhechao; Steinvall, Erik; Ghorbani, Ramin; Schmidt, Florian M

2016-04-05

Potassium (K) is an important element related to ash and fine-particle formation in biomass combustion processes. In situ measurements of gaseous atomic potassium, K(g), using robust optical absorption techniques can provide valuable insight into the K chemistry. However, for typical parts per billion K(g) concentrations in biomass flames and reactor gases, the product of atomic line strength and absorption path length can give rise to such high absorbance that the sample becomes opaque around the transition line center. We present a tunable diode laser atomic absorption spectroscopy (TDLAAS) methodology that enables accurate, calibration-free species quantification even under optically thick conditions, given that Beer-Lambert's law is valid. Analyte concentration and collisional line shape broadening are simultaneously determined by a least-squares fit of simulated to measured absorption profiles. Method validation measurements of K(g) concentrations in saturated potassium hydroxide vapor in the temperature range 950-1200 K showed excellent agreement with equilibrium calculations, and a dynamic range from 40 pptv cm to 40 ppmv cm. The applicability of the compact TDLAAS sensor is demonstrated by real-time detection of K(g) concentrations close to biomass pellets during atmospheric combustion in a laboratory reactor.

Sensor for headspace pressure and H2O concentration measurements in closed vials by tunable diode laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Cai, Tingdong; Wang, Guishi; Cao, Zhensong; Zhang, Weijun; Gao, Xiaoming

2014-07-01

The concentration of H2O and the pressure in the headspace of vials are simultaneously measured by a tunable diode laser sensor based on absorption spectroscopy techniques. The 7168.437 cm-1 spectral line of H2O is chosen as the sensing transition for its strong absorption strength and being reasonably far away from its neighboring molecular transitions. In order to prevent interference absorption by ambient water vapor in the room air, a difference between the measured signal and the referenced signal is used to calculate the pressure and H2O concentration in the headspace of vials, eliminating the need for inert gas purges and calibration with known gas. The validation of the sensor is conducted in a static vial, yielding an accuracy of 1.23% for pressure and 3.81% for H2O concentration. The sensitivity of the sensor is estimated to be about 2.5 Torr for pressure and 400 ppm for H2O concentration over a 3 cm absorption path length respectively. Accurate measurements for commercial freeze-dried products demonstrate the in-line applications of the sensor for the pharmaceutical industry.

[The Study on the Far-FTIR and THz Spectra of Azitromycin Drugs with Different Physical Forms].

PubMed

Yang, Yu-ping; Fan, Li-jie; Cui, Bin; Chen, Gen-xiang; Zhang, Zhen-wei; Zhang, Cun-lin

2015-11-01

Far Fourier transform infrared spectroscopy (Far-FTIR) and terahertz time-domain spectroscopy (THz-TDS) were used to measure the fingerprint spectra of Azitromycin suspension, capsule, tablet and dispersible tablet under vacuum and nitrogen conditions, respectively. In the frequency range of 0.2-15 THz, highly resolved spectral features for Azitromycin suspension were measured and some minor differences were observed between domestic and exotic Azitromycin Suspension, such as linewidth broadening and additional peaks. As same time, for the domestic Azitromycin capsule, tablet and dispersible tablet, the absorption baselines in the range of 0.2-2.7 THz rise with the increase of frequency while absorption peaks become weaker due to the scattering of bigger particles and smaller amount of Azitromycin. Also, the additional peaks are caused by the absorption of filling materials. In parallel with the qualitative measurement, the THz absorption spectra for mixtures of polyethylene (PE) powders and exotic Azithomycin suspension with different concentrations were also measured. According to the linear correlation between the concentration and the absorption intensity, the concentration of effective component can be evaluated accurately. This means that THz-TDS method is suitable for the quality inspection and evaluation of the mixed Azithromycin system.

Step-scan differential Fourier transform infrared photoacoustic spectroscopy (DFTIR-PAS): a spectral deconvolution method for weak absorber detection in the presence of strongly overlapping background absorptions.

PubMed

Liu, Lixian; Mandelis, Andreas; Huan, Huiting; Michaelian, Kirk H

2017-04-01

The determination of small absorption coefficients of trace gases in the atmosphere constitutes a challenge for analytical air contaminant measurements, especially in the presence of strongly absorbing backgrounds. A step-scan differential Fourier transform infrared photoacoustic spectroscopy (DFTIR-PAS) method was developed to suppress the coherent external noise and spurious photoacoustic (PA) signals caused by strongly absorbing backgrounds. The infrared absorption spectra of acetylene (C₂H₂) and local air were used to verify the performance of the step-scan DFTIR-PAS method. A linear amplitude response to C₂H₂ concentrations from 100 to 5000 ppmv was observed, leading to a theoretical detection limit of 5 ppmv. The differential mode was capable of eliminating the coherent noise and dominant background gas signals, thereby revealing the presence of the otherwise hidden C₂H₂ weak absorption. Thus, the step-scan DFTIR-PAS modality was demonstrated to be an effective approach for monitoring weakly absorbing gases with absorption bands overlapped by strongly absorbing background species.

Modern Progress and Modern Problems in High Resolution X-ray Absorption from the Cold Interstellar Medium

NASA Astrophysics Data System (ADS)

Corrales, Lia; Li, Haochuan; Heinz, Sebastian

2018-01-01

With accurate cross-sections and higher signal-to-noise, X-ray spectroscopy can directly measure Milky Way gas and dust-phase metal abundances with few underlying assumptions. The X-ray energy band is sensitive to absorption by all abundant interstellar metals — carbon, oxygen, neon, silicon, magnesium, and iron — whether they are in gas or dust form. High resolution X-ray spectra from Galactic X-ray point sources can be used to directly measure metal abundances from all phases of the interstellar medium (ISM) along singular sight lines. We show our progress for measuring the depth of photoelectric absorption edges from neutral ISM metals, using all the observations of bright Galactic X-ray binaries available in the Chandra HETG archive. The cross-sections we use take into account both the absorption and scattering effects by interstellar dust grains on the iron and silicate spectral features. However, there are many open problems for reconciling X-ray absorption spectroscopy with ISM observations in other wavelengths. We will review the state of the field, lab measurements needed, and ways in which the next generation of X-ray telescopes will contribute.

Measurements of high-pressure CO2 absorption near 2.0 μm and implications on tunable diode laser sensor design

NASA Astrophysics Data System (ADS)

Rieker, G. B.; Jeffries, J. B.; Hanson, R. K.

2009-01-01

A tunable diode laser (TDL) is used to measure the absorption spectra of the R46 through R54 transitions of the 20012 ←00001 band of CO2 near 2.0 μm (5000 cm-1) at room temperature and pressures to 10 atm (densities to 9.2 amagat). Spectra are recorded using direct absorption spectroscopy and wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) in a mixture containing 11% CO2 in air. The direct absorption spectra are influenced by non-Lorentzian effects including finite-duration collisions which perturb far-wing absorption, and an empirical χ-function correction to the Voigt line shape is shown to greatly reduce error in the spectral model. WMS-2f spectra are shown to be at least a factor of four less-influenced by non-Lorentzian effects in this region, making this approach more resistant to errors in the far-wing line shape model and allowing a comparison between the spectral parameters of HITRAN and a new database which includes pressure-induced shift coefficients. The implications of these measurements on practical, high-pressure CO2 sensor design are discussed.

The photoionization spectrum of neutral aluminium, Al I

NASA Technical Reports Server (NTRS)

Roig, R. A.

1975-01-01

The absorption spectrum of Al I has been studied for the wavelength range 1160 to 2000 A by the flash pyrolysis technique. Wavelengths and derived energy levels are reported for 70 new lines converging on the 3s3p(3)P(0) limits of Al II. The autoionization parameters of the 3p(2)P(0)-3p(2)(2)S doublet have been measured. Good agreement is obtained with the experiment of Kohl and Parkinson and the recent calculation of Le Dourneuf et al. The relative photoionization cross section has been measured in the wavelength region 1200 A to 2000 A.

The Spectrum of Single Bubble Sonoluminescence.

NASA Astrophysics Data System (ADS)

Hiller, Robert Anthony

1995-01-01

An acoustically levitated bubble in a liquid may be driven to produce short flashes of light synchronous with the sound field in a process called sonoluminescence. The spectrum of the emitted light is measured with a grating monochromator and calibrated for absolute spectral radiance. The spectrum has been measured for various gases dissolved in pure water and heavy water, and alcohols and other hydrocarbon liquids. At a bandpass of 10nm EWHM the spectra are broad -band, showing no sign of lines or absorptions, with a peak in the ultraviolet. The experimental apparatus, including a system for producing sonoluminescence in a sealed container, is described.

Method and apparatus for optoacoustic spectroscopy

DOEpatents

Amer, Nabil M.

1979-01-01

A method and apparatus that significantly increases the sensitivity and flexibility of laser optoacoustic spectroscopy, with reduced size. With the method, it no longer is necessary to limit the use of laser optoacoustic spectroscopy to species whose absorption must match available laser radiation. Instead, "doping" with a relatively small amount of an optically absorbing gas yields optoacoustic signatures of nonabsorbing materials (gases, liquids, solids, and aerosols), thus significantly increasing the sensitivity and flexibility of optoacoustic spectroscopy. Several applications of this method are demonstated and/or suggested.

X-ray Absorption Spectroscopy Study of the Effect of Rh doping in Sr2IrO4

PubMed Central

Sohn, C. H.; Cho, Deok-Yong; Kuo, C.-T.; Sandilands, L. J.; Qi, T. F.; Cao, G.; Noh, T. W.

2016-01-01

We investigate the effect of Rh doping in Sr2IrO4 using X-ray absorption spectroscopy (XAS). We observed appearance of new electron-addition states with increasing Rh concentration (x in Sr2Ir1−xRhxO4) in accordance with the concept of hole doping. The intensity of the hole-induced state is however weak, suggesting weakness of charge transfer (CT) effect and Mott insulating ground states. Also, Ir Jeff = 1/2 upper Hubbard band shifts to lower energy as x increases up to x = 0.23. Combined with optical spectroscopy, these results suggest a hybridisation-related mechanism, in which Rh doping can weaken the (Ir Jeff = 1/2)–(O 2p) orbital hybridisation in the in-planar Rh-O-Ir bond networks. PMID:27025538

Dynamic terahertz spectroscopy of gas molecules mixed with unwanted aerosol under atmospheric pressure using fibre-based asynchronous-optical-sampling terahertz time-domain spectroscopy

PubMed Central

Hsieh, Yi-Da; Nakamura, Shota; Abdelsalam, Dahi Ghareab; Minamikawa, Takeo; Mizutani, Yasuhiro; Yamamoto, Hirotsugu; Iwata, Tetsuo; Hindle, Francis; Yasui, Takeshi

2016-01-01

Terahertz (THz) spectroscopy is a promising method for analysing polar gas molecules mixed with unwanted aerosols due to its ability to obtain spectral fingerprints of rotational transition and immunity to aerosol scattering. In this article, dynamic THz spectroscopy of acetonitrile (CH3CN) gas was performed in the presence of smoke under the atmospheric pressure using a fibre-based, asynchronous-optical-sampling THz time-domain spectrometer. To match THz spectral signatures of gas molecules at atmospheric pressure, the spectral resolution was optimized to 1 GHz with a measurement rate of 1 Hz. The spectral overlapping of closely packed absorption lines significantly boosted the detection limit to 200 ppm when considering all the spectral contributions of the numerous absorption lines from 0.2 THz to 1 THz. Temporal changes of the CH3CN gas concentration were monitored under the smoky condition at the atmospheric pressure during volatilization of CH3CN droplets and the following diffusion of the volatilized CH3CN gas without the influence of scattering or absorption by the smoke. This system will be a powerful tool for real-time monitoring of target gases in practical applications of gas analysis in the atmospheric pressure, such as combustion processes or fire accident. PMID:27301319

Dynamic terahertz spectroscopy of gas molecules mixed with unwanted aerosol under atmospheric pressure using fibre-based asynchronous-optical-sampling terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Hsieh, Yi-Da; Nakamura, Shota; Abdelsalam, Dahi Ghareab; Minamikawa, Takeo; Mizutani, Yasuhiro; Yamamoto, Hirotsugu; Iwata, Tetsuo; Hindle, Francis; Yasui, Takeshi

2016-06-01

Terahertz (THz) spectroscopy is a promising method for analysing polar gas molecules mixed with unwanted aerosols due to its ability to obtain spectral fingerprints of rotational transition and immunity to aerosol scattering. In this article, dynamic THz spectroscopy of acetonitrile (CH3CN) gas was performed in the presence of smoke under the atmospheric pressure using a fibre-based, asynchronous-optical-sampling THz time-domain spectrometer. To match THz spectral signatures of gas molecules at atmospheric pressure, the spectral resolution was optimized to 1 GHz with a measurement rate of 1 Hz. The spectral overlapping of closely packed absorption lines significantly boosted the detection limit to 200 ppm when considering all the spectral contributions of the numerous absorption lines from 0.2 THz to 1 THz. Temporal changes of the CH3CN gas concentration were monitored under the smoky condition at the atmospheric pressure during volatilization of CH3CN droplets and the following diffusion of the volatilized CH3CN gas without the influence of scattering or absorption by the smoke. This system will be a powerful tool for real-time monitoring of target gases in practical applications of gas analysis in the atmospheric pressure, such as combustion processes or fire accident.

Crystal structure, Hirshfeld surfaces computational study and physicochemical characterization of the hybrid material (C7H10N)2[SnCl6]·H2O

NASA Astrophysics Data System (ADS)

BelhajSalah, S.; Abdelbaky, Mohammed S. M.; García-Granda, Santiago; Essalah, K.; Ben Nasr, C.; Mrad, M. L.

2018-01-01

A novel hybrid compound, bis(4-methylanilinium)hexachlorostannate(IV) monohydrate, formulated as (C7H10N)2[SnCl6]·H2O, has been prepared and characterized by powder and single crystal X-ray diffraction (XRD), Hirshfeld surface analysis, infrared spectroscopy (IR), optical study, differential thermal analysis(DTA) and X-ray photoelectron spectroscopy analysis (XPS). The title compound crystallizes in the monoclinic space group P21/c with a = 13.093(1)Å, b = 7.093(6)Å, c = 24.152(2)Å, β = 98.536(4)⁰ and V = 2218.4(4) Å3. Their crystal structure exhibits alternating inorganic layers parallel to the (ab) plane at z = n/2. The different entities, [SnCl6]2-, organic cations and water molecules, are connected via hydrogen bonds to form a three-dimensional network. The powder XRD data confirms the phase purity of the crystalline sample. The intermolecular interactions were investigated by Hirshfeld surfaces. The vibrational absorption bands were identified by IR spectroscopy and have been discussed. The optical properties of the crystal were studied by using optical absorption, UV-visible absorption and photoluminescence spectroscopy studies. The compound was also characterized by DTA to determine its thermal behavior with respect to the temperature. Finally, XPS technique is reported for analyzing the surface chemistry of this compound.