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Sample records for adeep-ultraviolet resonance raman

  1. On the Increasing Fragility of Human Teeth with Age: ADeep-Ultraviolet Resonance Raman Study

    Ager III, J.W.; Nalla, R.K.; Balooch, G.; Kim, G.; Pugach, M.; Habelitz, S.; Marshall, G.W.; Kinney, J.H.; Ritchie, R.O.

    2006-07-14

    Ultraviolet resonance Raman spectroscopy (UVRRS) using 244nm excitation was used to investigate the impact of aging on humandentin. The intensity of a spectroscopic feature from the peptide bondsin the collagen increases with tissue age, similar to a finding reportedpreviously for human cortical bone.

  2. Triplet State Resonance Raman Spectroscopy

    Wilbrandt, Robert Walter; Jensen, N. H.; Pagsberg, Palle Bjørn;

    1978-01-01

    Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied......Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied...

  3. Resonance Raman study of benzyl radical

    Langkilde, F.W.; Bajdor, K.; Wilbrandt, R.

    1992-01-01

    Time-resolved resonance Raman spectra are obtained of benzyl radicals created by laser flash photolysis of benzylchloride and diphenylacetone in solution. The spectra are obtained in resonance with the intense 2 2A2-1 B-2(2) transition of benzyl. The strong Raman bands are assigned to totally...... symmetric a1 modes. The remaining observed bands are tentatively assigned to fundamental modes of b1, a2, and b2 symmetry, and to overtones and combinations. The resonance Raman spectra are found to be quite different from previous fluorescence spectra of benzyl, and the origins of these differences are...

  4. Resonant Raman scattering off neutral quantum dots

    Resonant inelastic (Raman) light scattering off neutral GaAs quantum dots which contain a mean number, N=42, of electron-hole pairs is computed. We find Raman amplitudes corresponding to strongly collective final states (charge-density excitations) of similar magnitude as the amplitudes related to weakly collective or single-particle excitations. As a function of the incident laser frequency or the magnetic field, they are rapidly varying amplitudes. It is argued that strong Raman peaks should come out in the spin-density channels, not related to valence-band mixing effects in the intermediate states. (author)

  5. Resonance Raman Optical Activity and Surface Enhanced Resonance Raman Optical Activity analysis of Cytochrome C

    Johannessen, Christian; Abdali, Salim; White, Peter C.

    2007-01-01

    resonance enhanced skeletal porphyrin vibrations, more pronounced than any contribution from the protein back-bone. Combining the intrinsic resonance enhancement of cytochrome c with surface plasmon enhancement by colloidal silver particles, the Surface Enhanced Resonance Raman Scattering (SERRS) and Chiral...

  6. Resonance Raman spectroscopy and ultrafast chemical dynamics

    Biswas, Nandita; Umapathy, Siva

    1998-01-01

    Resonance Raman (RR) spectroscopy is normally used to study the excited state structure and dynamics of various photochemical and photophysical processes. In this article. we briefly discuss the various applications of RR spectroscopy and show how experimental RR intensities along with time-dependent wavepacket dynamical calculations can be used to study the excited state structure and ultrafast dynamics (\\sim 10(- 15) secs).

  7. Ultraviolet Resonant Raman Enhancements in the Detection of Explosives

    Short Jr., Billy Joe [Naval Postgraduate School, Monterey, CA (United States)

    2009-06-01

    Raman-based spectroscopy is potentially militarily useful for standoff detection of high explosives. Normal (non-resonance) and resonance Raman spectroscopies are both light scattering techniques that use a laser to measure the vibrational spectrum of a sample. In resonance Raman, the laser is tuned to match the wavelength of a strong electronic absorbance in the molecule of interest, whereas, in normal Raman the laser is not tuned to any strong electronic absorbance bands. The selection of appropriate excitation wavelengths in resonance Raman can result in a dramatic increase in the Raman scattering efficiency of select band(s) associated with the electronic transition. Other than the excitation wavelength, however, resonance Raman is performed experimentally the same as normal Raman. In these studies, normal and resonance Raman spectral signatures of select solid high explosive (HE) samples and explosive precursors were collected at 785 nm, 244 nm and 229 nm. Solutions of PETN, TNT, and explosive precursors (DNT & PNT) in acetonitrile solvent as an internal Raman standard were quantitatively evaluated using ultraviolet resonance Raman (UVRR) microscopy and normal Raman spectroscopy as a function of power and select excitation wavelengths. Use of an internal standard allowed resonance enhancements to be estimated at 229 nm and 244 nm. Investigations demonstrated that UVRR provided ~2000-fold enhancement at 244 nm and ~800-fold improvement at 229 nm while PETN showed a maximum of ~25-fold at 244 nm and ~190-fold enhancement at 229 nm solely from resonance effects when compared to normal Raman measurements. In addition to the observed resonance enhancements, additional Raman signal enhancements are obtained with ultraviolet excitation (i.e., Raman scattering scales as !4 for measurements based on scattered photons). A model, based partly on the resonance Raman enhancement results for HE solutions, is presented for estimating Raman enhancements for solid HE samples.

  8. Ultraviolet Resonant Raman Enhancements in the Detection of Explosives

    Raman-based spectroscopy is potentially militarily useful for standoff detection of high explosives. Normal (non-resonance) and resonance Raman spectroscopies are both light scattering techniques that use a laser to measure the vibrational spectrum of a sample. In resonance Raman, the laser is tuned to match the wavelength of a strong electronic absorbance in the molecule of interest, whereas, in normal Raman the laser is not tuned to any strong electronic absorbance bands. The selection of appropriate excitation wavelengths in resonance Raman can result in a dramatic increase in the Raman scattering efficiency of select band(s) associated with the electronic transition. Other than the excitation wavelength, however, resonance Raman is performed experimentally the same as normal Raman. In these studies, normal and resonance Raman spectral signatures of select solid high explosive (HE) samples and explosive precursors were collected at 785 nm, 244 nm and 229 nm. Solutions of PETN, TNT, and explosive precursors (DNT and PNT) in acetonitrile solvent as an internal Raman standard were quantitatively evaluated using ultraviolet resonance Raman (UVRR) microscopy and normal Raman spectroscopy as a function of power and select excitation wavelengths. Use of an internal standard allowed resonance enhancements to be estimated at 229 nm and 244 nm. Investigations demonstrated that UVRR provided ∼2000-fold enhancement at 244 nm and ∼800-fold improvement at 229 nm while PETN showed a maximum of ∼25-fold at 244 nm and ∼190-fold enhancement at 229 nm solely from resonance effects when compared to normal Raman measurements. In addition to the observed resonance enhancements, additional Raman signal enhancements are obtained with ultraviolet excitation (i.e., Raman scattering scales as 4 for measurements based on scattered photons). A model, based partly on the resonance Raman enhancement results for HE solutions, is presented for estimating Raman enhancements for solid HE

  9. Fast Resonance Raman Spectroscopy of Short-Lived Radicals

    Pagsberg, Palle Bjørn; Wilbrandt, Robert Walter; Hansen, Karina Benthin;

    1976-01-01

    We report the first application of pulsed resonance Raman spectroscopy to the study of short-lived free radicals produced by pulse radiolysis. A single pulse from a flash-lamp pumped tunable dye laser is used to excite the resonance Raman spectrum of the p-terphenyl anion radical with an initial...

  10. Observation of the Auger resonant Raman effect

    Monochromatized synchrotron radiation near the photoionization threshold was used to produce the [2p/sub 3/2/] vacancy state in atomic Xe. Deexcitation of the state through L3-M4M5(1G4) Auger-electron emission was measured. The 5d spectator-electron Auger satellite was observed. The satellite energy exhibits linear dispersion. The observed width of the 1G diagram line decreases by approx. 40% when the exciting photon energy reaches the vicinity of the Xe L3 binding energy. This radiationless process can thus be construed as the Auger analog of the x-ray resonant Raman effect. The 1G diagram line is shifted by -+3 eV due to post-collision interaction; this shift varies with excitation energy

  11. Resonant enhancement of Raman scattering in metamaterials with hybrid electromagnetic and plasmonic resonances

    Guddala, Sriram; Ramakrishna, S Anantha

    2016-01-01

    A tri-layer metamaterial perfect absorber of light, consisting of (Al/ZnS/Al) films with the top aluminium layer patterned as an array of circular disk nanoantennas, is investigated for resonantly enhancing Raman scattering from C-60 fullerene molecules deposited on the metamaterial. The metamaterial is designed to have resonant bands due to plasmonic and electromagnetic resonances at the Raman pump frequency (725 nm) as well as Stokes emission bands. The Raman scattering from C60 on the metamaterial with resonantly matched bands is measured to be enhanced by an order of magnitude more than from C60 on metamaterials with off-resonant absorption bands peaked at 1090 nm. The Raman pump is significantly enhanced due to the resonance with a propagating surface plasmon band, while the highly impedance matched electromagnetic resonance is expected to couple out the Raman emission efficiently. The nature and hybridization of the plasmonic and electromagnetic resonances to form compound resonances are investigated by...

  12. UV resonance Raman sensing of pharmaceutical drugs in hollow fibers

    Yan, D.; Popp, J.; Frosch, T.

    2014-05-01

    We report about the experimental combination of UV resonance Raman sensing (UV-RRS) and fiber enhanced Raman sensing (FERS) on pharmaceuticals. The results show that the chemical sensitivity is highly improved and at the same time the sample volume is reduced compared to conventional measurements. A hundreds-fold improvement of the limit of detection (LOD) has been achieved with the combination of resonance Raman enhancement and fiber enhancement. The enhanced Raman signal has a reliable linear relationship with the concentration of the analyte, and therefore shows great potential for quantitative analysis of pharmaceuticals.

  13. Bithiophene radical cation: Resonance Raman spectroscopy and molecular orbital calculations

    Grage, M.M.-L.; Keszthelyi, T.; Offersgaard, J.F.; Wilbrandt, R.

    1998-01-01

    The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution a...... the Raman spectrum excited in resonance with the absorption band at 425 nm. The spectrum was interpreted with the help of density functional theory calculations. (C) 1998 Elsevier Science B.V.......The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution and...

  14. Bithiophene radical cation: Resonance Raman spectroscopy and molecular orbital calculations

    Grage, M.M.-L.; Keszthelyi, T.; Offersgaard, J.F.;

    1998-01-01

    The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution a...... the Raman spectrum excited in resonance with the absorption band at 425 nm. The spectrum was interpreted with the help of density functional theory calculations. (C) 1998 Elsevier Science B.V....

  15. Investigation of anti-Stokes Raman processes at phonon-polariton resonance: from Raman oscillation, frequency upconversion to Raman amplification.

    Ding, Yujie J

    2015-03-01

    Raman oscillation, frequency upconversion, and Raman amplification can be achieved in a second-order nonlinear medium at the phonon-polariton resonance. By beating two optical fields, a second-order nonlinear polarization is generated inside the medium. Such a polarization induces a spatially uniform nonpropagating electric field at the beat frequency, which in turn mixes with the input optical field at the lower frequency to generate or amplify the anti-Stokes optical field. Raman oscillation can be efficiently reached for the copropagating configuration. In comparison, efficient frequency upconversion and large amplifications are achievable for the counterpropagating configuration. These Raman processes can be used to effectively remove transverse-optical phonons before decaying to lower-frequency phonons, achieve laser cooling, and significantly enhance coherent anti-Stokes Raman scattering. The counterpropagating configuration offers advantages for amplifying extremely weak signals. PMID:25723418

  16. Raman albedo and deep-UV resonance Raman signatures of explosives

    Yellampalle, Balakishore; Lemoff, Brian E.

    2013-05-01

    Deep-ultraviolet resonance Raman spectroscopy (DUVRRS) is a promising approach to stand-off detection of explosive traces due to large Raman cross-section and background free signatures. In order to design an effective sensor, one must be able to estimate the signal level of the DUVRRS signature for solid-phase explosive residues. The conventional approach to signal estimation uses scattering cross-sections and molar absorptivity, measured on solutions of explosives dissolved in an optically-transparent solvent. Only recently have researchers started to measure solid-state cross-sections. For most solid-phase explosives and explosive mixtures, neither the DUV Raman scattering cross sections nor the optical absorption coefficient are known, and they are very difficult to separately measure. Therefore, for a typical solid explosive mixture, it is difficult to accurately estimate Raman signal strength using conventional approaches. To address this issue, we have developed a technique to measure the Raman scattering strength of optically-thick (opaque) materials, or "Raman Albedo", defined as the total power of Raman-scattered light per unit frequency per unit solid angle divided by the incident power of the excitation source. We have measured Raman Albedo signatures for a wide range of solid explosives at four different DUV excitation wavelengths. These results will be presented, and we will describe the use of Raman Albedo measurements in the design and current construction of a novel stand-off explosive sensor, based on dual-excitation-wavelength DUVRRS.

  17. Periodontitis diagnostics using resonance Raman spectroscopy on saliva

    Gonchukov, S.; Sukhinina, A.; Bakhmutov, D.; Biryukova, T.; Tsvetkov, M.; Bagratashvily, V.

    2013-07-01

    In view of its wealth of molecular information, Raman spectroscopy has been the subject of active biomedical research. The aim of this work is Raman spectroscopy (RS) application for the determination of molecular biomarkers in saliva with the objective of early periodontitis detection. As was shown in our previous study, carotenoids contained in saliva can be molecular fingerprint information for the periodontitis level. It is shown here that the carotenoid RS lines at wavenumbers of 1156 and 1524 cm-1 can be easily detected and serve as reliable biomarkers of periodontitis using resonance Raman spectroscopy of dry saliva.

  18. Periodontitis diagnostics using resonance Raman spectroscopy on saliva

    In view of its wealth of molecular information, Raman spectroscopy has been the subject of active biomedical research. The aim of this work is Raman spectroscopy (RS) application for the determination of molecular biomarkers in saliva with the objective of early periodontitis detection. As was shown in our previous study, carotenoids contained in saliva can be molecular fingerprint information for the periodontitis level. It is shown here that the carotenoid RS lines at wavenumbers of 1156 and 1524 cm−1 can be easily detected and serve as reliable biomarkers of periodontitis using resonance Raman spectroscopy of dry saliva. (letter)

  19. Resonant Raman Scattering from Silicon Nanoparticles Enhanced by Magnetic Response

    Dmitriev, Pavel A; Milichko, Valentin A; Makarov, Sergey V; Mukhin, Ivan S; Samusev, Anton K; Krasnok, Alexander E; Belov, Pavel A; Kivshar, Yuri S

    2016-01-01

    Enhancement of optical response with high-index dielectric nanoparticles is attributed to the excitation of their Mie-type magnetic and electric resonances. Here we study Raman scattering from crystalline silicon nanoparticles and reveal that magnetic dipole modes have much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of Raman signal from individual silicon spherical nanoparticles at the magnetic dipole resonance. Our results confirm the importance of the optically-induced magnetic response of subwavelength dielectric nanoparticles for enhancing light-matter interactions.

  20. Resonant Raman scattering from silicon nanoparticles enhanced by magnetic response.

    Dmitriev, Pavel A; Baranov, Denis G; Milichko, Valentin A; Makarov, Sergey V; Mukhin, Ivan S; Samusev, Anton K; Krasnok, Alexander E; Belov, Pavel A; Kivshar, Yuri S

    2016-05-01

    Enhancement of optical response with high-index dielectric nanoparticles is attributed to the excitation of their Mie-type magnetic and electric resonances. Here we study Raman scattering from crystalline silicon nanoparticles and reveal that magnetic dipole modes have a much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of the Raman signal from individual silicon spherical nanoparticles at the magnetic dipole resonance. Our results confirm the importance of the optically-induced magnetic response of subwavelength dielectric nanoparticles for enhancing light-matter interactions. PMID:27113352

  1. Resonant Raman scattering in InGaN alloys

    Davydov, V.Yu.; Goncharuk, I.N.; Smirnov, A.N.; Sakharov, A.V.; Skvortsov, A.P.; Yagovkina, M.A. [A.F. Ioffe Physico-Technical Institute, 194021 St. Petersburg (Russian Federation); Klochikhin, A.A. [A.F. Ioffe Physico-Technical Institute, 194021 St. Petersburg (Russian Federation); Nuclear Physics Institute, 188350 St. Petersburg (Russian Federation); Lebedev, V.M. [Nuclear Physics Institute, 188350 St. Petersburg (Russian Federation); Lu, Hai; Schaff, William J. [Department of Electrical and Computer Engineering, Cornell University, Ithaca, New York 14853 (United States)

    2006-06-15

    A strong resonant behavior of the Raman scattering from LO-phonons in n-InGaN alloys at excitation near the interband absorption threshold was observed. An approach has been developed to describe the resonant Raman cross sectional profile in the presence of a Burstein-Moss shift of the interband optical transitions. It has been shown that a simultaneous study of absorption, photoluminescence, and Raman spectra provides reliable information about the band gap and can be efficient for the alloy characterization. Our data show that the band gap composition dependence of InGaN is characterized by the strongly nonlinear behavior with the large bowing parameter of 2.5-2.6 eV. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  2. Resonance Raman spectroscopy in one-dimensional carbon materials

    Dresselhaus Mildred S.

    2006-01-01

    Full Text Available Brazil has played an important role in the development and use of resonance Raman spectroscopy as a powerful characterization tool for materials science. Here we present a short history of Raman scattering research in Brazil, highlighting the important contributions to the field coming from Brazilian researchers in the past. Next we discuss recent and important contributions where Brazil has become a worldwide leader, that is on the physics of quasi-one dimensional carbon nanotubes. We conclude this article by presenting results from a very recent resonance Raman study of exciting new materials, that are strictly one-dimensional carbon chains formed by the heat treatment of very pure double-wall carbon nanotube samples.

  3. Photodissociation dynamics of dimethylnitrosamine studied by resonance Raman spectroscopy

    Lenderink, Egbert; Wiersma, Douwe A.

    1994-01-01

    The initial molecular dynamics in the dissociative S1 (n, pi*) state of dimethylnitrosamine (DMN) is investigated using resonance Raman spectroscopy. We find that photochemical N-N bond cleavage in DMN proceeds via a bent conformation around the amine N atom, which supports the outcome of ab initio

  4. Resonance Raman Spectroscopy of Free Radicals Produced by Ionizing Radiation

    Wilbrandt, Robert Walter

    1984-01-01

    Applications of time-resolved resonance Raman spectroscopy to the study of short-lived free radicals produced by ionizing radiation are briefly reviewed. Potential advantages and limitations of this technique are discussed in the light of given examples. The reduction of p-nitrobenzylchloride and...

  5. Resonant Raman scattering from silicon nanoparticles enhanced by magnetic response

    Dmitriev, Pavel A.; Baranov, Denis G.; Milichko, Valentin A.; Makarov, Sergey V.; Mukhin, Ivan S.; Samusev, Anton K.; Krasnok, Alexander E.; Belov, Pavel A.; Kivshar, Yuri S.

    2016-05-01

    Enhancement of optical response with high-index dielectric nanoparticles is attributed to the excitation of their Mie-type magnetic and electric resonances. Here we study Raman scattering from crystalline silicon nanoparticles and reveal that magnetic dipole modes have a much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of the Raman signal from individual silicon spherical nanoparticles at the magnetic dipole resonance. Our results confirm the importance of the optically-induced magnetic response of subwavelength dielectric nanoparticles for enhancing light-matter interactions.Enhancement of optical response with high-index dielectric nanoparticles is attributed to the excitation of their Mie-type magnetic and electric resonances. Here we study Raman scattering from crystalline silicon nanoparticles and reveal that magnetic dipole modes have a much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of the Raman signal from individual silicon spherical nanoparticles at the magnetic dipole resonance. Our results confirm the importance of the optically-induced magnetic response of subwavelength dielectric nanoparticles for enhancing light-matter interactions. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07965a

  6. Fast Resonance Raman Spectroscopy of a Free Radical

    Wilbrandt, Robert Walter; Pagsberg, Palle Bjørn; Hansen, K. B.;

    1975-01-01

    The resonance Raman spectrum of a 10−3 molar solution of the stable diphenyl-pikryl-hydrazyl radical in benzene was obtained using a single laser pulse of 10 mJ energy and 600 ns duration from a flashlamp pumped tunable dye laser. Spectra were recorded using an image intensifier coupled to a TV...

  7. Resonance electronic Raman scattering in rare earth crystals

    Williams, G.M.

    1988-11-10

    The intensities of Raman scattering transitions between electronic energy levels of trivalent rare earth ions doped into transparent crystals were measured and compared to theory. A particle emphasis was placed on the examination of the effect of intermediate state resonances on the Raman scattering intensities. Two specific systems were studied: Ce/sup 3 +/(4f/sup 1/) in single crystals of LuPO/sub 4/ and Er/sup 3 +/(4f/sup 11/) in single crystals of ErPO/sub 4/. 134 refs., 92 figs., 33 tabs.

  8. Resonance electronic Raman scattering in rare earth crystals

    The intensities of Raman scattering transitions between electronic energy levels of trivalent rare earth ions doped into transparent crystals were measured and compared to theory. A particle emphasis was placed on the examination of the effect of intermediate state resonances on the Raman scattering intensities. Two specific systems were studied: Ce3+(4f1) in single crystals of LuPO4 and Er3+(4f11) in single crystals of ErPO4. 134 refs., 92 figs., 33 tabs

  9. UV-resonance Raman spectroscopy of amino acids

    Höhl, Martin; Meinhardt-Wollweber, Merve; Schmitt, Heike; Lenarz, Thomas; Morgner, Uwe

    2016-03-01

    Resonant enhancement of Raman signals is a useful method to increase sensitivity in samples with low concentration such as biological tissue. The investigation of resonance profiles shows the optimal excitation wavelength and yields valuable information about the molecules themselves. However careful characterization and calibration of all experimental parameters affecting quantum yield is required in order to achieve comparability of the single spectra recorded. We present an experimental technique for measuring the resonance profiles of different amino acids. The absorption lines of these molecules are located in the ultraviolet (UV) wavelength range. One limitation for broadband measurement of resonance profiles is the limited availability of Raman filters in certain regions of the UV for blocking the Rayleigh scattered light. Here, a wavelength range from 244.8 nm to 266.0 nm was chosen. The profiles reveal the optimal wavelength for recording the Raman spectra of amino acids in aqueous solutions in this range. This study provides the basis for measurements on more complex molecules such as proteins in the human perilymph. The composition of this liquid in the inner ear is essential for hearing and cannot be analyzed non-invasively so far. The long term aim is to implement this technique as a fiber based endoscope for non-invasive measurements during surgeries (e. g. cochlear implants) making it available as a diagnostic tool for physicians. This project is embedded in the interdisciplinary cluster of excellence "Hearing for all" (H4A).

  10. Resonant electronic Raman scattering: A BCS-like system

    Rodrigues, Leonarde N.; Arantes, A.; Schüller, C.; Bell, M. J. V.; Anjos, V.

    2016-05-01

    In this paper we investigate the resonant intersubband Raman scattering of two-dimensional electron systems in GaAs-AlGaAs single quantum wells. Self-consistent calculations of the polarized and depolarized Raman cross sections show that the appearance of excitations at the unrenormalized single-particle energy are related to three factors: the extreme resonance regime, the existence of degeneracy in intersubband excitations of the electron gas, and, finally, degeneracy in the interactions between pairs of excitations. It is demonstrated that the physics that governs the problem is similar to the one that gives rise to the formation of the superconducting state in the BCS theory of normal metals. Comparison between experiment and theory shows an excellent agreement.

  11. Vortex solitons in an off-resonant Raman medium

    Gorbach, A V; Harvey, C N

    2008-01-01

    We investigate existence and linear stability of coupled vortex solitons supported by cascaded four-wave mixing in a Raman active medium excited away from the resonance. We present a detailed analysis for the two- and three-component vortex solitons and demonstrate the formation of stable and unstable vortex solitons, and associated spatio-temporal helical beams, under the conditions of the simultaneous frequency and vortex comb generation.

  12. Resonance Raman Optical Activity of Single Walled Chiral Carbon Nanotubes.

    Nagy, Péter R; Koltai, János; Surján, Péter R; Kürti, Jenő; Szabados, Ágnes

    2016-07-21

    Resonance (vibrational) Raman Optical Activity (ROA) spectra of six chiral single-walled carbon nanotubes (SWCNTs) are studied by theoretical means. Calculations are performed imposing line group symmetry. Polarizability tensors, computed at the π-electron level, are differentiated with respect to DFT normal modes to generate spectral intensities. This computational protocol yields a ROA spectrum in good agreement with the only experiment on SWCNT, available at present. In addition to the conventional periodic electric dipole operator we introduce magnetic dipole and electric quadrupole operators, suitable for conventional k-space calculations. Consequences of the complex nature of the wave function on the scattering cross section are discussed in detail. The resonance phenomenon is accounted for by the short time approximation. Involvement of fundamental vibrations in the region of the intermediate frequency modes is found to be more notable in ROA than in Raman spectra. Calculations indicate exceptionally strong resonance enhancement of SWCNT ROA signals. Resonance ROA profile of the (6,5) tube shows an interesting sign change that may be exploited experimentally for SWCNT identification. PMID:27315548

  13. Double resonance Raman effects in InN nanowires

    Domenech-Amador, N.; Cusco, R.; Artus, L. [Institut Jaume Almera, Consell Superior d' Investigacions Cientifiques (CSIC), Lluis Sole i Sabaris s.n., Barcelona, Catalonia (Spain); Calarco, R. [Institute of Bio- and Nanosystems, Research Center Juelich GmbH, Juelich (Germany); Paul-Drude-Institut fuer Festkoerperelektronik, Berlin (Germany); Yamaguchi, T.; Nanishi, Y. [Faculty of Science and Engineering, Ritsumeikan University, Noji-Higashi, Kusatsu, Shiga 525-8577 (Japan)

    2012-04-15

    We study the excitation wavelength dependence of the Raman spectra of InN nanowires. The E{sub 1}(LO) phonon mode, which is detected in backscattering configuration because of light entering through lateral faces, exhibits an upward frequency shift that can be explained by Martin's double resonance. The E{sub 1} (LO)/E{sub 2}{sup h} intensity ratio increases with the excitation wavelength more rapidly than the A{sub 1}(LO)/E{sub 2}{sup h} ratio measured in InN thin films. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  14. Transition polarizability model of induced resonance Raman optical activity

    Yamamoto, S.; Bouř, Petr

    2013-01-01

    Roč. 34, č. 25 (2013), s. 2152-2158. ISSN 0192-8651 R&D Projects: GA ČR GAP208/11/0105; GA ČR GA13-03978S; GA MŠk(CZ) LH11033 Grant ostatní: AV ČR(CZ) M200551205 Institutional support: RVO:61388963 Keywords : induced resonance Raman optical activity * europium complexes * density functional computations * light scattering Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.601, year: 2013

  15. Human brain cancer studied by resonance Raman spectroscopy

    Zhou, Yan; Liu, Cheng-Hui; Sun, Yi; Pu, Yang; Boydston-White, Susie; Liu, Yulong; Alfano, Robert R.

    2012-11-01

    The resonance Raman (RR) spectra of six types of human brain tissues are examined using a confocal micro-Raman system with 532-nm excitation in vitro. Forty-three RR spectra from seven subjects are investigated. The spectral peaks from malignant meningioma, stage III (cancer), benign meningioma (benign), normal meningeal tissues (normal), glioblastoma multiforme grade IV (cancer), acoustic neuroma (benign), and pituitary adenoma (benign) are analyzed. Using a 532-nm excitation, the resonance-enhanced peak at 1548 cm-1 (amide II) is observed in all of the tissue specimens, but is not observed in the spectra collected using the nonresonance Raman system. An increase in the intensity ratio of 1587 to 1605 cm-1 is observed in the RR spectra collected from meningeal cancer tissue as compared with the spectra collected from the benign and normal meningeal tissue. The peak around 1732 cm-1 attributed to fatty acids (lipids) are diminished in the spectra collected from the meningeal cancer tumors as compared with the spectra from normal and benign tissues. The characteristic band of spectral peaks observed between 2800 and 3100 cm-1 are attributed to the vibrations of methyl (-CH3) and methylene (-CH2-) groups. The ratio of the intensities of the spectral peaks of 2935 to 2880 cm-1 from the meningeal cancer tissues is found to be lower in comparison with that of the spectral peaks from normal, and benign tissues, which may be used as a distinct marker for distinguishing cancerous tissues from normal meningeal tissues. The statistical methods of principal component analysis and the support vector machine are used to analyze the RR spectral data collected from meningeal tissues, yielding a diagnostic sensitivity of 90.9% and specificity of 100% when two principal components are used.

  16. Laser Raman and resonance Raman spectroscopies of natural semiconductor mineral cinnabar, α-HgS, from various mines

    Natural minerals α-HgS from various mines have been studied by laser Raman spectroscopy and resonance Raman spectroscopy. The crystals differ from each other in the content of selenium impurity, included in samples from some mines. Based on the Raman spectra and the factor-group analysis the classification of the first order phonons and then the comparison of the results with the results from other works were carried out. The Raman spectra analysis of minerals from various mines show the selenium impurity gap vibration at 203 cm-1 and 226 cm-1 frequencies, respectively. On the basis of statistical measurements of the Raman spectra one can conclude that impurity frequencies of α-HgS may be generally used for the identification of the mine. Resonance Raman scattering for pure minerals has been studied by a dye laser. Phonon resonance in the indirect semiconductor α-HgS is found to be far more intense than the indirect resonance detected until now in various semiconductors in the proximity of the first indirect band Eg, for instance, in GaP. In our opinion, this may be conditioned by cinnabar band structure peculiarities. Low resonance has also been fixed in 'dirty' minerals at the spectral band frequency of 203 cm-1 characterizing gap vibration of isomorphic impurity Se in cinnabar

  17. Quantitative evaluation of proteins with bicinchoninic acid (BCA): resonance Raman and surface-enhanced resonance Raman scattering-based methods.

    Chen, Lei; Yu, Zhi; Lee, Youngju; Wang, Xu; Zhao, Bing; Jung, Young Mee

    2012-12-21

    A rapid and highly sensitive bicinchoninic acid (BCA) reagent-based protein quantitation tool was developed using competitive resonance Raman (RR) and surface-enhanced resonance Raman scattering (SERRS) methods. A chelation reaction between BCA and Cu(+), which is reduced by protein in an alkaline environment, is exploited to create a BCA-Cu(+) complex that has strong RR and SERRS activities. Using these methods, protein concentrations in solutions can be quantitatively measured at concentrations as low as 50 μg mL(-1) and 10 pg mL(-1). There are many advantages of using RR and SERRS-based assays. These assays exhibit a much wider linear concentration range and provide an additional one (RR method) to four (SERRS method) orders of magnitude increase in detection limits relative to UV-based methods. Protein-to-protein variation is determined using a reference to a standard curve at concentrations of BSA that exhibits excellent recoveries. These novel methods are extremely accurate in detecting total protein concentrations in solution. This improvement in protein detection sensitivity could yield advances in the biological sciences and medical diagnostic field and extend the applications of reagent-based protein assay techniques. PMID:23099478

  18. Origin invariance in vibrational resonance Raman optical activity

    Vidal, Luciano N., E-mail: lnvidal@utfpr.edu.br; Cappelli, Chiara, E-mail: chiara.cappelli@unipi.it [Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 3, 56124 Pisa (Italy); Egidi, Franco [Department of Chemistry, University of Washington, Seattle, Washington 98195 (United States); Barone, Vincenzo [Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa (Italy)

    2015-05-07

    A theoretical investigation on the origin dependence of the vibronic polarizabilities, isotropic and anisotropic rotational invariants, and scattering cross sections in Resonance Raman Optical Activity (RROA) spectroscopy is presented. Expressions showing the origin dependence of these polarizabilities were written in the resonance regime using the Franck-Condon (FC) and Herzberg-Teller (HT) approximations for the electronic transition moments. Differently from the far-from-resonance scattering regime, where the origin dependent terms cancel out when the rotational invariants are calculated, RROA spectrum can exhibit some origin dependence even for eigenfunctions of the electronic Hamiltonian. At the FC level, the RROA spectrum is completely origin invariant if the polarizabilities are calculated using a single excited state or for a set of degenerate states. Otherwise, some origin effects can be observed in the spectrum. At the HT level, RROA spectrum is origin dependent even when the polarizabilities are evaluated from a single excited state but the origin effect is expected to be small in this case. Numerical calculations performed for (S)-methyloxirane, (2R,3R)-dimethyloxirane, and (R)-4-F-2-azetidinone at both FC and HT levels using the velocity representation of the electric dipole and quadrupole transition moments confirm the predictions of the theory and show the extent of origin effects and the effectiveness of suggested ways to remove them.

  19. Resonant Raman effect in single-wall carbon nanotubes

    A resonant Raman study of single-wall carbon nanotubes (SWNT) using several laser lines between 0.94 and 3.05 eV is presented. A detailed lineshape analysis shows that the bands associated with the nanotube radial breathing mode are composed of a sum of individual peaks whose relative intensities depend strongly on the laser energy, in agreement with prior work. On the other hand, the shape of the Raman bands associated with the tangential C - C stretching motions in the 1500 - 1600 cm-1 range does not depend significantly on the laser energy for laser excitation energies in the ranges 0.94 - 1.59 eV and 2.41 - 3.05 eV. However, new C - C stretching modes are observed in the spectra collected using laser excitations with energies close to 1.9 eV. The new results are discussed in terms of the difference between the 1D electronic density of states for the semiconducting and metallic carbon nanotubes. copyright 1998 Materials Research Society

  20. Pre-resonance Raman spectra of some simple gases. [sulfur oxides, hydrogen sulfide, and nitrogen oxides

    Low, P. W.

    1974-01-01

    The pre-resonance Raman spectra of SO2, N2O, and H2S were investigated using the 4880 A, 4727 A, and 4579 A lines of the argon ion laser. Although these molecules have electronic absorption bands in the near ultraviolet, none exhibit any pre-resonance enhancement within our experimental error of + or - 10%. Possible explanations taking into account the current theories for resonance Raman are discussed.

  1. Resonant Raman scattering of x rays: Evidence for K-M scattering

    Resonant Raman x-ray scattering on molybdenum was studied using a Mo-anode x-ray tube and a LiF crystal monochromator. Beside the usual resonant Raman peak corresponding to the fluorescent Kα lines, another peak with a smaller energy loss was found. It is attributed to resonant Raman scattering with a final-state M-shell vacancy corresponding to the fluorescent Kβ lines. Both contributions are shown to be independent of the scattering angle. Absolute cross sections have been determined and compared with theoretical predictions

  2. Resonant Raman scattering of x rays: evidence for K--M scattering

    Resonant Raman x-ray scattering on molybdenum was studied using a Mo-anode x-ray tube and a LiF crystal monochromator. Beside the usual resonant Raman peak corresponding to the fluorescent Kα lines another peak with a smaller energy loss was found. It is attributed to resonant Raman scattering with a final state M-shell vacancy corresponding to the fluorescent Kβ lines. Both contributions are shown to be independent of the scattering angle. Absolute cross sections were determined and compared with theoretical predictions. 9 references

  3. High-sensitivity pesticide detection using particle-enhanced resonant Raman scattering

    Ranjan, Bikas; Saito, Yuika; Verma, Prabhat

    2016-03-01

    The use of pesticides in agriculture has raised concerns, as even a small residual of pesticide on food can be harmful. It is therefore of great importance to develop a robust technique to detect tiny amounts of pesticides. Although Raman spectroscopy is frequently used for chemical identification, it is not suitable for extremely low molecular concentrations. We propose a technique called particle-enhanced resonant Raman spectroscopy to detect extremely low concentrations of pesticides, where gold nanoparticles of desired plasmonic resonance are synthesized to match the resonance in Raman scattering. We successfully demonstrated the detection of extremely low amounts of pesticides on oranges.

  4. Near-field enhanced ultraviolet resonance Raman spectroscopy using aluminum bow-tie nano-antenna.

    Li, Ling; Fang Lim, Shuang; Puretzky, Alexander A; Riehn, Robert; Hallen, H D

    2012-09-10

    An aluminum bow-tie nano-antenna is combined with the resonance Raman effect in the deep ultraviolet to dramatically increase the sensitivity of Raman spectra to a small volume of material, such as benzene used here. We further demonstrate gradient-field Raman peaks for several strong infrared modes. We achieve a gain of [Formula: see text] in signal intensity from the near field enhancement due to the surface plasmon resonance in the aluminum nanostructure. The on-line resonance enhancement contributes another factor of several thousands, limited by the laser line width. Thus, an overall gain of hundreds of million is achieved. PMID:23066168

  5. Near-field enhanced ultraviolet resonance Raman spectroscopy using aluminum bow-tie nano-antenna

    Li, Ling; Fang Lim, Shuang; Puretzky, Alexander A.; Riehn, Robert; Hallen, H. D.

    2012-01-01

    An aluminum bow-tie nano-antenna is combined with the resonance Raman effect in the deep ultraviolet to dramatically increase the sensitivity of Raman spectra to a small volume of material, such as benzene used here. We further demonstrate gradient-field Raman peaks for several strong infrared modes. We achieve a gain of ∼105 in signal intensity from the near field enhancement due to the surface plasmon resonance in the aluminum nanostructure. The on-line resonance enhancement contributes ano...

  6. Intercalation between antitumor anthracyclines and DNA as probed by resonance and surface-enhanced Raman spectroscopy

    Smulevich, G.; Mantini, A. R.; Casu, M.; Marzocchi, M. P.

    1991-05-01

    The antiturnor anthracyclincs, idarubicin (IDA ), adrianiycin (ADM), epirubicin (EPI), carminomycin (CAR) and 1 1-deoxycarminornycin (DCM), whose siructural formula includes a substituted hydroxyanthraquirionc chrornophore and a sugar residue, form intercalation complexes with DNA. The stacking interaction between the chromophore and the base-pairs of DNA gives rise to noticeable ciTects on resonance Raman (RR) and surface-enhanced resonance Raman (SERRS) scattering as well as on the absorption (ABS), its second derivative (D2) and fluorescence emission (FEM) spectra.

  7. Investigating the Environment-dependent Photophysics of Chlorine Dioxide With Resonance Raman Intensities

    Esposito, Anthony P.; Foster, Catherine E.; Reid, Philip J.

    1999-01-01

    The condensed-phase excited-state reaction dynamics of chlorine dioxide are investigated using resonance Raman intensity analysis. Absolute Raman intensities are measured on resonance with the 2B2–2A2 electronic transition and used to establish the excited-state structural evolution which occurs on the 2A2 surface following photoexcitation. Analysis of the intensities demonstrates that excited-state relaxation occurs along all three normal coordinates; however, only modest evolution is observ...

  8. Hyper-Raman scattering and three-photon resonant ionization: Competitive effects

    A semiclassical theory of hyper-Raman scattering and three-photon resonant ionization via the coupled density-matrix and Maxwell equations is presented. A simplified three-level atom model is obtained, which includes two-photon resonant pumping and time dependent photoionization rates. We consider conditions typically encountered in atomic vapours to simulate numerically pulse propagation. A strong depletion of the photoionization probability in the hyper-Raman field saturation regime is predicted. (author). 17 refs, 8 figs

  9. On the inner Double-Resonance Raman scattering process in bilayer graphene

    Mafra, D. L.; Moujaes, E. A.; Nunes, R. W.; Pimenta, M. A.

    2010-01-01

    The dispersion of phonons and the electronic structure of graphene systems can be obtained experimentally from the double-resonance (DR) Raman features by varying the excitation laser energy. In a previous resonance Raman investigation of graphene, the electronic structure was analyzed in the framework of the Slonczewski-Weiss-McClure (SWM) model, considering the outer DR process. In this work we analyze the data considering the inner DR process, and obtain SWM parameters that are in better a...

  10. Resonant Raman and micro-Raman scattering from Si matrix with unburied beta-FeSi2 nanolayers.

    Marinova, M; Baleva, M; Zlateva, G

    2008-02-01

    Samples, representing Si matrix with nanolayers of the semiconducting beta-FeSi2 silicide are studied by Raman scattering. The unpolarized Raman spectra of the samples are measured in two different configurations. It is found that the characteristic beta-FeSi2 Raman modes are seen in the spectra, taken at incident angle of about 45 degrees , while only comparatively intensive broad feature is detected in a back-scattering geometry. The difference in the spectra is interpreted with the appearance of surface polariton modes of the optical phonons in the nanosized layers in near back-scattering geometry. The resonant Raman scattering is investigated at incident light angle of about 45 degrees and the energies of the interband transitions in the investigated energy range are determined. It is known that the resonant Raman scattering appears to be even more precise method for the determination of the interband transitions energies than the modulation spectroscopy. Thus we claim that the energies determined here are firstly determined with such a precision. PMID:18464405

  11. Resonant stimulation of Raman scattering from single-crystal thiophene/phenylene co-oligomers

    Amplified Raman scattering was observed from single crystals of thiophene/phenylene co-oligomers (TPCOs). Under ns-pulsed excitation, the TPCO crystals exhibited amplified spontaneous emission (ASE) at resonant absorption wavelengths. With increasing excitation wavelength to the 0-0 absorption edge, the stimulated resonant Raman peaks appeared both in the 0-1 and 0-2 ASE band regions. When the excitation wavelength coincided with the 0-1 ASE band energy, the Raman peaks selectively appeared in the 0-2 ASE band. Such unusual enhancement of the 0-2 Raman scattering was ascribed to resonant stimulation via vibronic coupling with electronic transitions in the uniaxially oriented TPCO molecules

  12. Resonance Raman Probes for Organelle-Specific Labeling in Live Cells

    Kuzmin, Andrey N.; Pliss, Artem; Lim, Chang-Keun; Heo, Jeongyun; Kim, Sehoon; Rzhevskii, Alexander; Gu, Bobo; Yong, Ken-Tye; Wen, Shangchun; Prasad, Paras N.

    2016-06-01

    Raman microspectroscopy provides for high-resolution non-invasive molecular analysis of biological samples and has a breakthrough potential for dissection of cellular molecular composition at a single organelle level. However, the potential of Raman microspectroscopy can be fully realized only when novel types of molecular probes distinguishable in the Raman spectroscopy modality are developed for labeling of specific cellular domains to guide spectrochemical spatial imaging. Here we report on the design of a next generation Raman probe, based on BlackBerry Quencher 650 compound, which provides unprecedentedly high signal intensity through the Resonance Raman (RR) enhancement mechanism. Remarkably, RR enhancement occurs with low-toxic red light, which is close to maximum transparency in the biological optical window. The utility of proposed RR probes was validated for targeting lysosomes in live cultured cells, which enabled identification and subsequent monitoring of dynamic changes in this organelle by Raman imaging.

  13. High-resolution inverse Raman and resonant-wave-mixing spectroscopy

    Rahn, L.A. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    These research activities consist of high-resolution inverse Raman spectroscopy (IRS) and resonant wave-mixing spectroscopy to support the development of nonlinear-optical techniques for temperature and concentration measurements in combustion research. Objectives of this work include development of spectral models of important molecular species needed to perform coherent anti-Stokes Raman spectroscopy (CARS) measurements and the investigation of new nonlinear-optical processes as potential diagnostic techniques. Some of the techniques being investigated include frequency-degenerate and nearly frequency-degenerate resonant four-wave-mixing (DFWM and NDFWM), and resonant multi-wave mixing (RMWM).

  14. Communication: Significant contributions of Albrecht's $A$ term to non-resonant Raman scattering processes

    Duan, Sai; Luo, Yi

    2015-01-01

    The Raman intensity can be well described by the famous Albrecht equation that consists of $A$ and $B$ terms. It has become a textbook knowledge that the contribution from Albrecht's $A$ term can be neglected without loss of accuracy for non-resonant Raman scattering processes. However, as demonstrated in this study, we have found that this widely accepted long-standing assumption fails drastically for totally symmetric vibration modes of molecules. Perturbed first principles calculations for water molecule show that strong constructive interference between the $A$ and $B$ terms occurs for the Raman intensity of the symmetric O-H stretching mode, which can account for about 40% of the total intensity. Meanwhile, a minor destructive interference is found for the angle bending mode. The state to state mapping between the Albrecht's theory and the perturbation theory allows us to verify the accuracy of the widely employed perturbation method for the dynamic/resonant Raman intensities. The model calculations show...

  15. Spatial correlation between chemical and topological defects in vitreous silica: UV-resonance Raman study

    A spatial correlation between chemical and topological defects in the tetrahedron network in vitreous silica produced by a fusion process of natural quartz crystals was found by synchrotron-based UV resonance Raman experiments. Furthermore, a quantitative correlation between these defects was obtained by comparing visible Raman and UV absorption spectra. These results indicate that in vitreous silica produced by the fusion process the topological defects disturb the surrounding tetrahedral silica network and induce further disorder regions with sub nanometric sizes

  16. Resonance Raman measurements of carotenoids using light emitting diodes

    Bergeson, S D; Eyring, N J; Fralick, J F; Stevenson, D N; Ferguson, S B

    2008-01-01

    We report on the development of a compact commercial instrument for measuring carotenoids in skin tissue. The instrument uses two light emitting diodes (LEDs) for dual-wavelength excitation and four photomultiplier tubes for multichannel detection. Bandpass filters are used to select the excitation and detection wavelengths. The f/1.3 optical system has high optical throughput and single photon sensitivity, both of which are crucial in LED-based Raman measurements. We employ a signal processing technique that compensates for detector drift and error. The sensitivity and reproducibility of the LED Raman instrument compares favorably to laser-based Raman spectrometers. This compact, portable instrument is used for non-invasive measurement of carotenoid molecules in human skin with a repeatability better than 10%.

  17. Aggregation-Induced Resonance Raman Optical Activity (AIRROA): A New Mechanism for Chirality Enhancement.

    Zajac, Grzegorz; Kaczor, Agnieszka; Pallares Zazo, Ana; Mlynarski, Jacek; Dudek, Monika; Baranska, Malgorzata

    2016-05-01

    Raman optical activity (ROA) spectroscopy is hampered by low sensitivity, with limited possibilities for enhancing the signal. In the present study, we report a new mechanism whereby chirality is enhanced using the resonance resulting from supramolecular aggregation. We have named this mechanism aggregation-induced resonance Raman optical activity (AIRROA). As an example, we study J-aggregates of astaxanthin (AXT), which show strong absorption of circularly polarized light in the range of ROA excitation. The implications of aggregation-induced signal enhancement for chiroptical spectroscopy are discussed. PMID:27057926

  18. Resonant Raman scattering in GaSe and GaS/sub x/Se/sub 1-x/

    Chiang, T.C.; Camassel, J.; Voitchovsky, J.P.; Shen, Y.R.

    1976-07-01

    Multiphonon resonant Raman scattering up to four phonons in GaSe and one and two phonon resonant Raman scattering in the mixed GaS/sub x/Se/sub 1 - x/ crystals with x less than or equal to 0.23 were investigated. The results can be explained by a simple theory in which the dispersion of the resonance behavior is mainly dominated by resonances with the 1s direct exciton state.

  19. Characterization of the pigment xanthomonadin in the bacterial genus Xanthomonas using micro- and resonance Raman spectroscopy

    Paret, Mathews L.; Sharma, Shiv K.; Misra, Anupam K.; Acosta, Tayro; deSilva, Asoka S.; Vowell, Tomie; Alvarez, Anne M.

    2012-06-01

    We used micro- and resonance Raman spectroscopy with 785 nm and 514.5 nm laser excitation, respectively, to characterize a plant pathogenic bacteria, Xanthomonas axonopodis pv. dieffenbachiae D150. The bacterial genus Xathomonas is closely related to bacterial genus Stenotrophomonas that causes an infection in humans. This study has identified for the first time the unique Raman spectra of the carotenoid-like pigment xanthomonadin of the Xanthomonas strain. Xanthomonadin is a brominated aryl-polyene pigment molecule similar to carotenoids. Further studies were conducted using resonance Raman spectroscopy with 514.5 nm laser excitation on several strains of the bacterial genus Xanthomonas isolated from numerous plants from various geographical locations. The current study revealed that the Raman bands representing the vibrations (v1, v2, v3) of the polyene chain of xanthomonadin are 1003-1005 (v3), 1135-1138 (v2), and 1530 (v1). Overtone bands representing xanthomonadin were identified as 2264-2275 (2v2), and combinational bands at 2653-2662 (v1+ v2). The findings from this study validate our previous finding that the Raman fingerprints of xanthomonadin are unique for the genus Xanthomonas. This facilitates rapid identification (~5 minutes) of Xanthomonas spp. from bacterial culture plates. The xanthomonadin marker is different from Raman markers of many other bacterial genus including Agrobacterium, Bacillus, Clavibacter, Enterobacter, Erwinia, Microbacterium, Paenibacillus, and Ralstonia. This study also identified Xanthomonas spp. from bacterial strains isolated from a diseased wheat sample on a culture plate.

  20. Resonance enhancement effects in Raman-enhancing pyramid-like V-shape groove microstructures

    Mechler, M; Mechler, A; McNaughton, D

    2009-01-01

    Microscopic pyramidal pits in a reflective surface, a geometry similar to a retroreflector, are frequently used to enhance signal strength. The enhancement effect is generally attributed to surface plasmons, however, the sub-wavelength to near-wavelength dimensions of the pyramidal 3D geometry suggest contributions from diffraction and near-field effects. Our theoretical analysis of the light intensity distribution in the similar (but simpler) 2D geometry assuming a perfect conductor screen, that is, in the absence of any plasmon effects, shows that interference patterns forming within the cavity cause a significant resonant increase in local intensity. Such effect can be important for many applications, especially for the widely used Raman spectroscopy. Resonant enhancement without plasmons of the emitted Raman signal due to enhanced local field amplitude is also possible, which implies that the geometry practically implements a Raman laser. Comparison of diffraction patterns obtained with near-field and far...

  1. Resonance raman and absorption spectra of isomeric retinals in their lowest excited triplet states

    Wilbrandt, Robert Walter; Jensen, N.-H.; Houee-Levin, C.

    1985-01-01

    The triplet-triplet absorption spectra of 9-cis and all-trans-retinal as well as the time-resolved resonance Raman spectra of the lowest electronically excited triplet states of 9-cis-, 11-cis, 13-cis and all-trans-retinal in aromatic solvents at room temperature were obtained under conditions en...

  2. Detection of Molecular Chirality by Induced Resonance Raman Optical Activity in Europium Complexes

    Yamamoto, Shigeki; Bouř, Petr

    2012-01-01

    Roč. 51, č. 44 (2012), s. 11058-11061. ISSN 1433-7851 R&D Projects: GA MŠk(CZ) LH11033; GA ČR GAP208/11/0105 Institutional support: RVO:61388963 Keywords : europium * complexes * raman optical activity * resonance Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 13.734, year: 2012

  3. Effect of atomic diffusion on the Raman-Ramsey CPT resonances

    Kuchina, Elena; Novikova, Irina

    2015-01-01

    We experimentally investigated the characteristics of two-photon transmission resonances in Rb vapor cells with different amount of buffer gas under the conditions of steady-state coherent population trapping (CPT) and pulsed Raman-Ramsey (RR-) CPT interrogation scheme. We particularly focused on the influence of the Rb atoms diffusing in and out of the laser beam. We showed that this effect modifies the shape of both CPT and Raman-Ramsey resonances, as well as their projected performance for CPT clock applications. In particular we found that at moderate buffer gas pressures RR-CPT did not improved the projected atomic clock stability compare to the regular steady-state CPT resonance.

  4. Raman scattering enhancement in photon-plasmon resonance mediated metal-dielectric microcavity

    Here, we report the photon-plasmon interaction scheme and enhanced field strengths resulted into the amplification of phonon in a novel microcavity. A metal-dielectric microcavity, with unified cavity photonic mode and localized surface plasmon resonances, is visualized by impregnating the gold nanoparticles into the deep see-through nano-sized pores of porous silicon microcavity. The intense optical field strengths resulting from the photon-plasmon interactions are probed by both resonant and non-resonant Raman scattering experiments. Due to photon-plasmon-phonon interaction mechanism, several orders of enhancement in the intensity of scattered Raman Stokes photon (at 500 cm−1) are observed. Our metal nanoparticle-microcavity hybrid system shows the potential to improve the sensing figure of merit as well as the applications of plasmonics for optoelectronics, photovoltaics, and related technologies

  5. Raman scattering enhancement in photon-plasmon resonance mediated metal-dielectric microcavity

    Guddala, Sriram; Narayana Rao, D., E-mail: dnr.laserlab@gmail.com, E-mail: dnrsp@uohyd.ernet.in [School of Physics, University of Hyderabad, Hyderabad 500 046 (India); Dwivedi, Vindesh K.; Vijaya Prakash, G. [Nanophotonics Laboratory, Department of Physics, IIT Delhi, New Delhi 110 016 (India)

    2013-12-14

    Here, we report the photon-plasmon interaction scheme and enhanced field strengths resulted into the amplification of phonon in a novel microcavity. A metal-dielectric microcavity, with unified cavity photonic mode and localized surface plasmon resonances, is visualized by impregnating the gold nanoparticles into the deep see-through nano-sized pores of porous silicon microcavity. The intense optical field strengths resulting from the photon-plasmon interactions are probed by both resonant and non-resonant Raman scattering experiments. Due to photon-plasmon-phonon interaction mechanism, several orders of enhancement in the intensity of scattered Raman Stokes photon (at 500 cm{sup −1}) are observed. Our metal nanoparticle-microcavity hybrid system shows the potential to improve the sensing figure of merit as well as the applications of plasmonics for optoelectronics, photovoltaics, and related technologies.

  6. Resonance-Enhanced Raman Spectroscopy on Explosives Vapor at Standoff Distances

    Anneli Ehlerding

    2012-01-01

    Full Text Available Resonance-enhanced Raman spectroscopy has been used to perform standoff measurements on nitromethane (NM, 2,4-DNT, and 2,4,6-TNT in vapor phase. The Raman cross sections for NM, DNT, and TNT in vapor phase have been measured in the wavelength range 210–300 nm under laboratory conditions, in order to estimate how large resonance enhancement factors can be achieved for these explosives. The results show that the signal is enhanced up to 250,000 times for 2,4-DNT and up to 60,000 times for 2,4,6-TNT compared to the nonresonant signal at 532 nm. Realistic outdoor measurements on NM in vapor phase at 13 m distance were also performed, which indicate a potential for resonance Raman spectroscopy as a standoff technique for detection of vapor phase explosives. In addition, the Raman spectra of acetone, ethanol, and methanol were measured at the same wavelengths, and their influence on the spectrum from NM was investigated.

  7. Resonance Raman scattering and excitonic spectra in TlInS{sub 2} crystals

    Zalamai, V.V. [Institute of Applied Physics, Academy of Sciences of Moldova, 5 Academy Street, 2028 Chisinau, Republic of Moldova (Moldova, Republic of); Stamov, I.G. [T.G. Shevchenko State University of Pridnestrovie, 25 Oktyabrya Street 107, 3300 Tiraspol, Republic of Moldova (Moldova, Republic of); Syrbu, N.N., E-mail: sirbunn@yahoo.com [Technical University of Moldova, 168 Stefan cel Mare Avenue, 2004 Chisinau, Republic of Moldova (Moldova, Republic of); Ursaki, V.V. [Institute of Applied Physics, Academy of Sciences of Moldova, 5 Academy Street, 2028 Chisinau, Republic of Moldova (Moldova, Republic of); Dorogan, V. [Technical University of Moldova, 168 Stefan cel Mare Avenue, 2004 Chisinau, Republic of Moldova (Moldova, Republic of)

    2015-04-15

    The excitons ground and excited states for E∥a and E∥b polarizations in absorption and reflection spectra of TlInS{sub 2} crystals were detected. The fundamental parameters of excitons and bands were determined at k=0. The resonance Raman spectra were investigated in the region of excitons transitions. The resonance Raman scattering spectra with participation of optical phonons that are active at the center of Brillouin zone were identified. The Raman scattering in Y(YX)Z and Y(ZX)Z geometries at 10 K with excitation by He–Ne laser was researched. Energies of phonons with A{sub g} and B{sub g} symmetries were determined. It was shown that the number of modes at 10 K was two times lower than expected according to theoretical calculations. - Highlights: • The resonance Raman scattering in geometry Y(YX)Z and Y(ZX)Z at 10 K was investigated. • Energies of phonons with A{sub g} and B{sub g} symmetries were determined. • The experimental and theoretical calculations completely conform if crystals are described by symmetry group D{sub 4h}{sup 15}. • The main parameters of excitons and bands were determined. • The model of electron transitions in k=0 was suggested.

  8. Quantum State Absorptions Coupled To Resonance Raman Spectroscopy Could Result In A General Explanation of TERS

    Schultz, Zachary D; Dekhter, Rimma; Anestopoulos, Dimitris; Grammatikopoulos, Spyridon; Papagelis, Kostantinos; Marr, James M; Lewis, David; Galiotis, Costas; Lev, Dimtry; Lewis, Aaron

    2016-01-01

    Tip enhanced Raman scattering (TERS) amplifies the intensity of vibrational Raman scattering by employing the tip of a probe interacting, in ultra close proximity, with a surface. Although a general understanding of the TERS process is still to be fully elucidated, scanning tunneling microscopy (STM) feedback is often applied with success in TERS to keep a noble metal probe in intimate proximity with a noble metal substrate. Since such STM TERS is a common modality, the possible implications of plasmonic fields that may be induced by the tunneling process are investigated and reported. In addition, TERS of a 2D resonant molecular system, a MoS2 bilayer crystal and a 2D non-resonant, lipid molecular bilayer is compared. Data with multiple excitation wavelengths and surfaces for the resonant system in the near- (TERS) and far-field regimes are reported. An interpretation based on weak coupling interactions within the framework of conventional resonance Raman scattering can explain the observed TERS enhancements...

  9. Resonance Raman spectroscopy with chemical state selectivity on histidine and acetamide using synchrotron radiation

    We report on ultraviolet resonance Raman scattering experiments carried out on two model substances: histidine and acetamide using a UV synchrotron radiation source. In the case of aqueous histidine solution each protonated state of histidine tautomers was selectively excited by tuning the incident wavelength and the vibrational state of each protonated state was studied. We also demonstrated that the local pH condition of histidine can be identified directly from the spectra above pH 9. In the case of acetamide, the resonance Raman bands of acetamide with a stronger hydrogen bond at the NH2 site and weaker hydrogen bond at the C=O site were selectively observed. These findings will extend the selectivity and sensitivity of RR spectroscopy that is helpful to understanding protein functionality. (author)

  10. Characterization of fluorine-doped silicon dioxide films by Raman spectroscopy and Electron-spin resonance

    We have measured Raman and Electron-spin resonance (ESR) spectra of fluorine-doped SiO2 films deposited by two different methods. In high-density plasma (HDP) films, the Raman band at about 490 cm-1 becomes drastically stronger as the F/Si ratio increases, whereas the Raman band from threefold ring defect is independent of the F/Si ratio. The unusual increase of the intensity of the 490 cm-1 band in HDP films has been interpreted in terms of the existence of Si-Si clusters. From a comparison between Raman spectra of HDP film and plasma chemical vapor deposition using tetraethoxysilane (p-TEOS) film with the same F/Si ratios it has been found that HDP film has more Si-Si bonds and threefold ring defects than p-TEOS film. Furthermore, the polarized Raman spectra in the 810 cm-1 bands indicate that inhomogeneous SiO2 clusters of various sizes should exist in the network structure of HDP film. The result of the ESR measurement shows that HDP films have fewer dangling bonds than p-TEOS films. It is considered that many Si-Si clusters, threefold ring defects, and inhomogeneous SiO2 cluster sizes, and the few dangling bonds in HDP films give rise to the film properties of low stress, good adhesion with Si substrate, and low water permeation

  11. Characterization of fluorine-doped silicon dioxide films by Raman spectroscopy and Electron-spin resonance

    Matsuda, K. [Toray Research Center, Inc. Sonoyama 3-3-7, Otsu, Shiga, 520-8567 (Japan)]. E-mail: keiko_matsuda@trc.toray.co.jp; Yamaguchi, Y. [Toray Research Center, Inc. Sonoyama 3-3-7, Otsu, Shiga, 520-8567 (Japan); Morita, N. [Toray Research Center, Inc. Sonoyama 3-3-7, Otsu, Shiga, 520-8567 (Japan); Matsunobe, T. [Toray Research Center, Inc. Sonoyama 3-3-7, Otsu, Shiga, 520-8567 (Japan); Yoshikawa, M. [Toray Research Center, Inc. Sonoyama 3-3-7, Otsu, Shiga, 520-8567 (Japan)

    2007-06-13

    We have measured Raman and Electron-spin resonance (ESR) spectra of fluorine-doped SiO{sub 2} films deposited by two different methods. In high-density plasma (HDP) films, the Raman band at about 490 cm{sup -1} becomes drastically stronger as the F/Si ratio increases, whereas the Raman band from threefold ring defect is independent of the F/Si ratio. The unusual increase of the intensity of the 490 cm{sup -1} band in HDP films has been interpreted in terms of the existence of Si-Si clusters. From a comparison between Raman spectra of HDP film and plasma chemical vapor deposition using tetraethoxysilane (p-TEOS) film with the same F/Si ratios it has been found that HDP film has more Si-Si bonds and threefold ring defects than p-TEOS film. Furthermore, the polarized Raman spectra in the 810 cm{sup -1} bands indicate that inhomogeneous SiO{sub 2} clusters of various sizes should exist in the network structure of HDP film. The result of the ESR measurement shows that HDP films have fewer dangling bonds than p-TEOS films. It is considered that many Si-Si clusters, threefold ring defects, and inhomogeneous SiO{sub 2} cluster sizes, and the few dangling bonds in HDP films give rise to the film properties of low stress, good adhesion with Si substrate, and low water permeation.

  12. Quantitative detection of astaxanthin and cantaxanthin in Atlantic salmon by resonance Raman spectroscopy

    Ermakov, Igor V.; Ermakova, Maia R.; Gellermann, Werner

    2006-02-01

    Two major carotenoids species found in salmonids muscle tissues are astaxanthin and cantaxanthin. They are taken up from fish food and are responsible for the attractive red-orange color of salmon filet. Since carotenoids are powerful antioxidants and biomarkers of nutrient consumption, they are thought to indicate fish health and resistance to diseases in fish farm environments. Therefore, a rapid, accurate, quantitative optical technique for measuring carotenoid content in salmon tissues is of economic interest. We demonstrate the possibility of using fast, selective, quantitative detection of astaxanthin and cantaxanthin in salmon muscle tissues, employing resonance Raman spectroscopy. Analyzing strong Raman signals originating from the carbon-carbon double bond stretch vibrations of the carotenoid molecules under blue laser excitation, we are able to characterize quantitatively the concentrations of carotenoids in salmon muscle tissue. To validate the technique, we compared Raman data with absorption measurements of carotenoid extracts in acetone. A close correspondence was observed in absorption spectra for tissue extract in acetone and a pure astaxanthin solution. Raman results show a linear dependence between Raman and absorption data. The proposed technique holds promise as a method of rapid screening of carotenoid levels in fish muscle tissues and may be attractive for the fish farm industry to assess the dietary status of salmon, risk for infective diseases, and product quality control.

  13. Raman Theory for a Molecule in a Vibrating Microcavity Oscillating in Fundamental Resonance

    YANG XiaoXue; WU Ying

    2001-01-01

    We propose a model to describe the energy structure and dynamics of a system of a molecule interacting with infinite photon modes in a vibrating microcavity whose boundary oscillates in the fundamental resonance. By constructing an so(2,1) Lie algebra for the infinite photon modes, we obtain analytical expressions of the energy eigenstates, energy eigenvalues and the system's evolution operator for this Raman model under certain conditions.``

  14. Electron paramagnetic resonance and Raman spectroscopy studies on carbon-doped

    Bateni, Ali; Somer, Mehmet Suat; Erdem, Emre; Repp, Sergej; Acar, SelÇuk; Kokal, İlkin; Haessler, Wolfgang; Weber, Stefan

    2015-01-01

    Undoped and carbon-doped magnesium diboride (MgB2) samples were synthesized using two sets of mixtures prepared from the precursors, amorphous nanoboron, and as-received amorphous carbon-doped nanoboron. The microscopic defect structures of carbon-doped MgB2 samples were systematically investigated using X-ray powder diffraction, Raman and electron paramagnetic resonance spectroscopy. Mg vacancies and C-related dangling-bond active centers could be distinguished, and sp(3)-hybridized carbon r...

  15. Surface plasmon enhanced interfacial electron transfer and resonance Raman, surface-enhanced resonance Raman studies of cytochrome C mutants

    Zheng, Junwei

    1999-11-08

    Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO{sub 2} were studied on electrochemically roughened silver electrode surfaces. The dependence of the photocurrent on photon energy, applied potential and concentration of nitrite demonstrates that the photoelectrochemical reduction proceeds via photoemission process followed by the capture of hydrated electrons. The excitation of plasmon resonances in nanosized metal structures resulted in the enhancement of the photoemission process. In the case of photoelectrocatalytic reduction of CO{sub 2}, large photoelectrocatalytic effect for the reduction of CO{sub 2} was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO{sub 2} in solution. Photoinduced reduction of microperoxidase-11 adsorbed on roughened silver electrode was also observed and attributed to the direct photoejection of free electrons of silver metal. Surface plasmon assisted electron transfer at nanostructured silver particle surfaces was further determined by EPR method.

  16. Application of resonance Raman spectroscopy as a nuclear proliferation detection technology

    Sedlacek, A.J. III; Chen, C.L.; Dougherty, D.R.

    1993-01-01

    Resonance Raman spectroscopy (RRS) potentially possesses many of the characteristics of an ideal verification technology. Some of these ideal traits are: very high selectivity and specificity to allow the deconvolution of a mixture of the chemicals of interest, high sensitivity in order to measure a species at trace levels, high reliability and long-term durability, applicability to a wide range of chemicals capability for sensing in a variety of environmental conditions, independence of the physical state of the chemical capability for quantitative analysis, and finally, but no less important capability for full signal development within seconds. In this presentation, the potential of RRS as a detection/identification technology for chemicals pertinent to nuclear materials production and processing will be assessed. A review of the basic principles behind this technique, both theoretical and experimental, will be discussed along with some recent results obtained in this laboratory. Raman scattering is a coherent, inelastic, two-photon scattering process where an exciting photon of energy hv promotes a molecule to a virtual level and the subsequently emitted photon is shifted in frequency in accordance with the rotational-vibrational structure of the irradiated species, therefore providing a unique fingerprint of the molecule. The enhancement of a Raman signal occurs when the excitation frequency is isoenergetic with an allowed electronic transition. Under resonance conditions, scattering cross-sections have been enhanced up to 6 orders of magnitude, thereby allowing the measurement of resonance Raman spectra from concentrations as dilute as 20 ppb for PAHs (with the potential of pptr). In detection/verification programs, this condition translates to increased sensitivity (ppm/ppb) and increased probing distance (m/km).

  17. Application of resonance Raman spectroscopy as a nuclear proliferation detection technology

    Sedlacek, A.J. III; Chen, C.L.; Dougherty, D.R.

    1993-03-01

    Resonance Raman spectroscopy (RRS) potentially possesses many of the characteristics of an ideal verification technology. Some of these ideal traits are: very high selectivity and specificity to allow the deconvolution of a mixture of the chemicals of interest, high sensitivity in order to measure a species at trace levels, high reliability and long-term durability, applicability to a wide range of chemicals capability for sensing in a variety of environmental conditions, independence of the physical state of the chemical capability for quantitative analysis, and finally, but no less important capability for full signal development within seconds. In this presentation, the potential of RRS as a detection/identification technology for chemicals pertinent to nuclear materials production and processing will be assessed. A review of the basic principles behind this technique, both theoretical and experimental, will be discussed along with some recent results obtained in this laboratory. Raman scattering is a coherent, inelastic, two-photon scattering process where an exciting photon of energy hv promotes a molecule to a virtual level and the subsequently emitted photon is shifted in frequency in accordance with the rotational-vibrational structure of the irradiated species, therefore providing a unique fingerprint of the molecule. The enhancement of a Raman signal occurs when the excitation frequency is isoenergetic with an allowed electronic transition. Under resonance conditions, scattering cross-sections have been enhanced up to 6 orders of magnitude, thereby allowing the measurement of resonance Raman spectra from concentrations as dilute as 20 ppb for PAHs (with the potential of pptr). In detection/verification programs, this condition translates to increased sensitivity (ppm/ppb) and increased probing distance (m/km).

  18. Krypton isotope analysis using near-resonant stimulated Raman spectroscopy

    A method for measuring low relative abundances of 85Kr in one liter or less samples of air has been under development here at Pacific Northwest Laboratory. The goal of the Krypton Isotope Laser Analysis (KILA) method is to measure ratios of 10-10 or less of 85Kr to more abundant stable krypton. Mass spectrometry and beta counting are the main competing technologies used in rare-gas trace analysis and are limited in application by such factors as sample size, counting times, and selectivity. The use of high-resolution lasers to probe hyperfine levels to determine isotopic abundance has received much attention recently. In this study, we report our progress on identifying and implementing techniques for trace 85Kr analysis on small gas samples in a static cell as well as limitations on sensitivity and selectivity for the technique. High-resolution pulsed and cw lasers are employed in a laser-induced fluorescence technique that preserves the original sample. This technique, is based on resonant isotopic depletion spectroscopy (RIDS) in which one isotope is optically depleted while preserving the population of a less abundant isotope. The KILA method consists of three steps. In the first step, the 1s5 metastable level of krypton is populated via radiative cascade following two-photon excitation of the 2p6 energy level. Next, using RBDS, the stable krypton isotopes are optically depleted to the ground state through the 1s4 level with the bulk of the 85Kr population being preserved. Finally, the remaining metastable population is probed to determine 85Kr concentration. The experimental requirements for each of these steps are outlined below

  19. Resonance Raman spectra of phthalocyanine monolayers on different supports. A normal mode analysis of zinc phthalocyanine by means of the MNDO method

    Palys, Barbara J.; Ham, van den Dirk M.W.; Briels, Wim; Feil, Dirk

    1995-01-01

    Resonance Raman spectra of monolayers of transition metal phthalocyanines reveal specific interaction with the support. To elucidate its mechanism, Raman spectra of zinc phthalocyanine monolayers were studied. The analysis was based largely on the results of MNDO calculations. Calculated wavenumbers

  20. Resonant Raman detectors for noninvasive assessment of carotenoid antioxidants in human tissue

    Gellermann, Werner; Sharifzadeh, Mohsen; Ermakova, Maia R.; Ermakov, Igor V.; Bernstein, P. S.

    2003-07-01

    Carotenoid antioxidants form an important part of the human body's anti-oxidant system and are thought to play an important role in disease prevention. Studies have shown an inverse correlation between high dietary intake of carotenoids and risk of certain cancers, heart disease and degenerative diseases. For example, the carotenoids lutein and zeaxanthin, which are present in high concentrations in the human retina, are thought to prevent age-related macular degeneration, the leading cause of blindness in the elderly in the Western world. We have developed various clinical prototype instruments, based on resonance Raman spectroscopy, that are able to measure carotenoid levels directly in the tissue of interest. At present we use the Raman technology to quantify carotenoid levels in the human retina, in skin, and in the oral cavity. We use resonant excitation of the π-conjugated molecules in the visible wavelength range and detect the molecules' carbon-carbon stretch frequencies. The spectral properties of the various carotenoids can be explored to selectively measure in some cases individual carotenoid species linked ot the prevention of cancer, in human skin. The instrumentation involves home-built, compact, high-throughput Raman systems capable of measuring physiological carotenoid concentrations in human subjects rapidly and quantitatively. The instruments have been demonstrated for field use and screening of tissue carotenoid status in large populations. In Epidemiology, the technology holds promise as a novel, noninvasive and objective biomarker of fruit and vegetable uptake.

  1. Stimulated Stokes and Antistokes Raman Scattering in Microspherical Whispering Gallery Mode Resonators.

    Farnesi, Daniele; Berneschi, Simone; Cosi, Franco; Righini, Giancarlo C; Soria, Silvia; Nunzi Conti, Gualtiero

    2016-01-01

    Dielectric microspheres can confine light and sound for a length of time through high quality factor whispering gallery modes (WGM). Glass microspheres can be thought as a store of energy with a huge variety of applications: compact laser sources, highly sensitive biochemical sensors and nonlinear phenomena. A protocol for the fabrication of both the microspheres and coupling system is given. The couplers described here are tapered fibers. Efficient generation of nonlinear phenomena related to third order optical non-linear susceptibility Χ((3)) interactions in triply resonant silica microspheres is presented in this paper. The interactions here reported are: Stimulated Raman Scattering (SRS), and four wave mixing processes comprising Stimulated Anti-stokes Raman Scattering (SARS). A proof of the cavity-enhanced phenomenon is given by the lack of correlation among the pump, signal and idler: a resonant mode has to exist in order to obtain the pair of signal and idler. In the case of hyperparametric oscillations (four wave mixing and stimulated anti-stokes Raman scattering), the modes must fulfill the energy and momentum conservation and, last but not least, have a good spatial overlap. PMID:27078752

  2. Resonant micro-Raman spectroscopy on few InAs quantum dots

    Koeppen, Tim; Brocke, Thomas; Kipp, Tobias; Schramm, Andreas; Heyn, Christian; Heitmann, Detlef [Institut fuer Angewandte Physik und Zentrum fuer Mikrostrukturforschung der Universitaet Hamburg, Jungiusstrasse 11, 20355 Hamburg (Germany)

    2007-07-01

    We investigate the electronic excitations in InAs quantum dots under the exploitation of resonant inelastic light scattering. In contrast to earlier measurements at the E{sub 0}+{delta} gap ({proportional_to}1.65 eV), we now excite resonantly at the E{sub 0} gap ({proportional_to}1.2 eV) using a TiSa-laser in the near-infrared regime. Furthermore we now use a microscope setup focussing the exciting laser to a diameter of about 1.8 {mu}m. Although there are still about 250 quantum dots under the laser spot, we observe very few sharp lines of individual quantum dots which arise due to resonant excitation. We can distinguish between Raman signals of electronic excitations and photoluminescence signals which reside in the same energy range.

  3. Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules

    Zhou Zeng-Hui; Liu Li; Wang Gui-Ying; Xu Zhi-Zhan

    2006-01-01

    Surface-enhanced resonance Raman scattering (SERRS) of Rhodamine 6G (R6G) adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even "breathing" of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.

  4. Simulations of resonant Raman response in bundles of semiconductor carbon nanotubes

    Roslyak, Oleksiy; Piryatinski, Andrei; Doorn, Stephen; Haroz, Erik; Telg, Hagen; Duque, Juan; Crochet, Jared; Simpson, J. R.; Hight Walker, A. R.; LANL Collaboration; Fordham Collaboration; NIST Collaboration

    This work is motivated by an experimental study of resonant Raman spectroscopy under E22 excitation, which shows a new, sharp feature associated with bundling in (6,5) semiconductor carbon nanotubes. In order to provide an insight into the experimental data, we model Raman excitation spectra using our modified discrete dipole approximation (DDA) method. The calculations account for the exciton states polarized along and across the nanotube axis that are characterized by a small energy splitting. Strong polarization of the nanotubes forming the bundle results in the exciton state mixing whose spectroscopic signatures such as peaks positions, line widths, and depolarization ratio are calculated and compared to the experiment. Furthermore, the effects of the energy and structural disorder, as well as structural defects within the bundle are also examined and compared with the experimental data.

  5. Thermal and stress influence on performance of SOI racetrack resonator Raman lasers

    In this paper, the detailed modeling of Raman lasers in silicon-on-insulator guided-wave racetrack resonant microcavities is developed. Modeling based on full-vectorial equations, including thermal and stress effects, is presented for the first time. Simulation results are compared with experimental and theoretical results in the literature, demonstrating very good agreement. Moreover, parametric investigations, including waveguide sizes, pump and Stokes coupling factors, cavity shape, polarization states, and waveguide orientation are presented; and the effects of these characteristics in conjunction with thermal and stress influence on laser features are discussed. (papers)

  6. Resonance Raman study on distorted symmetry of porphyrin in nickel octaethyl porphyrin

    S Tewari; R Das; A Chakraborty; Ramendu Bhattacharjee

    2004-11-01

    The resonance Raman (RR) spectra of nickel octaethyl porphyrin, Ni(OEP), in CH2Cl2 (solvent) at different excitations such as 514.5, 488.0, 441.6 and 406.7 nm are recorded and analysed. The results of the theory of distortion-induced RR intensity is applied to the observed spectra to determine the excited electronic state symmetry of porphyrin in Ni(OEP). It is concluded that the porphyrin molecule (D4h structure) attains a non-polar distorted structure of D2 symmetry rather than S4 symmetry in CH2Cl2 solution.

  7. Manifestation of Structure of Electron Bands in Double-Resonant Raman Spectra of Single-Walled Carbon Nanotubes.

    Stubrov, Yurii; Nikolenko, Andrii; Gubanov, Viktor; Strelchuk, Viktor

    2016-12-01

    Micro-Raman spectra of single-walled carbon nanotubes in the range of two-phonon 2D bands are investigated in detail. The fine structure of two-phonon 2D bands in the low-temperature Raman spectra of the mixture and individual single-walled carbon nanotubes is considered as the reflection of structure of their π-electron zones. The dispersion behavior of 2D band fine structure components in the resonant Raman spectra of single-walled carbon nanotube mixture is studied depending on the energy of excitating photons. The role of incoming and outgoing electron-phonon resonances in the formation of 2D band fine structure in Raman spectra of single-walled carbon nanotubes is analyzed. The similarity of dispersion behavior of 2D phonon bands in single-walled carbon nanotubes, one-layer graphene, and bulk graphite is discussed. PMID:26729220

  8. Driven spatially auto resonant stimulated Raman scattering in the kinetic regime

    The auto resonant behavior of Langmuir waves excited by stimulated Raman scattering (SRS) is clearly identified in particle-in-cell (PIC) simulations in an inhomogeneous plasma. As previously shown via a 3-wave coupling model [T. Chapman et al., Phys. Plasmas 17, 122317 (2010)], weakly kinetic effects such as trapping can be described via an amplitude-dependent frequency shift that compensates the dephasing of the resonance of SRS due to the inhomogeneity. The autoresonance (AR) leads to phase locking and to growth of the Langmuir wave beyond the spatial amplification expected from Rosenbluth's model in an inhomogeneous profile [M. N. Rosenbluth, Phys. Rev. Lett. 29, 565 (1972)]. Results from PIC simulations and from a 3-wave coupling code show very good agreement, leading to the conclusion that AR arises even beyond the so-called weakly kinetic regime. (authors)

  9. Resonance Raman spectroscopy for human cancer detection of key molecules with clinical diagnosis

    Zhou, Yan; Liu, Cheng-hui; Li, Jiyou; Zhou, Lixin; He, Jingsheng; Sun, Yi; Pu, Yang; Zhu, Ke; Liu, Yulong; Li, Qingbo; Cheng, Gangge; Alfano, Robert R.

    2013-03-01

    Resonance Raman (RR) has the potential to reveal the differences between cancerous and normal breast and brain tissues in vitro. This differences caused by the changes of specific biomolecules in the tissues were displayed in resonance enhanced of vibrational fingerprints. It observed that the changes of reduced collagen contents and the number of methyl may show the sub-methylation of DNA in cancer cells. Statistical theoretical models of Bayesian, principal component analysis (PCA) and support vector machine (SVM) were used for distinguishing cancer from normal based on the RR spectral data of breast and meninges tissues yielding the diagnostic sensitivity of 80% and 90.9%, and specificity of 100% and 100%, respectively. The results demonstrated that the RR spectroscopic technique could be applied as clinical optical pathology tool with a high accuracy and reliability.

  10. Resonance Raman mapping as a tool to monitor and manipulate Si nanocrystals in Si-SiO2 nanocomposite

    Specially designed laser heating experiment along with Raman mapping on Si-SiO2 nanocomposites elucidates the contribution of core and surface/interface in the intermediate frequency range (511–514 cm−1) Si phonons. The contribution of core to surface/interface increases with the size of Si nanocrystal, which itself increases on laser irradiation. Further, it is found that resonance Raman is crucial to the observance of surface/interface phonons and wavelength dependent Raman mapping can be corroborated with band edges observed in absorption spectra. This understanding can be gainfully used to manipulate and characterize Si-SiO2 nanocomposite, simultaneously for photovoltaic device applications

  11. Atypical Exciton-Phonon Interactions in WS2 and WSe2 Monolayers Revealed by Resonance Raman Spectroscopy.

    Del Corro, E; Botello-Méndez, A; Gillet, Y; Elias, A L; Terrones, H; Feng, S; Fantini, C; Rhodes, Daniel; Pradhan, N; Balicas, L; Gonze, X; Charlier, J-C; Terrones, M; Pimenta, M A

    2016-04-13

    Resonant Raman spectroscopy is a powerful tool for providing information about excitons and exciton-phonon coupling in two-dimensional materials. We present here resonant Raman experiments of single-layered WS2 and WSe2 using more than 25 laser lines. The Raman excitation profiles of both materials show unexpected differences. All Raman features of WS2 monolayers are enhanced by the first-optical excitations (with an asymmetric response for the spin-orbit related XA and XB excitons), whereas Raman bands of WSe2 are not enhanced at XA/B energies. Such an intriguing phenomenon is addressed by DFT calculations and by solving the Bethe-Salpeter equation. These two materials are very similar. They prefer the same crystal arrangement, and their electronic structure is akin, with comparable spin-orbit coupling. However, we reveal that WS2 and WSe2 exhibit quite different exciton-phonon interactions. In this sense, we demonstrate that the interaction between XC and XA excitons with phonons explains the different Raman responses of WS2 and WSe2, and the absence of Raman enhancement for the WSe2 modes at XA/B energies. These results reveal unusual exciton-phonon interactions and open new avenues for understanding the two-dimensional materials physics, where weak interactions play a key role coupling different degrees of freedom (spin, optic, and electronic). PMID:26998817

  12. Resonance Raman study on indoleamine 2,3-dioxygenase: Control of reactivity by substrate-binding

    Highlights: • Indoleamine 2,3-dioygenase has been studied by resonance Raman spectroscopy. • Trp-binding to the enzyme induces high frequency shift of the Fe–His stretching mode. • Increased imidazolate character of histidine promotes the O–O bond cleavage step. • A fine-tuning of the reactivity of the O–O bond cleavage reaction is identified. • The results are consistent with the sequential oxygen-atom-transfer mechanism. - Abstract: Resonance Raman spectra of ligand-bound complexes including the 4-phenylimidazole complex and of free and L-Trp-bound forms of indoleamine 2, 3-dioxygenase in the ferric state were examined. Effects on the vinyl and propionate substituent groups of the heme were detected in a ligand-dependent fashion. The effects of phenyl group of 4-phenylimidazole on the vinyl and propionate Raman bands were evident when compared with the case of imidazole ligand. Substrate binding to the ferrous protein caused an upshift of the iron–histidine stretching mode by 3 cm−1, indicating an increase in negativity of the imidazole ring, which favors the O–O bond cleavage. The substrate binding event is likely to be communicated from the heme distal side to the iron–histidine bond through heme substituent groups and the hydrogen-bond network which includes water molecules, as identified in an X-ray structure of a 4-phenylimidazole complex. The results provide evidence for fine-tuning of the reactivity of O–O bond cleavage by the oxygenated heme upon binding of L-Trp

  13. Resonance Raman study on indoleamine 2,3-dioxygenase: Control of reactivity by substrate-binding

    Yanagisawa, Sachiko; Hara, Masayuki [Graduate School of Life Science and Picobiology Institute, University of Hyogo, Koto 3-2-1, Kamigori-cho, Ako-gun, Hyogo 678-1297 (Japan); Sugimoto, Hiroshi; Shiro, Yoshitsugu [Biometal Science Laboratory, RIKEN SPring-8 Center, Harima Institute, Koto 1-1-1, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Ogura, Takashi, E-mail: ogura@sci.u-hyogo.ac.jp [Graduate School of Life Science and Picobiology Institute, University of Hyogo, Koto 3-2-1, Kamigori-cho, Ako-gun, Hyogo 678-1297 (Japan)

    2013-06-20

    Highlights: • Indoleamine 2,3-dioygenase has been studied by resonance Raman spectroscopy. • Trp-binding to the enzyme induces high frequency shift of the Fe–His stretching mode. • Increased imidazolate character of histidine promotes the O–O bond cleavage step. • A fine-tuning of the reactivity of the O–O bond cleavage reaction is identified. • The results are consistent with the sequential oxygen-atom-transfer mechanism. - Abstract: Resonance Raman spectra of ligand-bound complexes including the 4-phenylimidazole complex and of free and L-Trp-bound forms of indoleamine 2, 3-dioxygenase in the ferric state were examined. Effects on the vinyl and propionate substituent groups of the heme were detected in a ligand-dependent fashion. The effects of phenyl group of 4-phenylimidazole on the vinyl and propionate Raman bands were evident when compared with the case of imidazole ligand. Substrate binding to the ferrous protein caused an upshift of the iron–histidine stretching mode by 3 cm{sup −1}, indicating an increase in negativity of the imidazole ring, which favors the O–O bond cleavage. The substrate binding event is likely to be communicated from the heme distal side to the iron–histidine bond through heme substituent groups and the hydrogen-bond network which includes water molecules, as identified in an X-ray structure of a 4-phenylimidazole complex. The results provide evidence for fine-tuning of the reactivity of O–O bond cleavage by the oxygenated heme upon binding of L-Trp.

  14. Single-molecular surface-enhanced resonance Raman scattering as a quantitative probe of local electromagnetic field: The case of strong coupling between plasmonic and excitonic resonance

    Itoh, Tamitake; Yamamoto, Yuko S.; Tamaru, Hiroharu; Biju, Vasudevanpillai; Wakida, Shin-ichi; Ozaki, Yukihiro

    2014-05-01

    We investigate electromagnetic coupling between plasmonic and molecular electronic resonances using single-molecular surface-enhanced resonance Raman scattering (SERRS) from single silver nanoparticle dimers. When dimers exhibit SERRS activity, their elastic light scattering spectra show two lines, which are temporally closing toward each other. The higher energy line eventually disappears at the time of SERRS quenching. A coupled-oscillator model composed of plasmonic and molecular electronic resonances consistently reproduces the above interesting results by decreasing coupling energy, indicating that SERRS can be a quantitative probe for strong coupling between the two resonances.

  15. Vibrational techniques applied to photosynthesis: Resonance Raman and fluorescence line-narrowing.

    Gall, Andrew; Pascal, Andrew A; Robert, Bruno

    2015-01-01

    Resonance Raman spectroscopy may yield precise information on the conformation of, and the interactions assumed by, the chromophores involved in the first steps of the photosynthetic process. Selectivity is achieved via resonance with the absorption transition of the chromophore of interest. Fluorescence line-narrowing spectroscopy is a complementary technique, in that it provides the same level of information (structure, conformation, interactions), but in this case for the emitting pigment(s) only (whether isolated or in an ensemble of interacting chromophores). The selectivity provided by these vibrational techniques allows for the analysis of pigment molecules not only when they are isolated in solvents, but also when embedded in soluble or membrane proteins and even, as shown recently, in vivo. They can be used, for instance, to relate the electronic properties of these pigment molecules to their structure and/or the physical properties of their environment. These techniques are even able to follow subtle changes in chromophore conformation associated with regulatory processes. After a short introduction to the physical principles that govern resonance Raman and fluorescence line-narrowing spectroscopies, the information content of the vibrational spectra of chlorophyll and carotenoid molecules is described in this article, together with the experiments which helped in determining which structural parameter(s) each vibrational band is sensitive to. A selection of applications is then presented, in order to illustrate how these techniques have been used in the field of photosynthesis, and what type of information has been obtained. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. PMID:25268562

  16. The first photoexcitation step of ruthenium-based models for artificial photosynthesis highlighted by resonance Raman spectroscopy.

    Herrmann, Carmen; Neugebauer, Johannes; Presselt, Martin; Uhlemann, Ute; Schmitt, Michael; Rau, Sven; Popp, Jürgen; Reiher, Markus

    2007-05-31

    Ruthenium-polypyridine and related complexes play an important role as models for light-harvesting antenna systems to be employed in artificial photosynthesis. In this theoretical and experimental work, the first photoexcitation step of a tetranuclear [Ru2Pd2] complex composed of two ruthenium-bipyridyl subunits and two palladium-based fragments, {[(tbbpy)2Ru(tmbi)]2[Pd(allyl)]2}2+ (tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine, tmbi = 5,6,5',6'-tetramethyl-2,2'-bibenzimidazolate), is investigated by means of experimental and theoretical resonance Raman spectroscopy. The calculated spectra, which were obtained within the short-time approximation combined with time-dependent density functional theory (TDDFT), reproduce the experimental spectrum with excellent agreement. We also compared calculations on off-resonance Raman spectra, for which a completely different theoretical approach has to be used, to experimental ones and again found very good agreement. The [Ru2Pd2] complex represents the probably largest system for which a quantum chemical frequency analysis and a calculation of conventional Raman as well as resonance Raman spectra with reasonable basis sets have been performed. A comparison between the resonance Raman spectra of the [Ru2Pd2] complex and its mononuclear [Ru] building block [(tbbpy)2Ru(tmbi)]2+ and a normal-mode analysis reveal that the [Ru2Pd2] resonance Raman spectrum is composed uniquely from peaks arising from the [Ru] fragment. This observation and an analysis of the Kohn-Sham orbitals mainly involved in the initial electronic excitation in the TDDFT description of the [Ru2Pd2] system support the hypothesis that the initial photoexcitation step of [Ru2Pd2] is a charge-transfer excitation from the ruthenium atoms to the adjacent butyl-2,2'-bipyridine ligands. PMID:17489631

  17. Measurement of nitric oxide concentrations in flames by using electronic-resonance-enhanced coherent anti-Stokes Raman scattering.

    Kulatilaka, Waruna D; Chai, Ning; Naik, Sameer V; Laurendeau, Normand M; Lucht, Robert P; Kuehner, Joel P; Roy, Sukesh; Gord, James R

    2006-11-15

    We have measured nitric oxide (NO) concentrations in flames by using electronic-resonance-enhanced coherent anti-Stokes Raman spectroscopy (ERE-CARS). Visible pump and Stokes beams were tuned to a Q-branch vibrational Raman resonance of NO. A UV probe beam was tuned into resonance with specific rotational transitions in the (v"=1,v'=0) vibrational band in the A(2)Sigma(+)-X(2)Pi electronic transition, thus providing a substantial electronic-resonance enhancement of the resulting CARS signal. NO concentrations were measured at levels down to 50 parts in 10(6) in H(2)/air flames at atmospheric pressure. NO was also detected in heavily sooting C(2)H(2)/air flames at atmospheric pressure with minimal background interference. PMID:17072422

  18. Resonant Raman x-ray scattering at the S 2p edge of iron pyrite

    The x-ray absorption and resonant inelastic x-ray spectra of iron pyrite (FeS2) have been measured at the S 2p edge and compared with published electronic structure calculations. A minimum in the x-ray absorption intensity interpreted as indicating a gap in the unoccupied density of states is found from about 4 to 6 eV above the bottom of the conduction band, in agreement with some recent calculations. Resonant Raman scattering conditions were set up at the onset of S 2p3/2 absorption and a constant energy loss peak at 1.9 eV was observed. This is assigned to transitions from occupied tg to unoccupied eg states, both of which are predominantly of Fe 3d character but hybridized with the S valence states. This demonstrates that Fe dd excitations can be probed via S 2p resonant spectroscopy, as has been done recently at the O 1s edge for oxide materials

  19. Elucidation of reactive wavepackets by two-dimensional resonance Raman spectroscopy

    Traditional second-order kinetic theories fail to describe sub-picosecond photochemical reactions when solvation and vibrational dephasing undermine the assumption of equilibrium initial conditions. Four-wave mixing spectroscopies may reveal insights into such non-equilibrium processes but are limited by the single “population time” available in these types of experiments. Here, we use two-dimensional resonance Raman (2DRR) spectroscopy to expose correlations between coherent nuclear motions of the reactant and product in the photodissociation reaction of triiodide. It is shown that the transition of a nuclear wavepacket from the reactant (triiodide) to product (diiodide) states gives rise to a unique pattern of 2DRR resonances. Peaks associated with this coherent reaction mechanism are readily assigned, because they are isolated in particular quadrants of the 2DRR spectrum. A theoretical model in which the chemical reaction is treated as a vibronic coherence transfer transition from triiodide to diiodide reproduces the patterns of 2DRR resonances detected in experiments. These signal components reveal correlation between the nonequilibrium geometry of triiodide and the vibrational coherence frequency of diiodide. The 2DRR signatures of coherent reaction mechanisms established in this work may generalize to studies of ultrafast energy and charge transfer processes

  20. Gold split-ring resonators (SRRs) as substrates for surface-enhanced raman scattering

    Yue, Weisheng

    2013-10-24

    We used gold split ring resonators (SRRs) as substrates for surface-enhanced Raman scattering (SERS). The arrays of SRRs were fabricated by electron-beam lithography in combination with plasma etching. In the detection of rhodamine 6G (R6G) molecules, SERS enhancement factors of the order of 105 was achieved. This SERS enhancement increased as the size of the split gap decrease as a consequence of the matching between the resonance wavelength of the SRRs and the excitation wavelength of SERS. As the size of the split gap decreased, the localized surface plasmon resonance shifted to near the excitation wavelength and, thus, resulted in the increase in the electric field on the nanostructures. We used finite integration method (FIT) to simulate numerically the electromagnetic properties of the SRRs. The results of the simulation agreed well with our experimental observations. We anticipate this work will provide an approach to manipulate the SERS enhancement by modulating the size of split gap with SRRs without affecting the area and structural arrangement. © 2013 American Chemical Society.

  1. Plasmon-resonant Raman spectroscopy in metallic nanoparticles: Surface-enhanced scattering by electronic excitations

    Carles, R.; Bayle, M.; Benzo, P.; Benassayag, G.; Bonafos, C.; Cacciato, G.; Privitera, V.

    2015-11-01

    Since the discovery of surface-enhanced Raman scattering (SERS) 40 years ago, the origin of the "background" that is systematically observed in SERS spectra has remained questionable. To deeply analyze this phenomenon, plasmon-resonant Raman scattering was recorded under specific experimental conditions on a panel of composite multilayer samples containing noble metal (Ag and Au) nanoparticles. Stokes, anti-Stokes, and wide, including very low, frequency ranges have been explored. The effects of temperature, size (in the nm range), embedding medium (SiO2, Si3N4, or TiO2) or ligands have been successively analyzed. Both lattice (Lamb modes and bulk phonons) and electron (plasmon mode and electron-hole excitations) dynamics have been investigated. This work confirms that in Ag-based nanoplasmonics composite layers, only Raman scattering by single-particle electronic excitations accounts for the background. This latter appears as an intrinsic phenomenon independently of the presence of molecules on the metallic surface. Its spectral shape is well described by revisiting a model developed in the 1990s for analyzing electron scattering in dirty metals, and used later in superconductors. The gs factor, that determines the effective mean-free path of free carriers, is evaluated, gsexpt=0.33 ±0.04 , in good agreement with a recent evaluation based on time-dependent local density approximation gstheor=0.32 . Confinement and interface roughness effects at the nanometer range thus appear crucial to understand and control SERS enhancement and more generally plasmon-enhanced processes on metallic surfaces.

  2. Status of miniature integrated UV resonance fluorescence and Raman sensors for detection and identification of biochemical warfare agents

    Hug, William F.; Bhartia, Rohit; Taspin, Alexandre; Lane, Arthur; Conrad, Pamela; Sijapati, Kripa; Reid, Ray D.

    2005-11-01

    Laser induced native fluorescence (LINF) is the most sensitive method of detection of biological material including microorganisms, virus', and cellular residues. LINF is also a sensitive method of detection for many non-biological materials as well. The specificity with which these materials can be classified depends on the excitation wavelength and the number and location of observation wavelengths. Higher levels of specificity can be obtained using Raman spectroscopy but a much lower levels of sensitivity. Raman spectroscopy has traditionally been employed in the IR to avoid fluorescence. Fluorescence rarely occurs at wavelength below about 270nm. Therefore, when excitation occurs at a wavelength below 250nm, no fluorescence background occurs within the Raman fingerprint region for biological materials. When excitation occurs within electronic resonance bands of the biological target materials, Raman signal enhancement over one million typically occurs. Raman sensitivity within several hundred times fluorescence are possible in the deep UV where most biological materials have strong absorption. Since the Raman and fluorescence emissions occur at different wavelength, both spectra can be observed simultaneously, thereby providing a sensor with unique sensitivity and specificity capability. We will present data on our integrated, deep ultraviolet, LINF/Raman instruments that are being developed for several applications including life detection on Mars as well as biochemical warfare agents on Earth. We will demonstrate the ability to discriminate organic materials based on LINF alone. Together with UV resonance Raman, higher levels of specificity will be demonstrated. In addition, these instruments are being developed as on-line chemical sensors for industrial and municipal waste streams and product quality applications.

  3. Raman and fluorescence characteristics of resonant inelastic X-ray scattering from doped superconducting cuprates.

    Huang, H Y; Jia, C J; Chen, Z Y; Wohlfeld, K; Moritz, B; Devereaux, T P; Wu, W B; Okamoto, J; Lee, W S; Hashimoto, M; He, Y; Shen, Z X; Yoshida, Y; Eisaki, H; Mou, C Y; Chen, C T; Huang, D J

    2016-01-01

    Measurements of spin excitations are essential for an understanding of spin-mediated pairing for superconductivity; and resonant inelastic X-ray scattering (RIXS) provides a considerable opportunity to probe high-energy spin excitations. However, whether RIXS correctly measures the collective spin excitations of doped superconducting cuprates remains under debate. Here we demonstrate distinct Raman- and fluorescence-like RIXS excitations of Bi1.5Pb0.6Sr1.54CaCu2O(8+δ). Combining photon-energy and momentum dependent RIXS measurements with theoretical calculations using exact diagonalization provides conclusive evidence that the Raman-like RIXS excitations correspond to collective spin excitations, which are magnons in the undoped Mott insulators and evolve into paramagnons in doped superconducting compounds. In contrast, the fluorescence-like shifts are due primarily to the continuum of particle-hole excitations in the charge channel. Our results show that under the proper experimental conditions RIXS indeed can be used to probe paramagnons in doped high-Tc cuprate superconductors. PMID:26794437

  4. Single- and few-layer WTe2 and their suspended nanostructures: Raman signatures and nanomechanical resonances

    Lee, Jaesung; Ye, Fan; Wang, Zenghui; Yang, Rui; Hu, Jin; Mao, Zhiqiang; Wei, Jiang; Feng, Philip X.-L.

    2016-04-01

    Single crystal tungsten ditelluride (WTe2) has recently been discovered to exhibit non-saturating extreme magnetoresistance in bulk; it has also emerged as a new layered material from which atomic layer crystals can be extracted. While atomically thin WTe2 is attractive for its unique properties, little research has been conducted on single- and few-layer WTe2. Here we report the isolation of single- and few-layer WTe2, as well as the fabrication and characterization of the first WTe2 suspended nanostructures. We have observed new Raman signatures of single- and few-layer WTe2 that have been theoretically predicted but have not been reported to date, in both on-substrate and suspended WTe2 flakes. We have further probed the nanomechanical properties of suspended WTe2 structures by measuring their flexural resonances, and obtain a Young's modulus of EY ~ 80 GPa for the suspended WTe2 flakes. This study paves the way for future investigations and utilizations of the multiple new Raman fingerprints of single- and few-layer WTe2, and for explorations of mechanical control of WTe2 atomic layers.

  5. Distinguishing Unfolding and Functional Conformational Transitions of Calmodulin Using Ultraviolet Resonance Raman Spectroscopy

    Jones, Eric M.; Balakrishnan, G.; Squier, Thomas C.; Spiro, Thomas

    2014-06-14

    Calmodulin (CaM) is a ubiquitous moderator protein for calcium signaling in all eukaryotic cells. This small calcium-binding protein exhibits a broad range of structural transitions, including domain opening and folding-unfolding, that allow it to recognize a wide variety of binding partners in vivo. While the static structures of CaM associated with its various binding activities are fairly well known, it has been challenging to examine the dynamics of transition between these structures in real-time, due to a lack of suitable spectroscopic probes of CaM structure. In this paper, we examine the potential of ultraviolet resonance Raman (UVRR) spectroscopy for clarifying the nature of structural transitions in CaM. We find that the UVRR spectral change (with 229 nm excitation) due to thermal unfolding of CaM is qualitatively different from that associated with opening of the C-terminal domain in response to Ca2+ binding. This spectral difference is entirely due to differences in teritary contacts at the inter-domain tyrosine residue Tyr138, toward which other spectroscopic methods are not sensitive. We conclude that UVRR is ideally suited to identifying the different types of structural transitions in CaM and other proteins with conformation-sensitive tyrosine residues, opening a path to time-resolved studies of CaM dynamics using Raman spectroscopy.

  6. Surface-Enhanced Resonance Raman Scattering and Visible Extinction Spectroscopy of Copper Chlorophyllin: An Upper Level Chemistry Experiment

    Schnitzer, Cheryl S.; Reim, Candace Lawson; Sirois, John J.; House, Paul G.

    2010-01-01

    Advanced chemistry students are introduced to surface-enhanced resonance Raman scattering (SERRS) by studying how sodium copper chlorophyllin (CuChl) adsorbs onto silver colloids (CuChl/Ag) as a function of pH. Using both SERRS and visible extinction spectroscopy, the extent of CuChl adsorption and colloidal aggregation are monitored. Initially at…

  7. Electron paramagnetic resonance and Raman scattering in the natural diamond crystal implanted with 335 MeV nickel ions

    The influence of implantation with nickel ions of energy 335 MeV on the paramagnetic properties and crystal structure at room temperature of the natural Ia diamond crystal has been studied by electron paramagnetic resonance (EPR) and Raman scattering methods. (authors)

  8. Operational electrochemical stability of thiophene-thiazole copolymers probed by resonant Raman spectroscopy

    Wade, Jessica; Wood, Sebastian; Kim, Ji-Seon, E-mail: ji-seon.kim@imperial.ac.uk [Department of Physics and Centre for Plastic Electronics, Imperial College London, London SW7 2AZ (United Kingdom); Beatrup, Daniel; Hurhangee, Michael; McCulloch, Iain; Durrant, James R. [Department of Chemistry and Centre for Plastic Electronics, Imperial College London, London SW7 2AY (United Kingdom); Bronstein, Hugo [Department of Chemistry and Centre for Plastic Electronics, Imperial College London, London SW7 2AY (United Kingdom); Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom)

    2015-06-28

    We report on the electrochemical stability of hole polarons in three conjugated polymers probed by resonant Raman spectroscopy. The materials considered are all isostructural to poly(3-hexyl)thiophene, where thiazole units have been included to systematically deepen the energy level of the highest occupied molecular orbital (HOMO). We demonstrate that increasing the thiazole content planarizes the main conjugated backbone of the polymer and improves the electrochemical stability in the ground state. However, these more planar thiazole containing polymers are increasingly susceptible to electrochemical degradation in the polaronic excited state. We identify the degradation mechanism, which targets the C=N bond in the thiazole units and results in disruption of the main polymer backbone conjugation. The introduction of thiazole units to deepen the HOMO energy level and increase the conjugated backbone planarity can be beneficial for the performance of certain optoelectronic devices, but the reduced electrochemical stability of the hole polaron may compromise their operational stability.

  9. Selective resonance enhancement of Raman scattering intensity in photoinduced nonradiative charge transfer

    Bairamov, B. Kh.

    2016-04-01

    This paper reports on the formation of complexes consisting of isolated free-standing crystalline semiconductor quantum dots, for example, nc-Si/SiO2, functionalized by short oligonucleotides, for example, the single-stranded system d(20G, 20T). Here, d are deoxyribonucleotides, G and T are guanine and thymine nucleotides, respectively. It has been found that these complexes are unique objects for the elucidation of the specific features in the manifestation of new quantum-size effects in biomacromolecules. It has been demonstrated that the possibility exists of detecting and recording, in such complexes of biomacromolecules, spectrally selective resonance enhancement of Raman scattering intensity in fluctuations of nucleotide molecules due to coherent nonradiative transfer of a photoexcited electron and a hole at the interface of the complex. This dynamic optical imaging of spectral responses can be of applied interest for the development of nanobiophotonic technologies.

  10. Operational electrochemical stability of thiophene-thiazole copolymers probed by resonant Raman spectroscopy

    We report on the electrochemical stability of hole polarons in three conjugated polymers probed by resonant Raman spectroscopy. The materials considered are all isostructural to poly(3-hexyl)thiophene, where thiazole units have been included to systematically deepen the energy level of the highest occupied molecular orbital (HOMO). We demonstrate that increasing the thiazole content planarizes the main conjugated backbone of the polymer and improves the electrochemical stability in the ground state. However, these more planar thiazole containing polymers are increasingly susceptible to electrochemical degradation in the polaronic excited state. We identify the degradation mechanism, which targets the C=N bond in the thiazole units and results in disruption of the main polymer backbone conjugation. The introduction of thiazole units to deepen the HOMO energy level and increase the conjugated backbone planarity can be beneficial for the performance of certain optoelectronic devices, but the reduced electrochemical stability of the hole polaron may compromise their operational stability

  11. Harmonic-seeded resonant Raman amplification in strong-field ionized nitrogen molecules

    Yao, Jinping; Tian, Chuanshan; Li, Ziting; Wang, Zhanshan; Cheng, Ya

    2016-01-01

    Generation of free-space laser-like emissions of high spatiotemporal coherence and narrow bandwidth in atmosphere opens promising opportunities for remote spectroscopic sensing. Here, we report on generation of such laser-like emissions, which results from the combined contributions of perturbative and non-perturbative nonlinear optical effects in nitrogen molecules exposed to intense mid-infrared laser fields. We systematically investigate the dependence of the generated free-space laser spectrum on wavelength and power of the driver laser. It is revealed that the free-space laser is produced by resonant Raman amplification of the fifth harmonic of the driver pulses in rotational wavepacket of the molecular nitrogen ions.

  12. Magnetic-bead-based sub-femtomolar immunoassay using resonant Raman scattering signals of ZnS nanoparticles.

    Ding, Yadan; Cong, Tie; Chu, Xueying; Jia, Yan; Hong, Xia; Liu, Yichun

    2016-07-01

    Highly sensitive, specific, and selective immunoassays are of great significance for not only clinical diagnostics but also food safety, environmental monitoring, and so on. Enzyme-linked immunosorbent assays and fluorescence-based and electrochemical immunoassays are important intensively investigated immunoassay techniques. However, they might suffer from low sensitivity or false-positive results. In this work, a simple, reliable, and ultrasensitive magnetic-bead-based immunoassay was performed using biofunctionalized ZnS semiconductor nanocrystals as resonant Raman probes. The resonant Raman scattering of ZnS nanocrystals displays evenly spaced multi-phonon resonant Raman lines with narrow bandwidths and has strong resistance to environmental variation due to the nature of the electron-phonon interaction, thus rendering reliable signal readout in the immunoassays. The superparamagnetic Fe3O4 nanoparticles facilitated greatly the separation, purification, and concentration processes. It is beneficial for both reducing the labor intensity and amplifying the detection signals. The immobilization of antibodies on the surface of magnetic beads, the preparation of resonant Raman probes, and the immunological recognition between the antibody and analyte all occurred in the liquid phase, which minimized the diffusion barriers and boundary layer constraints. All these factors contributed to the ultralow detection limit of human IgG, which was determined to be about 0.5 fM (∼0.08 pg/ml). It is nearly the highest sensitivity obtained for IgG detection. This work shall facilitate the design of nanoplatforms for ultrasensitive detections of proteins, DNAs, bacteria, explosives, and so on. Graphical abstract An ultrasensitive magnetic-bead-based immunoassay was performed using multi-phonon resonant Raman lines of ZnS nanoparticles as detection signals. PMID:27173389

  13. Surface origin and control of resonance Raman scattering and surface band gap in indium nitride

    Alarcón-Lladó, Esther; Brazzini, Tommaso; Ager, Joel W.

    2016-06-01

    Resonance Raman scattering measurements were performed on indium nitride thin films under conditions where the surface electron concentration was controlled by an electrolyte gate. As the surface condition is tuned from electron depletion to accumulation, the spectral feature at the expected position of the (E 1, A 1) longitudinal optical (LO) near 590 cm‑1 shifts to lower frequency. The shift is reversibly controlled with the applied gate potential, which clearly demonstrates the surface origin of this feature. The result is interpreted within the framework of a Martin double resonance, where the surface functions as a planar defect, allowing the scattering of long wavevector phonons. The allowed wavevector range, and hence the frequency, is modulated by the electron accumulation due to band gap narrowing. A surface band gap reduction of over 500 meV is estimated for the conditions of maximum electron accumulation. Under conditions of electron depletion, the full InN bandgap (E g  =  0.65 eV) is expected at the surface. The drastic change in the surface band gap is expected to influence the transport properties of devices which utilize the surface electron accumulation layer.

  14. Resonant photo-thermal modification of vertical gallium arsenide nanowires studied using Raman spectroscopy

    Walia, Jaspreet; Boulanger, Jonathan; Dhindsa, Navneet; LaPierre, Ray; (Shirley Tang, Xiaowu; Saini, Simarjeet S.

    2016-06-01

    Gallium arsenide nanowires have shown considerable promise for use in applications in which the absorption of light is required. When the nanowires are oriented vertically, a considerable amount of light can be absorbed, leading to significant heating effects. Thus, it is important to understand the threshold power densities that vertical GaAs nanowires can support, and how the nanowire morphology is altered under these conditions. Here, resonant photo-thermal modification of vertical GaAs nanowires was studied using both Raman spectroscopy and electron microscopy techniques. Resonant waveguiding, and subsequent absorption of the excited optical mode reduces the irradiance vertical GaAs nanowires can support relative to horizontal ones, by three orders of magnitude before the onset of structural changes occur. A power density of only 20 W mm‑2 was sufficient to induce local heating in the nanowires, resulting in the formation of arsenic species. Upon further increasing the power, a hollow nanowire morphology was realized. These findings are pertinent to all optical applications and spectroscopic measurements involving vertically oriented GaAs nanowires. Understanding the optical absorption limitations, and the effects of exceeding these limitations will help improve the development of all III–V nanowire devices.

  15. The dynamic Jahn-Teller effect in C60: Self-trapped excitons and resonant Raman scattering

    The dynamic Jahn-Teller problem is solved for the lowest triplet and singlet self-trapped excitons of C60. The resultant tunnel-split 3T3g+3T1g states provide a good explanation for the available experimental data on the lowest triple states. The observable consequences of this dynamical symmetry breaking in the photo-induced multi-phonon resonant Raman scattering are explored in detail. The tunneling splitting itself should show up in the Raman spectrum, and the depolarization ratio (which can be normal or unusual, depending on exciting frequencies) is calculated explicitly. (author). 28 refs, 2 figs

  16. Interfacing capillary electrophoresis and surface-enhanced resonance Raman spectroscopy for the determination of dye compounds.

    Arráez Román, D; Efremov, E; Ariese, F; Segura Carretero, A; Gooijer, C

    2005-05-01

    The at-line coupling of capillary electrophoresis (CE) and surface-enhanced resonance Raman spectroscopy (SERRS) was optimized for the separation and subsequent spectroscopic identification of charged analytes (dye compounds). Raman spectra were recorded following deposition of the electropherogram onto a moving substrate. To this end a new interface was developed using a stainless steel needle as a (grounded) cathode. The outlet end of the CE capillary was inserted into this metal needle; CE buffer touching the needle tip served as the electrical connection for the CE separation. A translation table was used to move the TLC plate at a constant speed during the deposition. The distance between the tip of the fused silica column and the TLC plate was kept as small as possible in order to establish a constant bridge-flow, while avoiding direct contact. The dyes Basic Red 9 (BR9), Acid Orange 7 (AO7) and Food Yellow 3 (FY3) were used as test compounds. After CE separation in a 20 mM borate buffer at pH 10, after deposition, concentrated silver colloid was added to each analyte spot, followed by irradiation with 514.5 nm light from an argon ion laser to record the SERRS signal using a Raman microscope. Different types of silver colloids were tested: Lee-Meisel type (citrate), borate, and gold-coated silver. BR9 (positively charged) gave much more intense SERRS spectra than the two negatively charged dyes. For BR9 and AO7 the citrate-coated Lee-Meisel colloid yielded the most intense SERRS spectra. The CE-SERRS system was used to separate and detect the negatively charged dyes. Silver colloid and nitric acid (to improve adsorption) were added post-deposition. Even though their chemical structures are very similar, AO7 and FY3 could be readily distinguished based on their SERRS spectra. The limits of detection (S/N = 3) of the CE-SERRS system ranged from 6.7 x 10(-5) M (2.6 x 10(-12) mol injected) for FY3 down to 1.8 x 10(-6) M (7.0 x 10(-14) mol injected) for BR9. PMID

  17. Implantation effects on resonant Raman scattering in CdTe and Cd 0.23Hg 0.77Te

    Ramsteiner, M.; Lusson, A.; Wagner, J.; Koidl, P.; Bruder, M.

    1990-04-01

    We have studied In + implanted CdTe and Cd 0.23Hg 0.77Te by resonant Raman scattering. The laser excitation was in resonance with the EO + Δ O band gap in CdTe or the E1 gap in Cd 0.23Hg 0.77Te. Under these conditions dipole forbidden but defect ind scattering by one longitudinal optical (LO) phonon as well as Fröhlich-induced two-LO phonon scattering is observed. In both cases scattering is found to be strongly affected by ion implantation. In + was implanted at an ion energy of 350 keV with doses ranging from 10 11 to 5×10 14 ions/cm 2. The intensity ratio of the one-LO phonon lines is found to be a quantitative measure of the implantation damage in CdTe and Cd 0.23Hg 0.77Te even for doses as low as 10 11 ions/cm 2. It is shown that the observed effects of implantation damage on resonant Raman scattering by LO phonons are due to a broadening and an energy shift of the corresponding resonances in the Raman scattering efficiency.

  18. In Vitro Polarized Resonance Raman Study of N719 and N719-TBP in Dye Sensitized Solar Cells

    Hassing, Søren; Jernshøj, Kit Drescher; Lund, Torben;

    2016-01-01

    experimental results on N719/TiO2 – DSCs that by combining an analysis of the wave number dependent polarization of these modes with the small shifts observed in the visible absorption spectra of adsorbed, non-adsorbed molecules and degradation products new and more reliable information about dye stability and...... about the adsorption of the dye on TiO2 can be obtained. Furthermore it is found that the polarization fluorescence anisotropy is very different for adsorbed and non-adsorbed dye molecules. This information is automatically obtained when processing the Raman data. The conclusion is that if the...... TiO2substrate applied FTIR,un-polarized Raman (RS) and un-polarized resonance Raman (RRS) spectroscopy. In the un-polarized RRS studies of N719/TiO2 – DSCs the discussion of the adsorption of N719 was based on the rather weak carbonyl or carboxyl group stretching vibrations and on minor spectral...

  19. Many particle approach to resonance Raman scattering in crystals: Strong electron-phonon interaction and multi-phonon processes

    Graphical abstract: Raman scattering (RS) of light by crystals was studied theoretically taking into account the electron-electron and electron-phonon interactions. The partial diagonalization of the Hamiltonian using unitary transformation was fulfilled. It allowed the structure of the many phonon repetition of bands to be described as a function of the electron-phonon interaction constant. It is shown that the spectral relations obtained for the scattering intensity can describe both the RS and the resonance RS (RRS) processes. Numerical modelling calculations for different parameters were carried out and comparisons with the experimental data for CdS and ZnO crystals were made. Highlights: → Raman scattering of light by crystals studied theoretically. → Electron-electron and electron-phonon interactions taken into account. → Structure of many phonon repetition of bands described. → Both Raman and resonance Raman scattering covered. → Comparisons with experimental data for CdS and ZnO crystals. - Abstract: Raman scattering (RS) of light by crystals was studied theoretically taking into account the electron-electron and electron-phonon interactions. The partial diagonalization of the Hamiltonian using unitary transformation was fulfilled. It allowed the structure of the many phonon repetition of bands to be described as a function of the electron-phonon interaction constant. It is shown that the spectral relations obtained for the scattering intensity can describe both the RS and the resonance RS (RRS) processes. Numerical modelling calculations for different parameters were carried out and comparisons with the experimental data for CdS and ZnO crystals were made.

  20. Resonance Raman imaging as a tool to assess the atmospheric pollution level: carotenoids in Lecanoraceae lichens as bioindicators.

    Ibarrondo, I; Prieto-Taboada, N; Martínez-Arkarazo, I; Madariaga, J M

    2016-04-01

    Raman spectroscopy differentiation of carotenoids has traditionally been based on the ν 1 position (C = C stretching vibrations in the polyene chain) in the 1500-1600 cm(-1) range, using a 785 nm excitation laser. However, when the number of conjugated double bonds is similar, as in the cases of zeaxanthin and β-carotene, this distinction is still ambiguous due to the closeness of the Raman bands. This work shows the Raman results, obtained in resonance conditions using a 514 mm laser, on Lecanora campestris and Lecanora atra species, which can be used to differentiate and consequently characterize carotenoids. The presence of the carotenoid found in Lecanoraceae lichens has been demonstrated to depend on the atmospheric pollution level of the environment they inhabit. Astaxanthin, a superb antioxidant, appears as the principal xanthophyll in highly polluted sites, usually together with the UV screening pigment scytonemin; zeaxanthin is the major carotenoid in medium polluted environments, while β-carotene is the major carotenoid in cleaner environments. Based on these observations, an indirect classification of the stress suffered in a given environment can be assessed by simply analysing the carotenoid content in the Lecanoraceae lichens by using resonance Raman imaging. PMID:26620863

  1. Identification of a hydroxide ligand at the iron center of ribonucleotide reductase by resonance Raman spectroscopy

    The resonance Raman spectrum of protein B2 of ribonucleotide reductase from Escherichia coli shows several features related to its oxo-bridged binuclear iron center. A peak at 492 cm-1 is assigned to the symmetric stretch of the Fe-O-Fe moiety on the basis of its 13-cm-1 shift to lower energy upon 18O substitution. The 18O species shows an additional peak at 731 cm-1, which is a good candidate for the asymmetric stretch of the Fe-O-Fe moiety. Its exact location in the 16O species is obscured by the presence of a protein tryptophan vibration at 758 cm-1. A third resonance-enhanced peak at 598 cm-1 is identified as an Fe-OH vibration on the basis of its 24-cm-1 shift to lower energy in H218O, its 2-cm-1 shift to lower energy in D2O, and its pH-dependent intensity. A hydrogen-bonded μ-oxo bridge similar to that in hemerythrin is suggested by the unusually low frequency for the Fe-O-Fe symmetric stretch and the 3-cm-1 shift to higher energy of nu/sub s/ (Fe-O-Fe), an Fe-O-Fe angle of 1380 can be calculated. This small angle suggests that the iron center consists of a tribridged core as in hemerythrin. A model for the binuclear iron center of ribonucleotide reductase is presented in which the hydroxide ligand sites provide an explanation for the half-of-sites reactivity of the enzyme

  2. Directly probing redox-linked quinones in photosystem II membrane fragments via UV resonance Raman scattering.

    Chen, Jun; Yao, Mingdong; Pagba, Cynthia V; Zheng, Yang; Fei, Liping; Feng, Zhaochi; Barry, Bridgette A

    2015-01-01

    In photosynthesis, photosystem II (PSII) harvests sunlight with bound pigments to oxidize water and reduce quinone to quinol, which serves as electron and proton mediators for solar-to-chemical energy conversion. At least two types of quinone cofactors in PSII are redox-linked: QA, and QB. Here, we for the first time apply 257-nm ultraviolet resonance Raman (UVRR) spectroscopy to acquire the molecular vibrations of plastoquinone (PQ) in PSII membranes. Owing to the resonance enhancement effect, the vibrational signal of PQ in PSII membranes is prominent. A strong band at 1661 cm(-1) is assigned to ring CC/CO symmetric stretch mode (ν8a mode) of PQ, and a weak band at 469 cm(-1) to ring stretch mode. By using a pump-probe difference UVRR method and a sample jet technique, the signals of QA and QB can be distinguished. A frequency difference of 1.4 cm(-1) in ν8a vibrational mode between QA and QB is observed, corresponding to ~86 mV redox potential difference imposed by their protein environment. In addition, there are other PQs in the PSII membranes. A negligible anharmonicity effect on their combination band at 2130 cm(-1) suggests that the 'other PQs' are situated in a hydrophobic environment. The detection of the 'other PQs' might be consistent with the view that another functional PQ cofactor (not QA or QB) exists in PSII. This UVRR approach will be useful to the study of quinone molecules in photosynthesis or other biological systems. PMID:25791219

  3. CD and UV Resonance Raman Indicate Little arg-glu Side Chain α-helix Peptide Stabilization

    Hong, Zhenmin; Ahmed, Zeeshan; Asher, Sanford A.

    2011-01-01

    Electrostatic interactions between side chains can control the conformation and folding of peptides and proteins. We used CD and UV resonance Raman spectroscopy (UVRR) to examine the impact of side chain charge on the conformations of two 21 residue mainly polyala peptides with a few arg and glu residues. We expected that attractions between arg-10 and glu-14 side chains would stabilize the α-helix conformation compared to a peptide with an arg-14. Surprisingly, CD suggests that the peptide w...

  4. Two-dimensional resonance Raman spectroscopy of oxygen- and water-ligated myoglobins

    Molesky, Brian P.; Guo, Zhenkun; Cheshire, Thomas P.; Moran, Andrew M.

    2016-07-01

    Two-dimensional resonance Raman (2DRR) spectroscopy has recently been developed as a tool for studies of structural heterogeneity and photochemical dynamics in condensed phases. In this paper, 2DRR spectroscopy is used to investigate line broadening mechanisms of both oxygen- and water-ligated myoglobins. General signatures of anharmonicity and inhomogeneous line broadening are first established with model calculations to facilitate signal interpretation. It is shown that the present quasi-degenerate version of 2DRR spectroscopy is insensitive to anharmonicity, because signal generation is allowed for harmonic modes. Rather, the key information to be gained from 2DRR spectroscopy pertains to the line broadening mechanisms, which are fairly obvious by inspection of the data. 2DRR signals acquired for both heme protein systems reveal significant heterogeneity in the vibrational modes local to the heme's propionic acid side chains. These side chains are known to interact with solvent, because they protrude from the hydrophobic pocket that encloses the heme. Molecular dynamics simulations suggest that the heterogeneity detected in our 2DRR experiments reflects fluctuations in the geometries of the side chains. Knowledge of such thermal motions will be useful for understanding protein function (e.g., ligand binding) because the side chains are an effective "gateway" for the exchange of thermal energy between the heme and solvent.

  5. Redox State of Cytochromes in Frozen Yeast Cells Probed by Resonance Raman Spectroscopy.

    Okotrub, Konstantin A; Surovtsev, Nikolay V

    2015-12-01

    Cryopreservation is a well-established technique used for the long-term storage of biological materials whose biological activity is effectively stopped under low temperatures (suspended animation). Since most biological methods do not work in a low-temperature frozen environment, the mechanism and details of the depression of cellular activity in the frozen state remain largely uncharacterized. In this work, we propose, to our knowledge, a new approach to study the downregulation of the redox activity of cytochromes b and c in freezing yeast cells in a contactless, label-free manner. Our approach is based on cytochrome photobleaching effects observed in the resonance Raman spectra of live cells. Photoinduced and native redox reactions that contributed to the photobleaching rate were studied over a wide temperature range (from -173 to +25 °C). We found that ice formation influences both the rate of cytochrome redox reactions and the balance between the reduced and oxidized cytochromes. We demonstrate that the temperature dependence of native redox reaction rates can be well described by the thermal activation law with an apparent energy of 32.5 kJ/mol, showing that the redox reaction rate is ∼10(15) times slower at liquid nitrogen temperature than at room temperature. PMID:26636934

  6. Generation of multi-hundred petawatt pulses by resonant Raman amplification in plasma

    Wu, Zhaohui; Zuo, Yanlei; Su, Jingqin; Liu, Lanqin; Zhang, Zhimeng; Li, Zhilin; Jiao, Zhihong; Wei, Xiaofeng

    2015-03-01

    Backward Raman amplification (BRA) in plasma has been proposed to produce overcritical high-power laser pulses. In this paper, an application based on CPA and BRA is promoted to generate multi-hundred petawatt laser pulses. The compression of short-wavelength (around 351 nm) and picosecond pulses has been proposed for high output intensity and short plasma length. This principle was employed in an application and a scheme is demonstrated using a full-kinetic particle-in-cell (PIC) code. The PIC code is also used to optimize key parameters in the resonant interaction. According to the simulated result using optimized parameters, the output seed fluence is amplified to 6.5 kJ/cm2 and the full-width at half-maximum duration is compressed to 13 fs, showing an energy transfer over 60%. Extending the result to the multidimensional case, a total energy of 3.9 kJ and a laser power of 300 PW are achievable, in a 0.6 cm2 interaction spot. This result is helpful for the improvement of high-energy density physics.

  7. Temperature dependence of the resonance Raman spectra of plastocyanin and azurin between cryogenic and ambient conditions. [Pseudomonas; Spinacea oleracea

    Woodruff, W.H.; Norton, K.A.; Swanson, B.I.; Fry, H.A.

    1984-02-01

    Resonance Raman spectra of spinach plastocyanin and Pseudomonas aeruginosa azurin were studied as a function of temperature between 10 K and 300 K. The spectra are markedly improved both in signal/noise ratio and in resolution at low temperatures. The assignments of the resonance Raman-active vibrations are reinterpreted in view of the number and intensities of peaks observed in the low-temperature spectra. Features appear in the low-temperature spectra of azurin that may be due to copper-bound methionine. The plastocyanin spectra undergo a transition between 220 K and the melting point of water that results in dramatically narrowed peaks at lower temperature and a shift in the carbon-sulfur stretching frequency of the copper-bound cysteine, suggesting a structural change in the active site and an accompanying effect on vibrational dephasing. Considering that the structures and nonvibrational spectroscopies of these two proteins are similar, the substantial differences in the resonance Raman spectra are striking and significant. 40 references, 3 figures, 1 table.

  8. Time-resolved resonance Raman spectroscopy of 1,3,5-hexatrienes in the lowest excited triplet state. The potential energy surface in T1

    Wilbrandt, R; Langkilde, F.W.; Brouwer, A.M.; Negri, F; Orlandi, G.

    1990-01-01

    Time-resolved resonance Raman spectroscopy is applied to the study of the T1 state of 1,3,5-hexatriene and deuteriated and methylated derivatives in solution. The technique is described briefly. The experimentally obtained resonance Raman spectra are discussed in the light of theoretical Quantum Chemical Force Field calculations. Implications for the potential energy surface of the T1 state are discussed.

  9. Fano resonance of Li-doped KTa1-xNbxO3 single crystals studied by Raman scattering.

    Rahaman, M M; Imai, T; Sakamoto, T; Tsukada, S; Kojima, S

    2016-01-01

    The enhancement of functionality of perovskite ferroelectrics by local structure is one of current interests. By the Li-doping to KTa1-xNbxO3 (KTN), the large piezoelectric and electro-optic effects were reported. In order to give new insights into the mechanism of doping, the microscopic origin of the Fano resonance induced by the local structure was investigated in 5%Li-doped KTN single crystals by Raman scattering. The coupling between the continuum states and the transverse optical phonon near 196 cm(-1) (Slater mode) caused a Fano resonance. In the vicinity of the cubic-tetragonal phase transition temperature, TC-T = 31 °C, the almost disappearance of the Fano resonance and the remarkable change of the central peak (CP) intensity were observed upon heating. The local symmetry of the polar nanoregions (PNRs), which was responsible for the symmetry breaking in the cubic phase, was determined to E(x, y) symmetry by the angular dependence of Raman scattering. The electric field induced the significant change in the intensity of both CP and Fano resonance. From these experimental results, it is concluded that the origin of the Fano resonance in Li-doped KTN crystals is the coupling between polarization fluctuations of PNRs and the Slater mode, both belong to the E(x, y) symmetry. PMID:27049847

  10. Effects of Cation Disordering in Magnesium Aluminate Spinel on the Rectangular Parallelepiped Resonance and Raman Measurements of Vibrational Spectra

    Cynn, Hyunchae

    The effects of cation disordering of a natural MgAl_2O_4^inel on acoustic and optic vibration were measured for the first time using the rectangular parallelepiped resonance method and Raman measurements. In the resonant frequency measurements of a natural spinel at high temperatures over the temperature range 298 to 1068 K, a discontinuous increase in the measured acoustic resonant vibrations of the lower harmonic modes and a discontinuous decrease in the measured acoustic resonant vibrations of the higher harmonic modes were observed at around 1000 K. Similar differences among the resonant frequencies were also observed at ambient conditions between a less disordered spinel and the highly disordered states of a natural spinel. In the Raman measurements of the same natural spinel over the temperature range 298 to 1424 K, plots of the Raman vibrational frequencies of the external and internal vibrational modes versus temperature change slopes at around 1000 K. These two measurements clearly indicate that a major change occurred at 1000 K, which I label as a transition temperature. I interpret the change that occurred around 1000 K as the onset of cation disordering in the natural spinel. The interpretation is consistent with the following observations: (1) an abrupt decrease in oxygen positional parameter in an x-ray single crystal structure analysis of a synthetic spinel between 873 and 973 K; (2) a discontinuous decrease of linear thermal expansion coefficients in a synthetic spinel at 933 K by dilatometry, and (3) a discontinuous decrease of the unit cell parameter of a natural spinel at around 1073 K by x-ray diffraction. The adiabatic elastic moduli found here for the natural spinel are different from results which have been previously reported by others, however, the moduli of a disordered natural spinel are similar to those previously reported for synthetic spinels. These observations demonstrate that cation disordering of a spinel clearly affects the

  11. Resonant Raman spectroscopy study of swift heavy ion irradiated MoS2

    Guo, Hang; Sun, Youmei; Zhai, Pengfei; Zeng, Jian; Zhang, Shengxia; Hu, Peipei; Yao, Huijun; Duan, Jinglai; Hou, Mingdong; Liu, Jie

    2016-08-01

    Molybdenum disulphide (MoS2) crystal samples were irradiated by swift heavy ions (209Bi and 56Fe). Hillock-like latent tracks were observed on the surface of irradiated MoS2 by atomic force microscopy. The modifications of properties of irradiated MoS2 were investigated by resonant Raman spectroscopy and ultraviolet-visible spectroscopy (UV-Vis). A new peak (E1u2, ∼385.7 cm-1) occurs near the in-plane E2g1 peak (∼383.7 cm-1) after irradiation. The two peaks shift towards lower frequency and broaden due to structural defects and stress with increasing fluence. When irradiated with high fluence, two other new peaks appear at ∼ 190 and ∼ 230 cm-1. The peak at ∼230 cm-1 is disorder-induced LA(M) mode. The presence of this mode indicates defects induced by irradiation. The feature at ∼460 cm-1 is composed of 2LA(M) (∼458 cm-1) and A2u (∼466 cm-1) mode. With increasing fluence, the integrated intensity ratio between 2LA(M) and A2u increases. The relative enhancement of 2LA(M) mode is in agreement with the appearance of LA(M) mode, which both demonstrate structural disorder in irradiated MoS2. The ∼423-cm-1 peak shifts toward lower frequency due to the decrease in exciton energy of MoS2, and this was demonstrated by the results of UV-Vis spectra. The decrease in exciton energy could be due to introduction of defect levels into band gap.

  12. Resonance Raman study of the oxygenation cycle of optically trapped single red blood cells in a microfluidic system

    Ramser, Kerstin; Logg, Katarina; Enger, Jonas; Goksor, Mattias; Kall, Mikael; Hanstorp, Dag

    2004-10-01

    The average environmental response of red blood cells (RBCs) is routinely measured in ensemble studies, but in such investigations valuable information on the single cell level is obscured. In order to elucidate this hidden information is is important to enable the selection of single cells with certain properties while subsequent dynamics triggered by environmental stimulation are recorded in real time. It is also desirable to manipulate and control the cells under phsyiological conditions. As shown here, this can be achieved by combining optical tweezers with a confocal Raman set-up equipped with a microfluidic system. A micro-Raman set-up is combined with an optical trap with separate optical paths, lasers and objectives, which enables the acquisition of resonance Raman profils of single RBCs. The microfluidic system, giving full control over the media surrounding the cell, consists of a pattern of channels and reservoirs produced by electron beam lithography and moulded in PDMS. Fresh Hepes buffer or buffer containing sodium dithionite are transported through the channels using electro-osmotic flow, while the direct Raman response of the single optically trapped RBC is registered in another reservoir in the middle of the channel. Thus, it is possible to monitor the oxygenation cycle in a single cell and to study photo-induced chemistry. This experimental set-up has high potential for monitoring the drug response or conformational changes caused by other environmental stimuli for many types of single functional cells since "in vivo" conditions can be created.

  13. Raman Regime Energy Dependence of Alignment and Orientation of KrIi States Populated by Resonant Auger Effect

    Lagutin, B. M.; Petrov, I. D.; Sukhorukov, V. L.; Kammer, S.; Mickat, S.; Schill, R.; Schartner, K.-H.; Ehresmann, A.; Shutov, Yu. A.; Schmoranzer, H.

    2003-02-01

    The energy dependencies of alignment parameters A20 for KrII 4p45p states after the Auger decay of the KrI 3d9np resonances were investigated theoretically and experimentally for the first time in the Raman regime with the bandwidth of the exciting radiation (ΔEFWHM=20 meV) smaller than the natural width of the resonances (Γ≈80 meV). The observed energy dependence is due to the in­terference between the different resonance channels and the direct photoionization channel. A strong energy dependence for both the orientation parameter O10 and the photoelectron angular distribution parameter βel is also predicted.

  14. Temperature evolution of the band gap in BiFeO3 traced by resonant Raman scattering

    Weber, Mads Christof; Guennou, Mael; Toulouse, Constance; Cazayous, Maximilien; Gillet, Yannick; Gonze, Xavier; Kreisel, Jens

    2016-03-01

    Knowledge of the electronic band structure of multiferroic oxides, crucial for the understanding and tuning of photoinduced effects, remains very limited even in the model and thoroughly studied BiFeO3. Here, we investigate the electronic band structure of BiFeO3 using Raman scattering with twelve different excitation wavelengths ranging from the blue to the near infrared. We show that resonant Raman signatures can be assigned to direct and indirect electronic transitions, as well as in-gap electronic levels, most likely associated with oxygen vacancies. Their temperature evolution establishes that the remarkable and intriguing variation of the optical band gap can be related to the shrinking of an indirect electronic band gap, while the energies for direct electronic transitions remains nearly temperature independent.

  15. Electron paramagnetic resonance and Raman spectroscopy studies on carbon-doped MgB{sub 2} superconductor nanomaterials

    Bateni, Ali; Somer, Mehmet, E-mail: emre.erdem@physchem.uni-freiburg.de, E-mail: msomer@ku.edu.tr [Department of Chemistry, Koc University, RumelifeneriYolu, Sariyer, Istanbul (Turkey); Erdem, Emre, E-mail: emre.erdem@physchem.uni-freiburg.de, E-mail: msomer@ku.edu.tr; Repp, Sergej; Weber, Stefan [Institut für Physikalische Chemie, Universität Freiburg, Albertstr. 21, 79104 Freiburg (Germany); Acar, Selcuk; Kokal, Ilkin [Pavezyum Kimya Sanayi Dış Ticaret LTD. ŞTI., Tuzla, Istanbul (Turkey); Häßler, Wolfgang [Leibniz Institute for Solid State and Materials Research Dresden (IFW), P.O. Box 270116, 01171 Dresden (Germany)

    2015-04-21

    Undoped and carbon-doped magnesium diboride (MgB{sub 2}) samples were synthesized using two sets of mixtures prepared from the precursors, amorphous nanoboron, and as-received amorphous carbon-doped nanoboron. The microscopic defect structures of carbon-doped MgB{sub 2} samples were systematically investigated using X-ray powder diffraction, Raman and electron paramagnetic resonance spectroscopy. Mg vacancies and C-related dangling-bond active centers could be distinguished, and sp{sup 3}-hybridized carbon radicals were detected. A strong reduction in the critical temperature T{sub c} was observed due to defects and crystal distortion. The symmetry effect of the latter is also reflected on the vibrational modes in the Raman spectra.

  16. Quantum-mechanical analysis of the intensity distribution in spectra of resonant Raman scattering spectra of aqueous solutions of tyrosine

    Burova, T. G.; Shcherbakov, R. S.

    2016-05-01

    Quantum-mechanical calculations of the intensity distribution in the resonant Raman scattering spectra of aqueous solutions of tyrosine excited by laser radiation with wavelengths of 244, 229, 218, 200, and 193 nm, as well as in the nonresonant Raman scattering spectrum excited at a wavelength of 488 nm, are performed. Satisfactory agreement is achieved between the calculation results and the experimental data. It is shown that the changes in the intensity distribution observed in the spectra with a change in the excitation wavelength from 244 to 193 nm correlate with the determined changes in the contribution made by excited electronic states into the scattering tensor components. It is noted that it is necessary to take into account the Herzberg-Teller effect and that the number of excited electronic states taken into account considerably affects the calculated relative intensities of lines. The possibility of existence of several tyrosine conformers in aqueous solution at room temperature is shown.

  17. Electron paramagnetic resonance and Raman spectroscopy studies on carbon-doped MgB2 superconductor nanomaterials

    Undoped and carbon-doped magnesium diboride (MgB2) samples were synthesized using two sets of mixtures prepared from the precursors, amorphous nanoboron, and as-received amorphous carbon-doped nanoboron. The microscopic defect structures of carbon-doped MgB2 samples were systematically investigated using X-ray powder diffraction, Raman and electron paramagnetic resonance spectroscopy. Mg vacancies and C-related dangling-bond active centers could be distinguished, and sp3-hybridized carbon radicals were detected. A strong reduction in the critical temperature Tc was observed due to defects and crystal distortion. The symmetry effect of the latter is also reflected on the vibrational modes in the Raman spectra

  18. Polarized resonance Raman spectroscopy of single-wall carbon nanotubes within a polymer under strain

    Frogley, M. D.; Zhao, Q.; Wagner, H. D.

    2002-03-01

    The D* Raman band of single-wall carbon nanotubes aligned by shear flow in a polymer matrix has been measured as a function of tensile strain. The Raman intensity varies with the optical polarization direction, an effect which is used here to assess the degree of tube alignment. The strain dependence of the Raman shift depends strongly on the nanotube orientation and the polarization direction. We show that, using polarized light, unoriented nanotubes can be used as strain sensors so that no tube alignment is necessary and the strain can be measured in all directions in a single sample.

  19. Magnetic immunoassay for cancer biomarker detection based on surface-enhanced resonance Raman scattering from coupled plasmonic nanostructures.

    Rong, Zhen; Wang, Chongwen; Wang, Junfeng; Wang, Donggen; Xiao, Rui; Wang, Shengqi

    2016-10-15

    A surface-enhanced resonance Raman scattering (SERRS) sensor was developed for the ultrasensitive detection of cancer biomarkers. Capture antibody-coated silver shell magnetic nanoparticles (Fe3O4@Ag MNPs) were utilized as the CEA enrichment platform and the SERRS signal amplification substrate. Gold nanorods (AuNRs) were coated with a thin silver shell to be in resonance with the resonant Raman dye diethylthiatricarbocyanine iodide (DTTC) and the excitation wavelength at 785nm. The silver-coated AuNRs (Au@Ag NRs) were then modified with detection antibody as the SERRS tags. Sandwich immune complexes formed in the presence of the target biomarker carcinoembryonic antigen (CEA), and this formation induced the plasmonic coupling between the Au@Ag NRs and Fe3O4@Ag MNPs. The SERRS signal of DTTC molecules located in the coupled plasmonic nanostructures was significantly enhanced. As a result, the proposed SERRS sensor was able to detect CEA with a low limit of detection of 4.75fg/mL and a wide dynamic linear range from 10fg/mL to 100ng/mL. The sensor provides a novel SERRS strategy for trace analyte detection and has a potential for clinical applications. PMID:27149164

  20. Light-Driven Reconfiguration of a Xanthophyll Violaxanthin in the Photosynthetic Pigment-Protein Complex LHCII: A Resonance Raman Study.

    Grudzinski, Wojciech; Janik, Ewa; Bednarska, Joanna; Welc, Renata; Zubik, Monika; Sowinski, Karol; Luchowski, Rafal; Gruszecki, Wieslaw I

    2016-05-19

    Resonance Raman analysis of the photosynthetic complex LHCII, immobilized in a polyacrylamide gel, reveals that one of the protein-bound xanthophylls, assigned as violaxanthin, undergoes light-induced molecular reconfiguration. The phototransformation is selectively observed in a trimeric structure of the complex and is associated with a pronounced twisting and a trans-cis molecular configuration change of the polyene chain of the carotenoid. Among several spectral effects accompanying the reconfiguration there are ones indicating a carotenoid triplet state. Possible physiological importance of the light-induced violaxanthin reconfiguration as a mechanism associated with making the pigment available for enzymatic deepoxidation in the xanthophyll cycle is discussed. PMID:27133785

  1. Resonance Raman spectra of an O2-binding H-NOX domain reveal heme relaxation upon mutation†

    Tran, Rosalie; Boon, Elizabeth M.; Marletta, Michael A.; Mathies, Richard A.

    2009-01-01

    Resonance Raman spectra are measured for Tt H-NOX WT and three other Tt H-NOX proteins containing mutations at key conserved residues to determine the heme conformation in solution. The most dramatic changes in heme conformation occurred in the O2-bound forms, and the single Tt H-NOX P115A mutation was sufficient to generate a significant relaxation of the chromophore. Clear evidence of heme relaxation in the Tt H-NOX I5L, P115A, and I5L/P115A mutants in solution is demonstrated by the observ...

  2. Optical pathology of human brain metastasis of lung cancer using combined resonance Raman and spatial frequency spectroscopies

    Zhou, Yan; Liu, Cheng-hui; Pu, Yang; Cheng, Gangge; Zhou, Lixin; Chen, Jun; Zhu, Ke; Alfano, Robert R.

    2016-03-01

    Raman spectroscopy has become widely used for diagnostic purpose of breast, lung and brain cancers. This report introduced a new approach based on spatial frequency spectra analysis of the underlying tissue structure at different stages of brain tumor. Combined spatial frequency spectroscopy (SFS), Resonance Raman (RR) spectroscopic method is used to discriminate human brain metastasis of lung cancer from normal tissues for the first time. A total number of thirty-one label-free micrographic images of normal and metastatic brain cancer tissues obtained from a confocal micro- Raman spectroscopic system synchronously with examined RR spectra of the corresponding samples were collected from the identical site of tissue. The difference of the randomness of tissue structures between the micrograph images of metastatic brain tumor tissues and normal tissues can be recognized by analyzing spatial frequency. By fitting the distribution of the spatial frequency spectra of human brain tissues as a Gaussian function, the standard deviation, σ, can be obtained, which was used to generate a criterion to differentiate human brain cancerous tissues from the normal ones using Support Vector Machine (SVM) classifier. This SFS-SVM analysis on micrograph images presents good results with sensitivity (85%), specificity (75%) in comparison with gold standard reports of pathology and immunology. The dual-modal advantages of SFS combined with RR spectroscopy method may open a new way in the neuropathology applications.

  3. Observation of structural relaxation during exciton self-trapping via excited-state resonant impulsive stimulated Raman spectroscopy

    We detect the change in vibrational frequency associated with the transition from a delocalized to a localized electronic state using femtosecond vibrational wavepacket techniques. The experiments are carried out in the mixed-valence linear chain material [Pt(en)2][Pt(en)2Cl2]⋅(ClO4)4 (en = ethylenediamine, C2H8N2), a quasi-one-dimensional system with strong electron-phonon coupling. Vibrational spectroscopy of the equilibrated self-trapped exciton is carried out using a multiple pulse excitation technique: an initial pump pulse creates a population of delocalized excitons that self-trap and equilibrate, and a time-delayed second pump pulse tuned to the red-shifted absorption band of the self-trapped exciton impulsively excites vibrational wavepacket oscillations at the characteristic vibrational frequencies of the equilibrated self-trapped exciton state by the resonant impulsive stimulated Raman mechanism, acting on the excited state. The measurements yield oscillations at a frequency of 160 cm−1 corresponding to a Raman-active mode of the equilibrated self-trapped exciton with Pt-Cl stretching character. The 160 cm−1 frequency is shifted from the previously observed wavepacket frequency of 185 cm−1 associated with the initially generated exciton and from the 312 cm−1 Raman-active symmetric stretching mode of the ground electronic state. We relate the frequency shifts to the changes in charge distribution and local structure that create the potential that stabilizes the self-trapped state

  4. Detection of aniline oligomers on polyaniline-gold interface using resonance Raman scattering

    Trchová, Miroslava; Morávková, Zuzana; Dybal, Jiří; Stejskal, Jaroslav

    2014-01-01

    Roč. 6, č. 2 (2014), s. 942-950. ISSN 1944-8244 R&D Projects: GA ČR GAP205/12/0911; GA ČR(CZ) GA13-00270S Institutional support: RVO:61389013 Keywords : polyaniline * aniline oligomers * Raman spectroscopy Subject RIV: CD - Macromolecular Chemistry Impact factor: 6.723, year: 2014

  5. Raman spectroelectrochemistry of index-identified metallic carbon nanotubes: the resonance rule revisited

    Kavan, Ladislav; Kalbáč, Martin; Zukalová, Markéta; Dunsch, L.

    2006-01-01

    Roč. 243, č. 13 (2006), s. 3130-3133. ISSN 0370-1972 R&D Projects: GA MŠk LC510; GA AV ČR IAA4040306 Institutional research plan: CEZ:AV0Z40400503 Keywords : electrochemistry * Raman spectroelectrochemistry * radial breathing mode Subject RIV: CG - Electrochemistry Impact factor: 0.967, year: 2006

  6. Dynamics of Rhodobacter capsulatus [2Fe-2S] Ferredoxin VI and Aquifex aeolicus Ferredoxin 5 Via Nuclear Resonance Vibrational Spectroscopy (NRVS) and Resonance Raman Spectroscopy.

    Xiao, Yuming; Tan, Ming-Liang; Ichiye, Toshiko; Wang, Hongxin; Guo, Yisong; Smith, Matt C.; Meyer, Jacques; Sturhahn, Wolfgang; Alp, E. E.; Zhao, Jiyong; Yoda, Yoshitaka; Cramer, Stephen P.

    2008-06-24

    We have used (57)Fe nuclear resonance vibrational spectroscopy (NRVS) to study the Fe(2)S(2)(Cys)(4) sites in oxidized and reduced [2Fe-2S] ferredoxins from Rhodobacter capsulatus (Rc FdVI) and Aquifex aeolicus (Aa Fd5). In the oxidized forms, nearly identical NRVS patterns are observed, with strong bands from Fe-S stretching modes peaking around 335 cm(-1), and additional features observed as high as the B(2u) mode at approximately 421 cm(-1). Both forms of Rc FdVI have also been investigated by resonance Raman (RR) spectroscopy. There is good correspondence between NRVS and Raman frequencies, but because of different selection rules, intensities vary dramatically between the two kinds of spectra. For example, the B(3u) mode at approximately 288 cm(-1), attributed to an asymmetric combination of the two FeS(4) breathing modes, is often the strongest resonance Raman feature. In contrast, it is nearly invisible in the NRVS, as there is almost no Fe motion in such FeS(4) breathing. NRVS and RR analysis of isotope shifts with (36)S-substituted into bridging S(2-) ions in Rc FdVI allowed quantitation of S(2-) motion in different normal modes. We observed the symmetric Fe-Fe stretching mode at approximately 190 cm(-1) in both NRVS and RR spectra. At still lower energies, the NRVS presents a complex envelope of bending, torsion, and protein modes, with a maximum at 78 cm(-1). The (57)Fe partial vibrational densities of states (PVDOS) were interpreted by normal-mode analysis with optimization of Urey-Bradley force fields. Progressively more complex D(2h) Fe(2)S(2)S'(4), C(2h) Fe(2)S(2)(SCC)(4), and C(1) Fe(2)S(2)(Cys)(4) models were optimized by comparison with the experimental spectra. After modification of the CHARMM22 all-atom force field by the addition of refined Fe-S force constants, a simulation employing the complete protein structure was used to reproduce the PVDOS, with better results in the low frequency protein mode region. This process was then repeated

  7. Photoinduced intermolecular electron transfer and off-resonance Raman characteristics of Rhodamine 101/N,N-diethylaniline

    Highlights: • Mechanism of PIET reaction process for the Rh101+/DEA system is investigated. • The significant geometrical changes of the charge–transfer complex are explained. • Forward Electron transfer from DEA to Rh101+∗ occurs with lifetime of 425–560 fs. • Backward electron transfer occurs with a time constant of 46.16–51.40 ps. • Intramolecular vibrational relaxation occurs with lifetime of 2.77–5.39 ps. - Abstract: The ultrafast photoinduced intermolecular electron transfer (PIET) reaction of Rhodamine 101 (Rh101+) in N,N-diethylaniline (DEA) was investigated using off-resonance Raman, femtosecond time-resolved multiplex transient grating (TG) and transient absorption (TA) spectroscopies. The Raman spectra indicate that the C=C stretching vibration of the chromophore aromatic ring is more sensitive to ET compared with the C-C stretching mode. The ultrafast photoinduced intermolecular forward ET (FET) from DEA to Rh101+∗ occurs on a time scale of τFET = 425–560 fs. The backward ET (BET) occurs in the inverted region with a time constant of τBET = 46.16–51.40 ps. The intramolecular vibrational relaxation (IVR) process occurs on the excited state potential energy surface with the time constant of τIVR = 2.77–5.39 ps

  8. Optically confined polarized resonance Raman studies in identifying crystalline orientation of sub-diffraction limited AlGaN nanostructure

    An optical characterization tool of Raman spectroscopy with extremely weak scattering cross section tool is not popular to analyze scattered signal from a single nanostructure in the sub-diffraction regime. In this regard, plasmonic assisted characterization tools are only relevant in spectroscopic studies of nanoscale object in the sub-diffraction limit. We have reported polarized resonance Raman spectroscopic (RRS) studies with strong electron-phonon coupling to understand the crystalline orientation of a single AlGaN nanowire of diameter ∼100 nm. AlGaN nanowire is grown by chemical vapor deposition technique using the catalyst assisted vapor-liquid-solid process. The results are compared with the high resolution transmission electron microscopic analysis. As a matter of fact, optical confinement effect due to the dielectric contrast of nanowire with respect to that of surrounding media assisted with electron-phonon coupling of RRS is useful for the spectroscopic analysis in the sub-diffraction limit of 325 nm (λ/2N.A.) using an excitation wavelength (λ) of 325 nm and near ultraviolet 40× far field objective with a numerical aperture (N.A.) value of 0.50

  9. Guided-Mode Resonance Grating with Self-Assembled Silver Nanoparticles for Surface-Enhanced Raman Scattering Spectroscopy

    Jing Yang

    2014-10-01

    Full Text Available We designed and fabricated guided-mode resonance (GMR gratings on indium-tin-oxide (ITO thin film to generate a significantly enhanced local electric field for surface-enhanced Raman scattering (SERS spectroscopy. Ag nanoparticles (NPs were self-assembled onto the surface of the grating, which can provide a large amount of “hot-spots” for SERS sensing. The ITO gratings also exhibit excellent tolerance to fabrication deviations due to the large refractive index contrast of the ITO grating. Quantitative experimental results of 5,5’-dithiobis(2-nitrobenzoic acid (DTNB demonstrate the best enhancement factor of ~14× on ITO gratings when compared with Ag NPs on a flat ITO film, and the limit of detection (LOD of DTNB is as low as 10 pM.

  10. Electronic many-body effects at metal-organic interfaces studied with PES, NEXAFS and resonant Auger Raman spectroscopy

    Haeming, M.; Schoell, A.; Reinert, F. [Universitaet Wuerzburg, Experimentelle Physik VII, D-97074 Wuerzburg (Germany); Umbach, E. [Karlsruhe Institut fuer Technologie (KIT) D-76021 Karlsruhe (Germany)

    2011-07-01

    Electronic many-body and correlation effects have been studied intensively at transition metal compounds with localized d/f electrons. They are related to interesting material properties, e.g. Mott metal-insulator transitions, charge transfer satellites and superconductivity. Recent investigations of graphene,{sup 1} C{sub 60},{sup 2} and TTF-TCNQ{sup 3} showed that many-body effects can also be important for organic thin films. We have investigated several organic thin films (PTCDA, PTCDI, BTCDA, BTCDI, SnPc) deposited on a Ag(111) surfaces with photoelectron spectroscopy, NEXAFS and resonant Auger Raman spectroscopy. Our data provide significant indications for electronic many-body effects involving substrate-adsorbate charge transfer, which can be understood by concepts developed for charge transfer compounds. These results give insight into new, interesting aspects of physics at metal-organic interfaces. {sup 1} I.

  11. Empirical Equation Based Chirality (n, m Assignment of Semiconducting Single Wall Carbon Nanotubes from Resonant Raman Scattering Data

    Md Shamsul Arefin

    2012-12-01

    Full Text Available This work presents a technique for the chirality (n, m assignment of semiconducting single wall carbon nanotubes by solving a set of empirical equations of the tight binding model parameters. The empirical equations of the nearest neighbor hopping parameters, relating the term (2n, m with the first and second optical transition energies of the semiconducting single wall carbon nanotubes, are also proposed. They provide almost the same level of accuracy for lower and higher diameter nanotubes. An algorithm is presented to determine the chiral index (n, m of any unknown semiconducting tube by solving these empirical equations using values of radial breathing mode frequency and the first or second optical transition energy from resonant Raman spectroscopy. In this paper, the chirality of 55 semiconducting nanotubes is assigned using the first and second optical transition energies. Unlike the existing methods of chirality assignment, this technique does not require graphical comparison or pattern recognition between existing experimental and theoretical Kataura plot.

  12. Formation of high-valent iron-oxo species in superoxide reductase: characterization by resonance Raman spectroscopy.

    Bonnot, Florence; Tremey, Emilie; von Stetten, David; Rat, Stéphanie; Duval, Simon; Carpentier, Philippe; Clemancey, Martin; Desbois, Alain; Nivière, Vincent

    2014-06-01

    Superoxide reductase (SOR), a non-heme mononuclear iron protein that is involved in superoxide detoxification in microorganisms, can be used as an unprecedented model to study the mechanisms of O2 activation and of the formation of high-valent iron-oxo species in metalloenzymes. By using resonance Raman spectroscopy, it was shown that the mutation of two residues in the second coordination sphere of the SOR iron active site, K48 and I118, led to the formation of a high-valent iron-oxo species when the mutant proteins were reacted with H2O2. These data demonstrate that these residues in the second coordination sphere tightly control the evolution and the cleavage of the O-O bond of the ferric iron hydroperoxide intermediate that is formed in the SOR active site. PMID:24777646

  13. In Situ Resonance Raman Spectra of Organic Pigments in Momo Coral

    Fan Luwei; Yang Mingxing

    2008-01-01

    In this study, Raman scattering measurements were obtained for momo corals covering their typical range of colors. Three different excitation wavelengths (785, 633, 514 nm) are used for the same samples at the same points. All the samples show the two major Raman features of polyenic compounds assigned to double carbon-carbon (C=C) stretching vibration at approximately 1 500 cm-1 and single carbon-carbon (C--C) stretching vibration at approximately 1 130 cm-1 bond stretching mode. These peaks are not detected in the corresponding white parts of momo corals. However, somechanges in intensities, shape, and position of C=C stretching vibrations of the same point are observed by using different excitation wavelengths. The exact position of C-C stretching vibration of polyenic molecules depends strongly on the number of double bonds contained in their polyenic chain. In addition, the number of double bonds contained in the polyenic chains shows that different colors of the red momo coral are caused by different mixtures of polyenic compounds.

  14. A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds of Scots pine ( Pinus sylvestris) wood . Part I: Lipophilic compounds

    Nuopponen, M.; Willför, S.; Jääskeläinen, A.-S.; Sundberg, A.; Vuorinen, T.

    2004-11-01

    The wood resin in Scots pine ( Pinus sylvestris) stemwood and branch wood were studied using UV resonance Raman (UVRR) spectroscopy. UVRR spectra of the sapwood and heartwood hexane extracts, solid wood samples and model compounds (six resin acids, three fatty acids, a fatty acid ester, sitosterol and sitosterol acetate) were collected using excitation wavelengths of 229, 244 and 257 nm. In addition, visible Raman spectra of the fatty and resin acids were recorded. Resin compositions of heartwood and sapwood hexane extracts were determined using gas chromatography. Raman signals of both conjugated and isolated double bonds of all the model compounds were resonance enhanced by UV excitation. The oleophilic structures showed strong bands in the region of 1660-1630 cm -1. Distinct structures were enhanced depending on the excitation wavelength. The UVRR spectra of the hexane extracts showed characteristic bands for resin and fatty acids. It was possible to identify certain resin acids from the spectra. UV Raman spectra collected from the solid wood samples containing wood resin showed a band at ˜1650 cm -1 due to unsaturated resin components. The Raman signals from extractives in the resin rich branch wood sample gave even more strongly enhanced signals than the aromatic lignin.

  15. A Study of the Cis—Trans Isomers of β—Apo—12′—Carotenal By Resonance Raman Spectroscopy at Low Temperature

    YingHu; TadashiMizoguchi; 等

    1995-01-01

    Resonance Raman spectroscopy is a powerful technique to study the cis-trans configurations and the intermolecular interactions of carotenoids bound to pigmentprotein complexes[1,2].In the present invertigation,we studied a set of cis-trans isomers of β-Apo-12′-carotenal,the conjugated chain of which has a length in -between those of β-carotene and retinal,to examine whether the configurational key Raman lines which have been established for β-carotene are still valid for β-Apo-12′-caotenal[3

  16. Resonant surface enhancement of Raman scattering of Ag nanoparticles on silicon substrates fabricated by dc sputtering

    Ag nanoparticles (AgNPs) were deposited onto silicon substrates by direct current (dc) magnetron sputtering. The influences of sputtering power and sputtering time on the AgNP film morphology were studied using atomic force microscopy. The particle size was successfully tuned from 19 nm to 53 nm by varying the sputtering time at a dc power of 10 W. When Rhodamine 6 G (R6G) was used as the probe molecule, the AgNP films showed significant surface enhanced Raman scattering effect. In particular, it is found that larger particles show stronger enhancement for lower concentrations of R6G while smaller particles display stronger enhancement for higher concentrations of R6G.

  17. In Vitro Polarized Resonance Raman Study of N719 and N719-TBP in Dye Sensitized Solar Cells

    Hassing, Søren; Jernshøj, Kit Drescher; Nguyen, Phuong Tuyet;

    2016-01-01

    experimental results on N719/TiO2 – DSCs that by combining an analysis of the wave number dependent polarization of these modes with the small shifts observed in the visible absorption spectra of adsorbed, non-adsorbed molecules and degradation products new and more reliable information about dye stability and...... about the adsorption of the dye on TiO2 can be obtained. Furthermore it is found that the polarization fluorescence anisotropy is very different for adsorbed and non-adsorbed dye molecules. This information is automatically obtained when processing the Raman data. The conclusion is that if the...... TiO2substrate applied FTIR,un-polarized Raman (RS) and un-polarized resonance Raman (RRS) spectroscopy. In the un-polarized RRS studies of N719/TiO2 – DSCs the discussion of the adsorption of N719 was based on the rather weak carbonyl or carboxyl group stretching vibrations and on minor spectral...

  18. Resonant Raman spectra of grades of human brain glioma tumors reveal the content of tryptophan by the 1588 cm-1 mode

    Zhou, Yan; Liu, Cheng-hui; Zhou, Lixin; Zhu, Ke; Liu, Yulong; Zhang, Lin; Boydston-White, Susie; Cheng, Gangge; Pu, Yang; Bidyut, Das; Alfano, Robert R.

    2015-03-01

    RR spectra of brain normal tissue, gliomas in low grade I and II, and malignant glioma tumors in grade III and IV were measured using a confocal micro Raman spectrometer. This report focus on the relative contents of tryptophan (W) in various grades of brain glioma tumors by the intrinsic molecular resonance Raman (RR) spectroscopy method using the 1588cm-1 of tryptophan mode by 532 nm excitation. The RR spectra of key fingerprints of tryptophan, with a main vibrational mode at 1588cm-1 (W8b), were observed. It was found that tryptophan contribution was accumulated in grade I to IV gliomas and the mode of 1588cm-1 in grade III and IV malignant gliomas were enhanced by resonance.

  19. Detuning, wavebreaking, and Landau damping as limiting effects on laser compression by resonant backward Raman scattering

    Yampolsky, Nikolai

    2010-11-01

    Plasma waves mediate high-power pulse compression, where the persistence of the plasma wave is critical. In this scheme, the plasma wave mediates the energy transfer between long pump and short seed laser pulses through backward Raman scattering. High efficiency of the plasma wave excitation defines both the overall efficiency of the energy transfer and the duration of the amplified pulse. Based on recent extensive experiments, it is possible to deduce that the experimentally realized efficiency of the amplifier is likely constrained by two factors, namely the pump chirp and the plasma wavebreaking [1]. The limits arise because for compression the frequency of the plasma wave should match the bandwidth of the instability and the plasma wave amplitude should be small enough to be sustained by plasma. Both the detuning and the wavebreaking effects can be suppressed by using low pump intensity in plasma having the appropriate density gradient [1]. When these constraints are avoided, Landau damping will be the main limiting factor. However, the Landau damping rate can be significantly reduced in the presence of a strong plasma wave. Currently, nonlinear Landau damping can be described within two recently developed models [2,3]. We show that these two different descriptions result in the same dynamics for the plasma wave amplitude. We use the quasilinear description of nonlinear Landau damping [3] to identify a regime where initially high linear Landau damping can be significantly saturated. Because of the saturation effect, higher temperatures can be tolerated in achieving efficient amplification. Significantly, the plasma temperature can be as much as 50% larger compared to the case of unsaturated Landau damping.[4pt] [1] N.A. Yampolsky et al., Phys. Plasmas 15, 113104 (2008).[0pt] [2] D. Benisti et al., Phys. Rev. Lett. 103, 155002 (2009).[0pt] [3] N.A. Yampolsky and N.J. Fisch, Phys. Plasmas 16, 072104 (2009).

  20. Determination of Temperature-Dependent Stress State in Thin AlGaN Layer of AlGaN/GaN HEMT Heterostructures by Near-Resonant Raman Scattering

    Yanli Liu

    2015-01-01

    Full Text Available The temperature-dependent stress state in the AlGaN barrier layer of AlGaN/GaN heterostructure grown on sapphire substrate was investigated by ultraviolet (UV near-resonant Raman scattering. Strong scattering peak resulting from the A1(LO phonon mode of AlGaN is observed under near-resonance condition, which allows for the accurate measurement of Raman shifts with temperature. The temperature-dependent stress in the AlGaN layer determined by the resonance Raman spectra is consistent with the theoretical calculation result, taking lattice mismatch and thermal mismatch into account together. This good agreement indicates that the UV near-resonant Raman scattering can be a direct and effective method to characterize the stress state in thin AlGaN barrier layer of AlGaN/GaN HEMT heterostructures.

  1. Validating Resonance Raman Spectroscopy: a Non-invasive Assessment of Skin Carotenoids as a Biomarker of Fruit and Vegetable Intake in Children

    Aguilar, Sheryl Swain

    2013-01-01

    Background: Adult studies have found a strong correlation between serum carotenoids and skin carotenoids measured by resonance Raman spectroscopy (RRS). No published studies have examined correlations between skin and serum carotenoids among children. Objectives: (1) To validate skin RRS methodology against serum carotenoid measurements by high-performance liquid chromatography and (2) to determine if RRS skin carotenoids can be used as a valid biomarker of total fruit and vegetable (FV) inta...

  2. A density functional theory derived force field for p-cresol. Use of the ultraviolet resonance Raman intensities to check the vibrational analysis accuracy

    Lagant, P.; Gallouj, H.; Vergoten, G.

    1995-11-01

    An ab initio force field for p-cresol has been deduced from calculations based on density functional theory. A careful scaling of the internal force constants using correct vibrational assignments is shown to predict quite accurately the experimental vibrational frequencies and the potential energy distribution for p-cresol and all its deuterated analogs. Using this vibrational analysis, an attempt was made to predict the resonance Raman intensities for totally symmetric modes using the A-term part of the scattering tensor.

  3. Using resonance Raman cross-section data to estimate the spin state populations of Cytochromes P450.

    Mak, Piotr J; Zhu, Qianhong; Kincaid, James R

    2013-12-01

    The cytochromes P450 (CYPs) are heme proteins responsible for the oxidation of xenobiotics and pharmaceuticals and the biosynthesis of essential steroid products. In all cases, substrate binding initiates the enzymatic cycle, converting ferric low spin (LS) to high-spin (HS), with the efficiency of the conversion varying widely for different substrates, so documentation of this conversion for a given substrate is an important objective. Resonance Raman (rR) spectroscopy can effectively yield distinctive frequencies for the ν3 "spin state marker" bands. Here, employing a reference cytochrome P450 (CYP101), the intensities of the ν3 modes (ILS) and (IHS) relative to an internal standard (sodium sulfate) yield relative populations for the two spin states; i.e., a value of 1.24 was determined for the ratio of the relative cross sections for the ν3 modes. Use of this value was then shown to permit a reliable calculation of relative populations of the two spin states from rR spectra of several other Cytochromes P450. The importance of this work is that, using this information, it is now possible to conveniently document by rR the spin state population without conducting separate experiments requiring different analytical methods, instrumentation and additional sample. PMID:24443630

  4. Microanalysis of organic pigments and glazes in polychrome works of art by surface-enhanced resonance Raman scattering

    Leona, Marco

    2009-01-01

    Scientific studies of works of art are usually limited by severe sampling restrictions. The identification of organic colorants, a class of compounds relevant for attribution and provenance studies, is further complicated by the low concentrations at which these compounds are used and by the interference of the protein-, gum-, or oil-binding media present in pigment and glaze samples. Surface-enhanced resonance Raman scattering (SERRS) was successfully used to identify natural organic colorants in archaeological objects, polychrome sculptures, and paintings from samples smaller than 25 μm in diameter. The key factors in achieving the necessary sensitivity were a highly active stabilized silver colloid, obtained by the reproducible microwave-supported reduction of silver sulfate with glucose and sodium citrate, and a non-extractive hydrolysis sample treatment procedure that maximizes dye adsorption on the colloid. Among the examples presented are the earliest so far found occurrence of madder lake (in a 4,000 years old Egyptian object dating to the Middle Kingdom period), and the earliest known occurrence in Europe of the South Asian dyestuff lac (in the Morgan Madonna, a 12th century polychrome sculpture from Auvergne, France). PMID:19667181

  5. Investigation of the electronic structure of CuO by means of resonant X-ray Raman scattering

    Doering, G

    2001-01-01

    excited state. By means of a perturbation theoretical treatment of the Coulomb interaction between the core-hole and the 3d-electrons an expression for the cross-section of the shakeup-process is derived. Thereby the observed excitation energy dependence of the shakeup-satellite's intensity and its position in the energy loss spectrum can be explained. Furthermore, its intensity shows a strong dependence on the scattering angle in certain scattering geometries. By means of a model calculation this dependence is attributed to a polarisation-effect. In this thesis the electronic structure of CuO is investigated utilizing resonant X-ray Raman Scattering. The special properties of this transition metal oxide are emphasized and the potential of the method is shown. First it is explained how one can draw conclusions about the unoccupied density of states of CuO and its symmetry from measurements of the copper K-alpha fluorescence by using an excitation energy of a few eV below the absorption threshold. By this mean...

  6. Stimulated Raman adiabatic passage and dark resonances in an open three-level Λ-system

    The evolution of populations and fluorescence of atoms or molecules interacting with two fields whose frequencies are close to the transition frequencies between the ground and excited states and excited and metastable ones (Lambda-system) is investigated. The system is assumed to be open. The spontaneous decay from the upper state to the other states of the system is taken into account too. The expressions for dependence of fluorescence and the population of the dark state on two-photon detuning are derived by the perturbation theory. The small parameter of the theory is the non-adiabaticity of the atom-field interaction. The cases of constant and pulse fields are discussed. It is shown that the frequency fluctuation can substantially reduce the population of the dark state and the deepness of the dark resonance but does not affect the width of the two-photon lineshape which is inversely proportional to the square root of the interaction time. The analytical results are confirmed by the numerical simulation

  7. Resonance Raman Spectra of Five-Coordinate Heme-Nitrosyl Cytochromes c': Effect of the Proximal Heme-NO Environment.

    Servid, Amy E; McKay, Alison L; Davis, Cherry A; Garton, Elizabeth M; Manole, Andreea; Dobbin, Paul S; Hough, Michael A; Andrew, Colin R

    2015-06-01

    Five-coordinate heme nitrosyl complexes (5cNO) underpin biological heme-NO signal transduction. Bacterial cytochromes c' are some of the few structurally characterized 5cNO proteins, exhibiting a distal to proximal 5cNO transition of relevance to NO sensing. Establishing how 5cNO coordination (distal vs proximal) depends on the heme environment is important for understanding this process. Recent 5cNO crystal structures of Alcaligenes xylosoxidans cytochrome c' (AXCP) and Shewanella frigidimarina cytochrome c' (SFCP) show a basic residue (Arg124 and Lys126, respectively) near the proximal NO binding sites. Using resonance Raman (RR) spectroscopy, we show that structurally characterized 5cNO complexes of AXCP variants and SFCP exhibit a range of ν(NO) (1651-1671 cm(-1)) and ν(FeNO) (519-536 cm(-1)) vibrational frequencies, depending on the nature of the proximal heme pocket and the sample temperature. While the AXCP Arg124 residue appears to have little impact on 5cNO vibrations, the ν(NO) and ν(FeNO) frequencies of the R124K variant are consistent with (electrostatically) enhanced Fe(II) → (NO)π* backbonding. Notably, RR frequencies for SFCP and R124A AXCP are significantly displaced from the backbonding trendline, which in light of recent crystallographic data and density functional theory modeling may reflect changes in the Fe-N-O angle and/or extent of σ-donation from the NO(π*) to the Fe(II) (dz(2)) orbital. For R124A AXCP, correlation of vibrational and crystallographic data is complicated by distal and proximal 5cNO populations. Overall, this study highlights the complex structure-vibrational relationships of 5cNO proteins that allow RR spectra to distinguish 5cNO coordination in certain electrostatic and steric environments. PMID:25961377

  8. Assignment of fingerprint vibrations in the resonance Raman spectra of rhodopsin, isorhodopsin, and bathorhodopsin: implications for chromophore structure and environment

    13C- and 2H-labeled retinal derivatives have been used to assign normal modes in the 1100-1300-cm-1 fingerprint region of the resonance Raman spectra of rhodopsin, isorhodopsin, and bathorhodopsin. On the basis of the 13C shifts, C8-C9 stretching character is assigned at 1217 cm-1 in rhodopsin, at 1206 cm-1 in isorhodopsin, and at 1214 cm-1 in bathorhodopsin. C10-C11 stretching character is localized at 1098 cm-1 in rhodopsin, at 1154 cm-1 in isorhodopsin, and at 1166 cm-1 in bathorhodopsin. C14-C15 stretching character is found at 1190 cm-1 in rhodopsin, at 1206 cm-1 in isorhodopsin, and at 1210 cm-1 in bathorhodopsin. C12-C13 stretching character is much more delocalized, but the characteristic coupling with the C14H rock allows the authors to assign the C12-C13 stretch at ∼1240 cm-1 in rhodopsin, isorhodopsin, and bathorhodopsin. The insensitivity of the C14-C15 stretching mode to N-deuteriation in all three pigments demonstrates that each contains a trans (anti) protonated Schiff base bond. The relatively high frequency of the C10-C11 mode of bathorhodopsin demonstrates that bathorhodopsin is s-trans about the C10-C11 single bond. This provides strong evidence against the model of bathorhodopsin proposed by Liu and Asato, which suggests a C10-C11 s-cis structure. Comparison of the fingerprint modes of rhodopsin with those of the 11-cis-retinal protonated Schiff base in methanol shows that the frequencies of the C-C stretching modes are largely unperturbed by protein binding. The implications of these observations for the mechanism of wavelength regulation in visual pigments and energy storage in bathorhodopsin are discussed

  9. Electronic and resonance Raman spectra of [Au2(CS3)2]2-. Spectroscopic properties of a "short" Au(I)-Au(I) bond.

    Cheng, E C; Leung, K H; Miskowski, V M; Yam, V W; Phillips, D L

    The anion [Au2(CS3)2]2- has an unusually short Au-Au distance (2.80 A) for a binuclear Au(I) complex. We report detailed Raman studies of the nBu4N+ salt of this complex, including FT-Raman of the solid and UV/vis resonance Raman of dimethyl sulfoxide solutions. All five totally symmetric vibrations of the anion have been located and assigned. A band at delta nu = 125 cm-1 is assigned to nu (Au2). The visible-region electronic absorption bands (384 (epsilon 30,680) and 472 nm (epsilon 610 M-1 cm-1)) are attributable to CS3(2-) localized transitions, as confirmed by the dominance of nu sym(C-Sexo) (delta nu = 951 cm-1) in RR spectra measured in this region. An absorption band at 314 nm (22,250 M-1 cm-1) is assigned as the metal-metal 1(d sigma*-->p sigma) transition, largely because nu sym(C-Sexo) is not strongly enhanced in RR involving this band. Observation of the expected strong resonance enhancement of nu (Au2) was precluded as a result of masking by intense solvent Rayleigh scattering in the UV. PMID:11196834

  10. Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

    Ye, ChuanXiang [Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); Zhao, Yi, E-mail: yizhao@xmu.edu.cn, E-mail: liangwz@xmu.edu.cn [State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Liang, WanZhen, E-mail: yizhao@xmu.edu.cn, E-mail: liangwz@xmu.edu.cn [Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

    2015-10-21

    The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra with respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT.

  11. Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

    The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra with respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT

  12. A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds in Scots pine ( Pinus sylvestris) wood . Part II. Hydrophilic compounds

    Nuopponen, M.; Willför, S.; Jääskeläinen, A.-S.; Vuorinen, T.

    2004-11-01

    Hydrophilic extracts of Scots pine ( Pinus sylvestris) heartwood and sapwood and a solid Scots pine knotwood sample were studied by UV resonance Raman spectroscopy (UVRRS). In addition, UVRR spectra of two hydrophilic model compounds (pinosylvin and chrysin) were analysed. UV Raman spectra were collected using 244 and 257 nm excitation wavelengths. The chemical composition of the acetone:water (95:5 v/v) extracts were also determined by gas chromatography. The aromatic and oleophilic structures of pinosylvin and chrysin showed three intense resonance enhanced bands in the spectral region of 1649-1548 cm -1. Pinosylvin showed also a relatively intense band in the aromatic substitution region at 996 cm -1. The spectra of the heartwood acetone:water extract showed many bands typical of pinosylvin. In addition, the extract included bands distinctive for resin and fatty acids. The sapwood acetone:water extract showed bands due to oleophilic structures at 1655-1650 cm -1. The extract probably also contained oligomeric lignans because the UVRR spectra were in parts similar to that of guaiacyl lignin. The characteristic band of pinosylvin (996 cm -1) was detected in the UVRR spectrum of the resin rich knotwood. In addition, several other bands typical for wood resin were observed, which indicated that the wood resin in the knotwood was resonance enhanced even more than lignin.

  13. Resonant surface-enhanced Raman scattering by optical phonons in a monolayer of CdSe nanocrystals on Au nanocluster arrays

    Milekhin, Alexander G.; Sveshnikova, Larisa L.; Duda, Tatyana A.; Rodyakina, Ekaterina E.; Dzhagan, Volodymyr M.; Sheremet, Evgeniya; Gordan, Ovidiu D.; Himcinschi, Cameliu; Latyshev, Alexander V.; Zahn, Dietrich R. T.

    2016-05-01

    Here we present the results on an investigation of resonant Stokes and anti- Stokes surface-enhanced Raman scattering (SERS) by optical phonons in colloidal CdSe nanocrystals (NCs) homogeneously deposited on arrays of Au nanoclusters using the Langmuir-Blodgett technology. The thickness of deposited NCs, determined by transmission and scanning electron microscopy, amounts to approximately 1 monolayer. Special attention is paid to the determination of the localized surface plasmon resonance (LSPR) energy in the arrays of Au nanoclusters as a function of the nanocluster size by means of micro-ellipsometry. SERS by optical phonons in CdSe NCs shows a significant enhancement factor with a maximal value of 2 × 103 which depends resonantly on the Au nanocluster size and thus on the LSPR energy. The deposition of CdSe NCs on the arrays of Au nanocluster dimers enabled us to study the polarization dependence of SERS. It was found that a maximal SERS signal is observed for the light polarization along the dimer axis. Finally, SERS by optical phonons was observed for CdSe NCs deposited on the structures with a single Au dimer. A difference of the LO phonon energy is observed for CdSe NCs on different single dimers. This effect is explained as the confinement-induced shift which depends on the CdSe nanocrystal size and indicates quasi-single NC Raman spectra being obtained.

  14. Vibrational spectroscopy of the electronically excited state. 4. Nanosecond and picosecond time-resolved resonance Raman spectroscopy of carotenoid excited states

    Resonance Raman and electronic absorption spectra are reported for the S0 and T1 states of the carotenoids β-carotene, zeaxanthin, echinenone, canthaxanthin, dihydroxylycopene, astaxanthin, decapreno(C50)-β-carotene, β-apo-8'-carotenal, and ethyl β-apo-8'-carotenoate. The results reveal qualitatively similar ground-state spectra and similar frequency shifts in all observed resonance Raman modes between S0 and T1, regardless of carotenoid structure. Examinations of the relationship of the putative C--C and C==C frequencies in S0 and T1 reveals anomalous shifts to lower frequency in the ''single-bond'' mode upon electronic excitation. These shifts may be due to molecular distortions in the excited state which force changes in molecular motions comprising the observed modes. However, another possibility requiring no distortion is that the interaction (off-diagonal) force constants connecting the C--C and C==C modes change sign upon electronic excitation. This latter phenomenon may provide a unitary explanation for the ''anomalous'' frequency shifts in the C--C and C==C modes, both in the T1 states of carotenoids and in the S1 states of simpler polyenes, without postulating large, unpredicted structural changes upon excitation or general errors in existing vibrational or theoretical analyses. Resonance Raman and absorbance studies with 35-ps time resolution suggest that S1 lifetime (of the 1B/sub u/ and/or the 1A/sub g/* states) of β-carotene in benzene is less than 1 ps

  15. Vibrational spectroscopy of the electronically excited state. 4. Nanosecond and picosecond time-resolved resonance Raman spectroscopy of carotenoid excited states

    Dallinger, R.F.; Farquharson, S.; Woodruff, W.H.; Rodgers, M.A.J.

    1981-12-16

    Resonance Raman and electronic absorption spectra are reported for the S/sub 0/ and T/sub 1/ states of the carotenoids ..beta..-carotene, zeaxanthin, echinenone, canthaxanthin, dihydroxylycopene, astaxanthin, decapreno(C/sub 50/)-..beta..-carotene, ..beta..-apo-8'-carotenal, and ethyl ..beta..-apo-8'-carotenoate. The results reveal qualitatively similar ground-state spectra and similar frequency shifts in all observed resonance Raman modes between S/sub 0/ and T/sub 1/, regardless of carotenoid structure. Examinations of the relationship of the putative C--C and C==C frequencies in S/sub 0/ and T/sub 1/ reveals anomalous shifts to lower frequency in the ''single-bond'' mode upon electronic excitation. These shifts may be due to molecular distortions in the excited state which force changes in molecular motions comprising the observed modes. However, another possibility requiring no distortion is that the interaction (off-diagonal) force constants connecting the C--C and C==C modes change sign upon electronic excitation. This latter phenomenon may provide a unitary explanation for the ''anomalous'' frequency shifts in the C--C and C==C modes, both in the T/sub 1/ states of carotenoids and in the S/sub 1/ states of simpler polyenes, without postulating large, unpredicted structural changes upon excitation or general errors in existing vibrational or theoretical analyses. Resonance Raman and absorbance studies with 35-ps time resolution suggest that S/sub 1/ lifetime (of the /sup 1/B/sub u/ and/or the /sup 1/A/sub g/* states) of ..beta..-carotene in benzene is less than 1 ps.

  16. Experimental and theoretical study of red-shifted solitonic resonant radiation in photonic crystal fibers and generation of radiation seeded Raman soliton

    Redshifted solitonic resonant radiation (RR) is a fascinating phase-matching phenomenon that occurs when an optical pulse, launched in the normal dispersion regime of photonic crystal fiber, radiates across the zero-dispersion point. The formation of such phase-matched radiation is independent of the generation of any optical soliton and mainly governed by the leading edge of an input pump which forms a shock front. The radiation is generated at the anomalous dispersion regime and found to be confined both in the time and frequency domain. We experimentally investigate the formation of such radiation in fabricated photonic crystal fiber for two different pulse width regimes (femtosecond and picosecond) with detailed theoretical analyses. Theoretically predicted results corroborate well with experimental results and confirm the existence of such unique radiation which is robust in nature. Further, we extend the study to long-length fiber and investigate the interplay between redshifted solitonic RR and intrapulse Raman scattering (IPRS). The consequence of the formation of such solitonic RR in an anomalous dispersion domain is found to be very interesting where it seeds a series of Raman solitons and behaves like a secondary source. These Raman solitons are now continuously redshifted and open up the possibility of wideband supercontinuum generation even in normal dispersion pumping. We fabricate a suitable photonic crystal fiber and experimentally demonstrate the RR-seeded IPRS process. (paper)

  17. Raman spectroscopy in graphene

    Recent Raman scattering studies in different types of graphene samples are reviewed here. We first discuss the first-order and the double resonance Raman scattering mechanisms in graphene, which give rise to the most prominent Raman features. The determination of the number of layers in few-layer graphene is discussed, giving special emphasis to the possibility of using Raman spectroscopy to distinguish a monolayer from few-layer graphene stacked in the Bernal (AB) configuration. Different types of graphene samples produced both by exfoliation and using epitaxial methods are described and their Raman spectra are compared with those of 3D crystalline graphite and turbostratic graphite, in which the layers are stacked with rotational disorder. We show that Resonance Raman studies, where the energy of the excitation laser line can be tuned continuously, can be used to probe electrons and phonons near the Dirac point of graphene and, in particular allowing a determination to be made of the tight-binding parameters for bilayer graphene. The special process of electron-phonon interaction that renormalizes the phonon energy giving rise to the Kohn anomaly is discussed, and is illustrated by gated experiments where the position of the Fermi level can be changed experimentally. Finally, we discuss the ability of distinguishing armchair and zig-zag edges by Raman spectroscopy and studies in graphene nanoribbons in which the Raman signal is enhanced due to resonance with singularities in the density of electronic states.

  18. Peculiarities of the temperature dependence of electron spin resonance and Raman studies of Zn1-xNixO/NiO two-phase nanocomposites

    Joshi, D. C.; Nayak, S.; Kumar, A.; Mohanta, A.; Pamu, D.; Thota, S.

    2016-02-01

    A meticulous investigation of electron-spin-resonance (ESR) and Raman spectroscopy of the two-phase nanocomposites of Zn1-xNixO/NiO is reported. The temperature variation of X-band ESR parameters viz., resonance field HR(T) and line-width ΔHPP(T) follows the power-law variation (δHR = (ΔHPP)n) of Nagata and Ishihara model, which was used to understand the orientation of statistical ensemble of particles with respect to a given direction of the anisotropy axis. This analysis yields the exponent "n" ≃ 2.13 and 2.85 for the composite system Zn1-xNixO/NiO and pure NiO suggesting the presence of partial and randomly oriented ellipsoidal nanocrystallites, respectively. The Raikher and Stepanov model has been employed to probe the role of amorphous Ni3+ clusters on the observed ESR spectra. Interestingly, after Ni substitution, a new zone boundary phonon mode was noticed at 129 cm-1 for all the samples, which is usually forbidden in the first-order Raman scattering for wurtzite ZnO. In addition to the 2M magnon mode, two extra modes appear at 558 and 900 cm-1 due to the increased volume fraction of NiO within the Zn1-xNixO matrix. A systematic correlation of the above results with a comparative analysis of their bulk counterpart has been presented.

  19. Excited state proton transfer dynamics of thioacetamide in S2(ππ*) state: resonance Raman spectroscopic and quantum mechanical calculations study.

    Chen, Xiao; Zhao, Yanying; Zhang, Haibo; Xue, Jiadan; Zheng, Xuming

    2015-02-01

    The photophysics and photochemistry of thioacetamide (CH3CSNH2) after excitation to the S2 electronic state were investigated by using resonance Raman spectroscopy in conjunction with the complete active space self-consistent field (CASSCF) method and density functional theory (DFT) calculations. The A-band resonance Raman spectra in acetonitrile, methanol, and water were obtained at 299.1, 282.4, 266.0, 252.7, and 245.9 nm excitation wavelengths to probe the structural dynamics of thioacetamide in the S2 state. CASSCF calculations were done to determine the transition energies and structures of the lower-lying excited states, the conical intersection points CI(S2/S1) and CI(S1/S0), and intersystem crossing points. The structural dynamics of thioacetamide in the S2 state was revealed to be along eight Franck-Condon active vibrational modes ν15, ν11, ν14, ν10, ν8, ν12, ν18, and ν19, mostly in the CC/CS/CN stretches and the CNH8,9/CCH5,6,7/CCN/CCS in-plane bends as indicated by the corresponding normal mode descriptions. The S2 → S1 decay process via the S2/S1 conical intersection point as the major channel were excluded. The thione-thiol photoisomerization reaction mechanism of thioacetamide via the S2,FC → S'1,min excited state proton transfer (ESPT) reaction channel was proposed. PMID:25559740

  20. Resonance Raman Intensities Demonstrate that C5 Substituents Affect the Initial Excited-State Structural Dynamics of Uracil More than C6 Substituents.

    Teimoory, Faranak; Loppnow, Glen R

    2016-05-01

    Resonance Raman derived initial excited-state structural dynamics provide insight into the photochemical mechanisms of pyrimidine nucleobases, in which the photochemistry appears to be dictated by the C5 and C6 substituents. The absorption and resonance Raman spectra and excitation profiles of 5,6-dideuterouracil were measured to further test this photochemical dependence on the C5 and C6 substituents. The resulting set of excited-state reorganization energies of the observed internal coordinates were calculated and compared to those of other 5- and 6-substituted uracils. The results show that the initial excited-state dynamics along the C5C6 stretch responds to changes in mass at C5 and C6 in the same manner but that the in-plane bends at C5 and C6 are more sensitive to substituents at the C5 position than at the C6 position. In addition, the presence of two deuterium substituents at C5 and C6 decreases the initial excited-state structural dynamics along these in-plane bends, in contrast to what is observed in the presence of two CH3 groups on C5 and C6. The results are discussed in the context of DNA nucleobase photochemistry. PMID:26717253

  1. Resonance-Enhanced Raman Scattering of Ring-Involved Vibrational Modes in the (1)B(2u) Absorption Band of Benzene, Including the Kekule Vibrational Modes ν(9) and ν(10).

    Willitsford, Adam H; Chadwick, C Todd; Kurtz, Stewart; Philbrick, C Russell; Hallen, Hans

    2016-02-01

    Resonance Raman spectroscopy provides much stronger Raman signal levels than its off-resonant counterpart and adds selectivity by excitation tuning. Raman preresonance of benzene has been well studied. On-resonance studies, especially at phonon-allowed absorptions, have received less attention. In this case, we observe resonance of many of the vibration modes associated motion of the carbons in the ring while tuning over the (1)B2u absorption, including the related ν9 (CC stretch Herzberg notation, ν14 Wilson notation) and ν10 (CH-parallel bend Herzberg notation, ν15 Wilson notation) vibrational modes along with the ν2 (CC-stretch or ring-breathing Herzberg notation, ν1 Wilson notation) mode and multiples of the ν18 (CCC-parallel bend Herzberg notation, ν6 Wilson notation) vibrational mode. The ring-breathing mode is found to mix with the b2u modes creating higher frequency composites. Through the use of an optical parametric oscillator (OPO) to tune through the (1)B2u absorption band of liquid benzene, a stiffening (increase in energy) of the vibrational modes is observed as the excitation wavelength nears the (1)B2u absorption peak of the isolated molecule (vapor) phase. The strongest resonance amplitude observed is in the 2 × ν18 (e2g) mode, with nearly twice the intensity of the ring-breathing mode, ν2. Several overtones and combination modes, especially with ν2 (a1g), are also observed to resonate. Raman resonances on phonon-allowed excitations are narrow and permit the measurement of vibrations not Raman-active in the ground state. PMID:26731431

  2. Resonance Raman and electronic absorption spectra of O3- ions in γ-irradiated KC1O3 and NaC1O3

    Resonance Raman and electronic absorption spectra have been measured for the ozonide ion, O-3, produced in single crystals of KClO3 and NaClO3 by irradiation with γ rays. The O-3 ions are oriented in four to six symmetrically nonequivalent positions in KClO3 and appear to be oriented in two nonequivalent positions in NaClO3. Differences between the nonequivalent orientations affect both the ground and excited electronic states of O-3 as well as its ground vibrational states. The progressions of ν1 observed in the electronic spectra show that the vibrational spacing of ν1 in the excited electronic state is about 857 cm/sup -1/ as compared with the ground state spacing of about 1020 cm/sup -1/. Measurements of relative Raman intensities obtained with different exciting lines indicate that excitation near the center of a vibronic transition (0--n') produces extra enhancement of the intensity of the nν1 vibrational transition

  3. Resonant Raman scattering in Nd2O3 and the electronic structure of Sr2RuO4 studied by synchrotron radiation excitation

    This paper is intended to illustrate two points. The first being the extensive growth of resonant Raman soft x-ray scattering due to the emergence of third-generation x-ray sources. With these sources, the ubiquitous presence of Raman scattering near the 3d and 4d ionization thresholds has been used to elucidate the excitation process in a number of rare earth and transition metal compounds. Such scattering can produce dramatic changes in the emission spectrum, as we show in our example of inelastic scattering at the 3d threshold of Nd2O3. Photon-in photon-out soft x-ray spectroscopy is adding a new dimension to soft x-ray spectroscopy by providing many opportunities for exciting research, especially at third-generation synchrotrons light sources. Second, it is very effective to use theory and experiment to characterize the electronic properties of materials. In particular we confirmed in-plane oxygen-ruthenium bonding in Sr2RuO4, this first copperless perovskite superconductor, by analyses using calculations, soft x-ray emission spectroscopy (SXE) and photoelectron spectroscopy (PES). Measurements of this type illustrate the importance of combining SXE and PES measurements with theoretical calculations

  4. Probing the nitrite and nitric oxide reductase activity of cbb3 oxidase: resonance Raman detection of a six-coordinate ferrous heme-nitrosyl species in the binuclear b3/CuB center.

    Loullis, Andreas; Pinakoulaki, Eftychia

    2015-12-21

    In this work we report the first spectroscopic evidence demonstrating that cbb3 oxidase catalyzes the reduction of nitrite to nitrous oxide under reducing anaerobic conditions. The reaction proceeds through the formation of a ferrous six-coordinate heme b3-nitrosyl species that has been characterized by resonance Raman spectroscopy. PMID:26465875

  5. Potential sodium D2 resonance radiation generated by intra-cavity SHG of a c-cut Nd:YVO4 self-Raman laser.

    Duan, Yanmin; Zhu, Haiyong; Huang, Chenghui; Zhang, Ge; Wei, Yong

    2011-03-28

    Intra-cavity frequency doubling with 589 nm emission from a compact c-cut Nd:YVO4 crystal self-Raman laser was investigated. A 15-cm-length LBO with non-critical phase-matching cut (θ = 90°, ϕ = 0°) was used for efficient second-harmonic generation. At a pump power of 16.2 W and a pulse repetition frequency of 40 kHz, output power up to 2.15 W was achieved with a pulse width of 16 ns and a conversion efficiency of 13.3% with respect to the diode pump power. The center wavelength was measured to be 589.17 nm with a Half-Maximum-Full-Width of 0.2 nm, which was well in accordance with the sodium D2 resonance radiation. PMID:21451660

  6. Investigation of magnetic field enriched surface enhanced resonance Raman scattering performance using Fe3O4@Ag nanoparticles for malaria diagnosis

    Yuen, Clement; Liu, Quan

    2014-03-01

    Recently, we have demonstrated the magnetic field-enriched surface-enhanced resonance Raman spectroscopy (SERRS) of β-hematin by using nanoparticles with iron oxide core and silver shell (Fe3O4@Ag) for the potential application in the early malaria diagnosis. In this study, we investigate the dependence of the magnetic field-enriched SERRS performance of β-hematin on the different core and shell sizes of the Fe3O4@Ag nanoparticles. We note that the core and shell parameters are critical in the realization of the optimal magnetic field-enrich SERRS β-hematin signal. These results are consistent with our simulations that will guide the optimization of the magnetic SERRS performance for the potential early diagnosis in the malaria disease.

  7. Molecular near-field antenna effect in resonance hyper-Raman scattering: Intermolecular vibronic intensity borrowing of solvent from solute through dipole-dipole and dipole-quadrupole interactions

    We quantitatively interpret the recently discovered intriguing phenomenon related to resonance Hyper-Raman (HR) scattering. In resonance HR spectra of all-trans-β-carotene (β-carotene) in solution, vibrations of proximate solvent molecules are observed concomitantly with the solute β-carotene HR bands. It has been shown that these solvent bands are subject to marked intensity enhancements by more than 5 orders of magnitude under the presence of β-carotene. We have called this phenomenon the molecular-near field effect. Resonance HR spectra of β-carotene in benzene, deuterated benzene, cyclohexane, and deuterated cyclohexane have been measured precisely for a quantitative analysis of this effect. The assignments of the observed peaks are made by referring to the infrared, Raman, and HR spectra of neat solvents. It has been revealed that infrared active and some Raman active vibrations are active in the HR molecular near-field effect. The observed spectra in the form of difference spectra (between benzene/deuterated benzene and cyclohexane/deuterated cyclohexane) are quantitatively analyzed on the basis of the extended vibronic theory of resonance HR scattering. The theory incorporates the coupling of excited electronic states of β-carotene with the vibrations of a proximate solvent molecule through solute–solvent dipole–dipole and dipole–quadrupole interactions. It is shown that the infrared active modes arise from the dipole–dipole interaction, whereas Raman active modes from the dipole–quadrupole interaction. It is also shown that vibrations that give strongly polarized Raman bands are weak in the HR molecular near-field effect. The observed solvent HR spectra are simulated with the help of quantum chemical calculations for various orientations and distances of a solvent molecule with respect to the solute. The observed spectra are best simulated with random orientations of the solvent molecule at an intermolecular distance of 10 Å

  8. Molecular near-field antenna effect in resonance hyper-Raman scattering: Intermolecular vibronic intensity borrowing of solvent from solute through dipole-dipole and dipole-quadrupole interactions

    Shimada, Rintaro; Hamaguchi, Hiro-o, E-mail: hhama@nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 University Road, Hsinchu 30010, Taiwan (China)

    2014-05-28

    We quantitatively interpret the recently discovered intriguing phenomenon related to resonance Hyper-Raman (HR) scattering. In resonance HR spectra of all-trans-β-carotene (β-carotene) in solution, vibrations of proximate solvent molecules are observed concomitantly with the solute β-carotene HR bands. It has been shown that these solvent bands are subject to marked intensity enhancements by more than 5 orders of magnitude under the presence of β-carotene. We have called this phenomenon the molecular-near field effect. Resonance HR spectra of β-carotene in benzene, deuterated benzene, cyclohexane, and deuterated cyclohexane have been measured precisely for a quantitative analysis of this effect. The assignments of the observed peaks are made by referring to the infrared, Raman, and HR spectra of neat solvents. It has been revealed that infrared active and some Raman active vibrations are active in the HR molecular near-field effect. The observed spectra in the form of difference spectra (between benzene/deuterated benzene and cyclohexane/deuterated cyclohexane) are quantitatively analyzed on the basis of the extended vibronic theory of resonance HR scattering. The theory incorporates the coupling of excited electronic states of β-carotene with the vibrations of a proximate solvent molecule through solute–solvent dipole–dipole and dipole–quadrupole interactions. It is shown that the infrared active modes arise from the dipole–dipole interaction, whereas Raman active modes from the dipole–quadrupole interaction. It is also shown that vibrations that give strongly polarized Raman bands are weak in the HR molecular near-field effect. The observed solvent HR spectra are simulated with the help of quantum chemical calculations for various orientations and distances of a solvent molecule with respect to the solute. The observed spectra are best simulated with random orientations of the solvent molecule at an intermolecular distance of 10 Å.

  9. Growth temperature dependent surface plasmon resonances of densely packed gold nanoparticles’ films and their role in surface enhanced Raman scattering of Rhodamine6G

    Highlights: • Growth temperature produces and tunes the surface plasmon resonance (SPR) of gold films. • Optimum thickness and growth temperature combination results narrow SPR band. • Alumina capping red-shifted the SPR band and showed marginal re-sputtering of films. • Densely packed gold nanoparticles of varying sizes can be realized by pulsed laser deposition. • High SERS intensity of dye from gold films of large SPR strength at excitation wavelength. - Abstract: Localized surface plasmon resonance (LSPR) characteristics of gold nanoparticles films grown at different substrate temperatures and mass thicknesses with and without alumina capping were studied. At different film mass thicknesses, the LSPR response was observed mainly in the films grown at high substrate temperatures. About 300 °C substrate temperature was found to be optimum for producing narrow and strong LSPR band in both uncapped and alumina capped gold nanoparticles films. The LSPR wavelength could be tuned in the range of 600–750 nm by changing either number of ablation pulses or decreasing target to substrate distance (TSD) and alumina layer capping. Though the alumina capping re-sputtered the gold films still these films exhibited stronger LSPR response compared to the uncapped films. Atomic force microscopic analysis revealed formation of densely packed nanoparticles films exhibiting strong LSPR response which is consistent with the package density of the nanoparticles predicted by the theoretical calculations. The average size of nanoparticles increased with substrate temperature, number of ablation pulses and decreasing the TSD. For the same mass thickness of gold films grown at different substrate temperatures the surface enhanced Raman scattering (SERS) intensity of Rhodamine6G dye was found to be significantly different which had direct correlation with the LSPR strength of the films at the excitation wavelength

  10. Growth temperature dependent surface plasmon resonances of densely packed gold nanoparticles’ films and their role in surface enhanced Raman scattering of Rhodamine6G

    Verma, Shweta, E-mail: shwetaverma@rrcat.gov.in [Laser Materials Processing Division, Raja Ramanna Centre for Advanced Technology, Indore 452 013 (India); Rao, B. Tirumala [Laser Materials Processing Division, Raja Ramanna Centre for Advanced Technology, Indore 452 013 (India); Bhartiya, S. [Laser Materials Development and Devices Division, Raja Ramanna Centre for Advanced Technology, Indore 452 013 (India); Sathe, V. [UGC-DAE Consortium for Scientific Research, Indore 452 001 (India); Kukreja, L.M. [Laser Materials Processing Division, Raja Ramanna Centre for Advanced Technology, Indore 452 013 (India)

    2015-08-15

    Highlights: • Growth temperature produces and tunes the surface plasmon resonance (SPR) of gold films. • Optimum thickness and growth temperature combination results narrow SPR band. • Alumina capping red-shifted the SPR band and showed marginal re-sputtering of films. • Densely packed gold nanoparticles of varying sizes can be realized by pulsed laser deposition. • High SERS intensity of dye from gold films of large SPR strength at excitation wavelength. - Abstract: Localized surface plasmon resonance (LSPR) characteristics of gold nanoparticles films grown at different substrate temperatures and mass thicknesses with and without alumina capping were studied. At different film mass thicknesses, the LSPR response was observed mainly in the films grown at high substrate temperatures. About 300 °C substrate temperature was found to be optimum for producing narrow and strong LSPR band in both uncapped and alumina capped gold nanoparticles films. The LSPR wavelength could be tuned in the range of 600–750 nm by changing either number of ablation pulses or decreasing target to substrate distance (TSD) and alumina layer capping. Though the alumina capping re-sputtered the gold films still these films exhibited stronger LSPR response compared to the uncapped films. Atomic force microscopic analysis revealed formation of densely packed nanoparticles films exhibiting strong LSPR response which is consistent with the package density of the nanoparticles predicted by the theoretical calculations. The average size of nanoparticles increased with substrate temperature, number of ablation pulses and decreasing the TSD. For the same mass thickness of gold films grown at different substrate temperatures the surface enhanced Raman scattering (SERS) intensity of Rhodamine6G dye was found to be significantly different which had direct correlation with the LSPR strength of the films at the excitation wavelength.

  11. Anti-Stokes Resonance Raman of Ir Illuminated Dendrimer Iron (III)-Porphyrins%红外辐照下树枝状铁(iii)卟啉的反斯托克斯共振拉曼

    MO Yu-jun; D.L.Jiang; M.Uymura; T.Aida; T.Kitagawa

    2005-01-01

    The benzene dendrimers of Fe(Ⅲ) tetraphenyl porphyrin chloride[LnFe(Ⅲ)TPPCl] with n = 3, 4, and 5 (n: number of layers) have been synthesized and the IR illumination effects at benzene bands were examined with anti- Stokes resonance Raman speetroseopy for their dioxane solutions.Boltzman temperatures were determined from the Stokes to anti - Stokes intensity ratio for the speetra excited at 413.1 nm in the presence and absence of IR illumination.

  12. A general time-dependent route to Resonance-Raman spectroscopy including Franck-Condon, Herzberg-Teller and Duschinsky effects

    Baiardi, Alberto; Barone, Vincenzo [Scuola Normale Superiore, piazza dei Cavalieri 7, I-56126 Pisa (Italy); Bloino, Julien [Scuola Normale Superiore, piazza dei Cavalieri 7, I-56126 Pisa (Italy); Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti OrganoMetallici (ICCOM-CNR), UOS di Pisa, Area della Ricerca CNR, Via G. Moruzzi 1, I-56124 Pisa (Italy)

    2014-09-21

    We present a new formulation of the time-dependent theory of Resonance-Raman spectroscopy (TD-RR). Particular attention has been devoted to the generality of the framework and to the possibility of including different effects (Duschinsky mixing, Herzberg-Teller contributions). Furthermore, the effects of different harmonic models for the intermediate electronic state are also investigated. Thanks to the implementation of the TD-RR procedure within a general-purpose quantum-chemistry program, both solvation and leading anharmonicity effects have been included in an effective way. The reliability and stability of our TD-RR implementation are validated against our previously proposed and well-tested time-independent procedure. Practical applications are illustrated with some closed- and open-shell medium-size molecules (anthracene, phenoxyl radical, benzyl radical) and the simulated spectra are compared to the experimental results. More complex and larger systems, not limited to organic compounds, can be also studied, as shown for the case of Tris(bipyridine)ruthenium(II) chloride.

  13. A general time-dependent route to Resonance-Raman spectroscopy including Franck-Condon, Herzberg-Teller and Duschinsky effects

    Baiardi, Alberto; Bloino, Julien; Barone, Vincenzo

    2014-09-01

    We present a new formulation of the time-dependent theory of Resonance-Raman spectroscopy (TD-RR). Particular attention has been devoted to the generality of the framework and to the possibility of including different effects (Duschinsky mixing, Herzberg-Teller contributions). Furthermore, the effects of different harmonic models for the intermediate electronic state are also investigated. Thanks to the implementation of the TD-RR procedure within a general-purpose quantum-chemistry program, both solvation and leading anharmonicity effects have been included in an effective way. The reliability and stability of our TD-RR implementation are validated against our previously proposed and well-tested time-independent procedure. Practical applications are illustrated with some closed- and open-shell medium-size molecules (anthracene, phenoxyl radical, benzyl radical) and the simulated spectra are compared to the experimental results. More complex and larger systems, not limited to organic compounds, can be also studied, as shown for the case of Tris(bipyridine)ruthenium(II) chloride.

  14. Comparison of simplified sum-over-state expressions to calculate resonance Raman intensities including Franck-Condon and Herzberg-Teller effects

    Guthmuller, Julien

    2016-02-01

    Sum-over-state (SOS) expressions to simulate absorption spectroscopy and resonance Raman (RR) scattering including Franck-Condon (FC) and Herzberg-Teller (HT) effects are described. Starting from the general SOS method, several simplified SOS formulae are derived. In particular, within the so-called independent mode displaced harmonic oscillator model, it is shown that including the vibronic structure in the absorption and RR spectra only requires the calculation of FC overlap integrals of the type , where g, e, and v stand for the electronic ground state, excited state, and vibrational quantum number, respectively. Additionally, an approximation of the latter approach is introduced, referred as the simplified Φe method, in which the FC factors are neglected. This method is advantageous from the computational point of view and it is demonstrated that it reproduces the main characteristics of the more involved approaches. The merits and drawbacks of the different methods are discussed by applying them to the prototypical compound of Rhodamine 6G. Overall, this work intends to unravel and clarify some differences in the SOS theories of RR scattering.

  15. Structure-dependent localized surface plasmon resonance characteristics and surface enhanced Raman scattering performances of quasi-periodic nanoarrays: Measurements and analysis

    Chen, Dong; Zhou, Jun, E-mail: zhoujun@nbu.edu.cn [Institute of Photonics, Faculty of Science, Ningbo University, Ningbo 315211 (China); Rippa, Massimo; Petti, Lucia [Institute of Applied Sciences and Intelligent Systems “E. Caianiello” of CNR, Via Campi Flegrei 34, 80072 Pozzuoli (Italy)

    2015-10-28

    A set of periodic and quasi-periodic Au nanoarrays with different morphologies have been fabricated by using electron beam lithography technique, and their optical properties have been examined experimentally and analyzed theoretically by scanning near-field optical microscope and finite element method, respectively. Results present that the localized surface plasmon resonance of the as-prepared Au nanoarrays exhibit the structure-depended characteristics. Comparing with the periodic nanoarrays, the quasi-periodic ones demonstrate stronger electric field enhancement, especially for Thue-Morse nanoarray. Meanwhile, the surface enhanced Raman scattering (SERS) spectra of 4-mercaptobenzoic acid molecular labeled nanoarrays show that the quasi-periodic nanoarrays exhibit distinct SERS enhancement, for example, a higher enhancement factor of ∼10{sup 7} is obtained for the Thue-Morse nanoarray consisted of square pillars of 100 nm size. Therefore, it is significant to optimally design and fabricate the chip-scale quasi-periodic nanoarrays with high localized electric field enhancement for SERS applications in biosensing field.

  16. Bayesian Extraction of Deep UV Resonance Raman Signature of Fibrillar Cross-β Sheet Core based on H-D Exchange Data

    Shashilov, V. A.; Lednev, I. K.

    2007-11-01

    Amyloid fibrils are associated with many neurodegenerative diseases. The application of conventional biophysical techniques including solution NMR and X-ray crystallography for structural characterization of fibrils is limited because they are neither crystalline nor soluble. The Bayesian approach was utilized for extracting the deep UV resonance Raman (DUVRR) spectrum of the lysozyme fibrillar β-sheet based on the hydrogen-deuterium exchange spectral data. The problem was shown to be unsolvable when using blind source separation or conventional chemometrics methods because of the 100% correlation of the concentration profiles of the species under study. Information about the mixing process was incorporated by forcing the columns of the concentration matrix to be proportional to the expected concentration profiles. The ill-conditioning of the matrix was removed by concatenating it to the diagonal matrix with entries corresponding to the known pure spectra (sources). Prior information about the spectral features and characteristic bands of the spectra was taken into account using the Bayesian signal dictionary approach. The extracted DUVRR spectrum of the cross-β sheet core exhibited sharp bands indicating the highly ordered structure. Well resolved sub-bands in Amide I and Amide III regions enabled us to assign the fibril core structure to anti-parallel β-sheet and estimate the amide group facial angle Ψ in the cross-β structure. The elaborated Bayesian approach was demonstrated to be applicable for studying correlated biochemical processes.

  17. Distinguishing individual vibrational fingerprints: single-molecule surface-enhanced resonance raman scattering from one-to-one binary mixtures in Langmuir-Blodgett monolayers.

    Goulet, Paul J G; Aroca, Ricardo F

    2007-04-01

    Here, it is demonstrated that similar chemical species within a multicomponent sample can be distinguished, down to the single-molecule level, by means of their surface-enhanced vibrational fingerprints. Surface-enhanced resonance Raman scattering spectra and 2D spatial intensity maps are recorded from thin Ag nanoparticle films coated with fatty acid Langmuir-Blodgett monolayers containing one-to-one binary mixtures, at varying concentrations, of two dye molecules of similar absorption and scattering cross section (n-pentyl-5-salicylimidoperylene and octadecylrhodamine B). The results reveal the change in the distribution of the two dyes within the monolayer, and the breakdown of ensemble spectral averaging, which occur as the single-molecule regime is approached. It is found that the unimolecular level is reached when 1-10 molecules of each dye occupy the 1-microm2 scattering areas probed by the laser. These signals are attributed to the rare spatial coincidence of isolated target analyte molecules and localized electromagnetic hot spots in the nanostructured metal film. The bianalyte nature of the samples provides strong corroborative support for the attribution of spectra to single molecules at high dilution, while the effect of domain formation/aggregation is found to be important at higher concentrations. PMID:17311464

  18. Resonances

    an impetus or drive to that account: change, innovation, rupture, or discontinuity. Resonances: Historical Essays on Continuity and Change explores the historiographical question of the modes of interrelation between these motifs in historical narratives. The essays in the collection attempt to...... realize theoretical consciousness through historical narrative ‘in practice’, by discussing selected historical topics from Western cultural history, within the disciplines of history, literature, visual arts, musicology, archaeology, philosophy, and theology. The title Resonances indicates the overall...

  19. Raman Spectroscopy for Homeland Security Applications

    Gregory Mogilevsky

    2012-01-01

    Full Text Available Raman spectroscopy is an analytical technique with vast applications in the homeland security and defense arenas. The Raman effect is defined by the inelastic interaction of the incident laser with the analyte molecule’s vibrational modes, which can be exploited to detect and identify chemicals in various environments and for the detection of hazards in the field, at checkpoints, or in a forensic laboratory with no contact with the substance. A major source of error that overwhelms the Raman signal is fluorescence caused by the background and the sample matrix. Novel methods are being developed to enhance the Raman signal’s sensitivity and to reduce the effects of fluorescence by altering how the hazard material interacts with its environment and the incident laser. Basic Raman techniques applicable to homeland security applications include conventional (off-resonance Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS, resonance Raman spectroscopy, and spatially or temporally offset Raman spectroscopy (SORS and TORS. Additional emerging Raman techniques, including remote Raman detection, Raman imaging, and Heterodyne imaging, are being developed to further enhance the Raman signal, mitigate fluorescence effects, and monitor hazards at a distance for use in homeland security and defense applications.

  20. Coupled electron-nuclear dynamics in resonant 1 σ →2 π x-ray Raman scattering of CO molecules

    Couto, Rafael C.; Guarise, Marco; Nicolaou, Alessandro; Jaouen, Nicolas; Chiuzbǎian, Gheorghe S.; Lüning, Jan; Ekholm, Victor; Rubensson, Jan-Erik; Sâthe, Conny; Hennies, Franz; Guimarães, Freddy F.; Ågren, Hans; Gel'mukhanov, Faris; Journel, Loïc; Simon, Marc; Kimberg, Victor

    2016-03-01

    We present a detailed experimental-theoretical analysis of O K -edge resonant 1 σ -2 π inelastic x-ray scattering (RIXS) from carbon monoxide with unprecedented energy resolution. We employ high-level ab initio calculations to compute the potential energy curves of the states involved in the RIXS process and simulate the measured RIXS spectra using the wave-packet-propagation formalism, including Coulomb coupling in the final-state manifold. The theoretical analysis allows us to explain all the key features of the experimental spectra, including some that were not seen before. First, we clearly show the interference effect between different RIXS channels corresponding to the transition via orthogonal Π1x and Π1y core-excited states of CO. Second, the RIXS region of 13 eV energy loss presents a triple structure, revealed only by the high-resolution measurement. In previous studies, this region was attributed solely to a valence state. Here we show a strong Coulomb mixing of the Rydberg and valence final states, which opens the forbidden RIXS channels to the "dark" final Rydberg states and drastically changes the RIXS profile. Third, using a combination of high-resolution experiment and high-level theory, we improve the |4 σ-12 π1> final-state potential-energy curve by fitting its bottom part with the experiment. Also, the coupling constants between Rydberg and valence states were refined via comparison with the experiment. Our results illustrate the large potential of the RIXS technique for advanced studies of highly excited states of neutral molecules.

  1. Structure of enzyme-bound substrates: resonance Raman and kinetic evidence for differential enzyme-substrate contacts in N-(Pentafluoro-benzoyl)glycine dithioacyl and thioacyl papain

    Lee, H.; Angus, R. H.; Storer, A. C.; Carey, P. R.

    1989-12-01

    Resonance Raman (RR) spectroscopy is used to probe the structure of the substrate in the substrate-enzyme complex N-pentafluorobenzoyl) glycine (dithioacyl) papain (C 6F 5C(=O) NHCH 2C(=S)S-papain). This system was chosen since the high electron withdrawing capacity of the C 6F 5 group markedly affects electron density of the -NH- moiety which, in turn, is known to change catalytic activity. The RR spectrum of the enzyme-substrate complex is interpreted by reference to the model compound N-(pentafluorobenzoyl) glycine ethyl dithioester (C 6F 5(CO))NHCH 2C(=S)SC 2H 5. The RR spectra of this compound in aqueous or organic solvents can be understood in terms of the known conformational states of N-acylglycine dithioesters. Comparison of model with enzyme-substrate RR spectra shows that the substrate is binding in the active site in a conformer known as conformer B characterized by a small-NHCH 2CS(thiol) torsional angle and close N-to-S (thiol) contact. Kinetic rate-structure correlations are developed involving k3, the rate constant for deacylation, and the strength of the N-to-S (thiol) interaction. N-(Pentafluorobenzoyl) glycine dithioacyl papain fits the rate-structure correlation whereas the corresponding pentafluorobenzoyl glycine thiol intermediate does not. It is proposed that the difference in the size of the CS compared to the CO group brings about a small change in the dithioacyl papain compared to the thiolacyl papain conformation such that enzyme-substrate contacts involving ortho and meta F atoms in the thiol acyl enzyme case are weakened or removed in the case of the dithioacyl papain.

  2. Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach

    A time-dependent approach is presented to simulate the two-photon absorption (TPA) and resonance hyper-Raman scattering (RHRS) spectra including Duschinsky rotation (mode-mixing) and Herzberg-Teller (HT) vibronic coupling effects. The computational obstacles for the excited-state geometries, vibrational frequencies, and nuclear derivatives of transition dipole moments, which enter the expressions of TPA and RHRS cross sections, are further overcome by the recently developed analytical excited-state energy derivative approaches in the framework of time-dependent density functional theory. The excited-state potential curvatures are evaluated at different levels of approximation to inspect the effects of frequency differences, mode-mixing and HT on TPA and RHRS spectra. Two types of molecules, one with high symmetry (formaldehyde, p-difluorobenzene, and benzotrifluoride) and the other with non-centrosymmetry (cis-hydroxybenzylidene-2,3-dimethylimidazolinone in the deprotonated anion state (HDBI−)), are used as test systems. The calculated results reveal that it is crucial to adopt the exact excited-state potential curvatures in the calculations of TPA and RHRS spectra even for the high-symmetric molecules, and that the vertical gradient approximation leads to a large deviation. Furthermore, it is found that the HT contribution is evident in the TPA and RHRS spectra of HDBI− although its one- and two-photon transitions are strongly allowed, and its effect results in an obvious blueshift of the TPA maximum with respect to the one-photon absorption maximum. With the HT and solvent effects getting involved, the simulated blueshift of 1291 cm−1 agrees well with the experimental measurement

  3. Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach

    Ma, HuiLi; Zhao, Yi; Liang, WanZhen

    2014-03-01

    A time-dependent approach is presented to simulate the two-photon absorption (TPA) and resonance hyper-Raman scattering (RHRS) spectra including Duschinsky rotation (mode-mixing) and Herzberg-Teller (HT) vibronic coupling effects. The computational obstacles for the excited-state geometries, vibrational frequencies, and nuclear derivatives of transition dipole moments, which enter the expressions of TPA and RHRS cross sections, are further overcome by the recently developed analytical excited-state energy derivative approaches in the framework of time-dependent density functional theory. The excited-state potential curvatures are evaluated at different levels of approximation to inspect the effects of frequency differences, mode-mixing and HT on TPA and RHRS spectra. Two types of molecules, one with high symmetry (formaldehyde, p-difluorobenzene, and benzotrifluoride) and the other with non-centrosymmetry (cis-hydroxybenzylidene-2,3-dimethylimidazolinone in the deprotonated anion state (HDBI-)), are used as test systems. The calculated results reveal that it is crucial to adopt the exact excited-state potential curvatures in the calculations of TPA and RHRS spectra even for the high-symmetric molecules, and that the vertical gradient approximation leads to a large deviation. Furthermore, it is found that the HT contribution is evident in the TPA and RHRS spectra of HDBI- although its one- and two-photon transitions are strongly allowed, and its effect results in an obvious blueshift of the TPA maximum with respect to the one-photon absorption maximum. With the HT and solvent effects getting involved, the simulated blueshift of 1291 cm-1 agrees well with the experimental measurement.

  4. Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach

    Ma, HuiLi [State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Institute of Fujian Provincial Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); Zhao, Yi; Liang, WanZhen, E-mail: liangwz@xmu.edu.cn [State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Institute of Fujian Provincial Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

    2014-03-07

    A time-dependent approach is presented to simulate the two-photon absorption (TPA) and resonance hyper-Raman scattering (RHRS) spectra including Duschinsky rotation (mode-mixing) and Herzberg-Teller (HT) vibronic coupling effects. The computational obstacles for the excited-state geometries, vibrational frequencies, and nuclear derivatives of transition dipole moments, which enter the expressions of TPA and RHRS cross sections, are further overcome by the recently developed analytical excited-state energy derivative approaches in the framework of time-dependent density functional theory. The excited-state potential curvatures are evaluated at different levels of approximation to inspect the effects of frequency differences, mode-mixing and HT on TPA and RHRS spectra. Two types of molecules, one with high symmetry (formaldehyde, p-difluorobenzene, and benzotrifluoride) and the other with non-centrosymmetry (cis-hydroxybenzylidene-2,3-dimethylimidazolinone in the deprotonated anion state (HDBI{sup −})), are used as test systems. The calculated results reveal that it is crucial to adopt the exact excited-state potential curvatures in the calculations of TPA and RHRS spectra even for the high-symmetric molecules, and that the vertical gradient approximation leads to a large deviation. Furthermore, it is found that the HT contribution is evident in the TPA and RHRS spectra of HDBI{sup −} although its one- and two-photon transitions are strongly allowed, and its effect results in an obvious blueshift of the TPA maximum with respect to the one-photon absorption maximum. With the HT and solvent effects getting involved, the simulated blueshift of 1291 cm{sup −1} agrees well with the experimental measurement.

  5. Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model.

    Petrenko, Taras; Neese, Frank

    2012-12-21

    In this work, an improved method for the efficient automatic simulation of optical band shapes and resonance Raman (rR) intensities within the "independent mode displaced harmonic oscillator" is described. Despite the relative simplicity of this model, it is able to account for the intensity distribution in absorption (ABS), fluorescence, and rR spectra corresponding to strongly dipole allowed electronic transitions with high accuracy. In order to include temperature-induced effects, we propose a simple extension of the time dependent wavepacket formalism developed by Heller which enables one to derive analytical expressions for the intensities of hot bands in ABS and rR spectra from the dependence of the wavepacket evolution on its initial coordinate. We have also greatly optimized the computational procedures for numerical integration of complicated oscillating integrals. This is important for efficient simulations of higher-order rR spectra and excitation profiles, as well as for the fitting of experimental spectra of large molecules. In particular, the multimode damping mechanism is taken into account for efficient reduction of the upper time limit in the numerical integration. Excited state energy gradient as well as excited state geometry optimization calculations are employed in order to determine excited state dimensionless normal coordinate displacements. The gradient techniques are highly cost-effective provided that analytical excited state derivatives with respect to nuclear displacements are available. Through comparison with experimental spectra of some representative molecules, we illustrate that the gradient techniques can even outperform the geometry optimization method if the harmonic approximation becomes inadequate. PMID:23267471

  6. Subpicosecond oxygen trapping in the heme pocket of the oxygen sensor FixL observed by time-resolved resonance Raman spectroscopy.

    Kruglik, Sergei G; Jasaitis, Audrius; Hola, Klara; Yamashita, Taku; Liebl, Ursula; Martin, Jean-Louis; Vos, Marten H

    2007-05-01

    Dissociation of oxygen from the heme domain of the bacterial oxygen sensor protein FixL constitutes the first step in hypoxia-induced signaling. In the present study, the photodissociation of the heme-O2 bond was used to synchronize this event, and time-resolved resonance Raman (TR(3)) spectroscopy with subpicosecond time resolution was implemented to characterize the heme configuration of the primary photoproduct. TR(3) measurements on heme-oxycomplexes are highly challenging and have not yet been reported. Whereas in all other known six-coordinated heme protein complexes with diatomic ligands, including the oxymyoglobin reported here, heme iron out-of-plane motion (doming) occurs faster than 1 ps after iron-ligand bond breaking; surprisingly, no sizeable doming is observed in the oxycomplex of the Bradyrhizobium japonicum FixL sensor domain (FixLH). This assessment is deduced from the absence of the iron-histidine band around 217 cm(-1) as early as 0.5 ps. We suggest that efficient ultrafast oxygen rebinding to the heme occurs on the femtosecond time scale, thus hindering heme doming. Comparing WT oxy-FixLH, mutant proteins FixLH-R220H and FixLH-R220Q, the respective carbonmonoxy-complexes, and oxymyoglobin, we show that a hydrogen bond of the terminal oxygen atom with the residue in position 220 is responsible for the observed behavior; in WT FixL this residue is arginine, crucially implicated in signal transmission. We propose that the rigid O2 configuration imposed by this residue, in combination with the hydrophobic and constrained properties of the distal cavity, keep dissociated oxygen in place. These results uncover the origin of the "oxygen cage" properties of this oxygen sensor protein. PMID:17446273

  7. Raman facility

    Federal Laboratory Consortium — Raman scattering is a powerful light scattering technique used to diagnose the internal structure of molecules and crystals. In a light scattering experiment, light...

  8. Mapping of Low-Frequency Raman Modes in CVD-Grown Transition Metal Dichalcogenides: Layer Number, Stacking Orientation and Resonant Effects

    Maria O’Brien; Niall McEvoy; Damien Hanlon; Toby Hallam; Coleman, Jonathan N.; Duesberg, Georg S.

    2016-01-01

    Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intens...

  9. Development of a femtosecond time-resolved near-IR multiplex stimulated Raman spectrometer in resonance with transitions in the 900-1550 nm region.

    Takaya, Tomohisa; Iwata, Koichi

    2016-07-21

    Charge transfer and charge delocalisation processes play key roles in the functions of large biomolecular systems and organic/inorganic devices. Many of the short-lived transients involved in these processes can be sensitively detected by monitoring their low-energy electronic transitions in the near-IR region. Ultrafast time-resolved near-IR Raman spectroscopy is a promising tool for investigating the structural dynamics of the short-lived transients as well as their electronic dynamics. In this study, we have developed a femtosecond time-resolved near-IR multiplex stimulated Raman spectrometer using the Raman pump pulse at 1190 nm and a broadband probe pulse covering the 900-1550 nm region. Spectral and temporal instrument responses of the spectrometer are estimated to be 5 cm(-1) and 120 fs, respectively. Time-resolved near-IR stimulated Raman spectra of poly(3-dodecylthiophene) (P3DDT) are recorded in toluene solution for investigating its structural changes following the photoexcitation. The spectra strongly indicate conformational changes of P3DDT in excited states associated with the elongation of its effective conjugation length. The results on P3DDT fully demonstrate the effectiveness of the newly developed femtosecond time-resolved near-IR stimulated Raman spectrometer. PMID:27327140

  10. La spectrométrie Raman de résonance résolue dans le temps : une puissante méthode d'investigation en temps réel de la réactivité photochimique Time Resolved Resonance Raman Spectrometry: a Powerful Method for the Real-Time Investigation of Photochemical Reactivity

    Buntinx G.

    2006-11-01

    Full Text Available La spectroscopie Raman de résonance résolue dans le temps est une technique récente particulièrement bien adaptée à la caractérisation des intermédiaires réactionnels mis en jeu dans les réactions photochimiques (états excités, radicaux, paires d'ions, . . . . Elle permet de visualiser finement les variations de géométrie et de distribution électronique des espèces transitoires tout au long du chemin réactionnel. Nous présentons dans cet article une compilation des résultats obtenus dans notre laboratoire sur des molécules aromatiques dérivées du biphényle. Ces résultats constituent une bonne illustration des potentialités de cette technique à apporter des informations sur la réactivité de cette famille de composés. Après une partie consacrée à la description du dispositif expérimental utilisé dans de telles expériences, nous abordons l'étude structurale par spectrométrie Raman de résonance résolue dans le temps des radicaux cations et des états triplets de dérivés du biphényle. La dernière partie de cet article est consacrée à l'étude de la réactivité photochimique de dérivés de la pyridine (4,4'-bipyridine, 2,2'-bipyridine, 4-phénylpyridine, 2--phénylpyridine dans les solvants organiques par spectrométrie Raman de résonance résolue dans le temps. Time resolved resonance Raman spectroscopy is a recent technique that is particularly well suited for characterizing reaction intermediates involved in photochemical reactions (excited states, radicals, ion pair, etc. . It can finely visualize variations in geometry and electron distribution of transient species along the entire reaction path. This article describes a compilation of the results obtained in our laboratory on aromatic molecules derived from biphenyl. These results are a good illustration of the potentialities of this technique for providing information on the reactivity of this family of compounds. After a section devoted to

  11. Fabrication of partially oxidized ultra-thin nanocrystalline silver films: effect of surface plasmon resonance on fluorescence quenching and surface enhanced Raman scattering

    Plasmonically active nanocrystalline silver (Ag) films of mass thickness ∼1 nm were fabricated using thermal evaporation followed by air annealing process temperature varying from 50 °C to 250 °C. The effect of air annealing on surface morphology and optical absorbance of quasi-amorphous and nanocrystalline Ag films was studied. The possibility of formation of silver oxide (AgO) at the surface level of Ag nanostructures due to air annealing was studied using a confocal Raman spectrometer. Surface enhanced Raman scattering (SERS) enhancement and its reverse mechanism known as fluorescence quenching corresponding to Rhodamine-6G (Rh6G) molecules were studied on Ag films through altering crystallinity, interparticles distance, size distribution and number density of Ag nanopartices (NPs). (papers)

  12. Raman Imaging

    Stewart, Shona; Priore, Ryan J.; Nelson, Matthew P.; Treado, Patrick J.

    2012-07-01

    The past decade has seen an enormous increase in the number and breadth of imaging techniques developed for analysis in many industries, including pharmaceuticals, food, and especially biomedicine. Rather than accept single-dimensional forms of information, users now demand multidimensional assessment of samples. High specificity and the need for little or no sample preparation make Raman imaging a highly attractive analytical technique and provide motivation for continuing advances in its supporting technology and utilization. This review discusses the current tools employed in Raman imaging, the recent advances, and the major applications in this ever-growing analytical field.

  13. An Anomalous Enhancement of the A(g)(2) Mode in the Resonance Raman Spectra of C-60 Embedded in Single-Walled Carbon Nanotubes during Anodic Charging

    Kalbáč, Martin; Zólyomi, V.; Rusznyák, A.; Koltai, J.; Kürti, J.; Kavan, Ladislav

    2010-01-01

    Roč. 114, č. 6 (2010), 2505-2511. ISSN 1932-7447 R&D Projects: GA AV ČR IAA400400804; GA AV ČR IAA400400911; GA AV ČR KAN200100801; GA ČR GC203/07/J067 Institutional research plan: CEZ:AV0Z40400503 Keywords : spectroelectrochemie * Raman spectra * SWNT Subject RIV: CG - Electrochemistry Impact factor: 4.520, year: 2010

  14. PULSED KGd(WO42 RAMAN LASER: TOWARDS EMISSION LINEWIDTH NARROWING

    V. G. Savitski

    2015-01-01

    Full Text Available The linewidth of a KGd(WO42 pulsed Raman laser is analysed experimentally for different configurations of the Raman and pump resonators: with narrow and broadband pump emission profiles, with and without linewidth narrowing elements in the Raman laser resonator, with and without injection seeding into the Raman cavity. The benefits of a narrow linewidth pump source in combination with linewidth narrowing elements in the Raman laser cavity for the efficient linewidth narrowing of the Raman emission are explained. 20 kW peak-power pulses at 1156 nm with 0,43 cm -1 emission linewidth are demonstrated from an injection seeded KGW Raman laser. 

  15. 1H NMR, electronic-absorption and resonance-Raman spectra of isomeric okenone as compared with those of isomeric β-carotene, canthaxanthin, β-apo-8'-carotenal and spheroidene

    Fujii, Ritsuko; Chen, Chun-Hai; Mizoguchi, Tadashi; Koyama, Yasushi

    1998-05-01

    Eleven cis- trans isomers of okenone were isolated by means of HPLC using a silica-gel column from an isomeric mixture which was obtained by iodine-sensitized photo-isomerization of the all- trans isomer. The configurations of eight isomers among them were determined by NMR spectroscopy using the isomerization shifts of the olefinic 1Hs and the 1H- 1H NOE correlations to be all- trans, 7- cis, 7- cis,8-s- cis, 9- cis, 9'- cis, 13- cis, 13'- cis and 9,9'-di- cis, and their electronic-absorption and resonance-Raman spectra were recorded. Based on the results: (1) the chemical shifts of the olefinic 1Hs in NMR; (2) the wavelength of the A g-→B u+ transition; and (3) the relative intensity of the A g-→A g+ versus the A g-→B u+ transition in electronic absorption; (4) the CC stretching frequency; and (5) the relative intensity of the C10-C11 (C10'-C11') versus the C14-C15 (C14'-C15') stretching vibration in resonance Raman were compared among the all- trans, 7- cis, 9- cis (9'- cis) and 13- cis (13'- cis) isomers of β-carotene, canthaxanthin, β-apo-8'-carotenal, neurosporene, spheroidene and okenone. Relevance of the systematic changes in the above five different parameters originally found in β-carotene was examined in the rest of the carotenoids, and the effects of the peripheral groups on them were explained in terms of the length and asymmetry of the conjugated system consisting of the CC and CO bonds.

  16. Fermi resonance and solvent dependence of the vC=O frequency shifts of Raman spectra: cyclohexanone and 2-cyclohexene-1-one

    Nam, S I; Lee, M S; Jung, Y M

    2001-01-01

    The carbonyl stretching vibration, vC=O of 2-cyclohexene-1-one , is in Fermi resonance with a combination tone. The amount of Fermi resonance interaction between these two modes is dependent upon the amount of solute/solvent interaction due to hydrogen bonding between the carbonyl oxygen and the solvent proton. The corrected vC=O frequency of 2-cyclohexene-1-one occurs at a lower frequency than the observed vC=O mode of cyclohexanone, possibly caused by expanded conjugation effects. The carbonyl stretching modes of cyclic ketones were also affected by interaction with the ROH/CCl sub 4 mixed solvent system.

  17. State detection using coherent Raman repumping and two-color Raman transfers

    We demonstrate state detection based on coherent Raman repumping and a two-color Raman state transfer. The Raman coupling during detection selectively eliminates unwanted dark states in the fluorescence cycle without compromising the immunity of the desired dark state to off-resonant scattering. We demonstrate this technique using 137Ba+ where a combination of Raman coupling and optical pumping leaves the metastable state, D3/2 |F''=3,mF''=3>, optically dark and immune to off-resonant scattering. All other states are strongly coupled to the upper P1/2 levels. We achieve a single-shot state-detection efficiency of 89.6(3)% in a 1-ms integration time, limited almost entirely by technical imperfections. Shelving to |F''=3,mF''=3> before detection is performed via a two-color Raman transfer with a fidelity of 1.00(3).

  18. Applications of Raman Spectroscopy to Virology and Microbial Analysis

    Harz, Michaela; Stöckel, Stephan; Ciobotă, Valerian; Cialla, Dana; Rösch, Petra; Popp, Jürgen

    This chapter reports from the utilization of Raman spectroscopic techniques like Raman microscopy, Raman optical activity (ROA), UV-resonance Raman (UVRR)-spectroscopy, surface enhanced Raman spectroscopy (SERS), and tip-enhanced Raman spectroscopy (TERS) for the investigation of viruses and microorganisms, especially bacteria and yeasts for medical and pharmaceutical applications. The application of these Raman techniques allows for the analysis of chemical components of cells and subcellular regions, as well as the monitoring of chemical differences occurring as a result of the growth of microorganisms. In addition, the interaction of microorganisms with active pharmaceutical agents can be investigated. In combination with chemometric methods Raman spectroscopy can also be applied to identify microorganisms both in micro colonies and even on single cells.

  19. X-ray M4,5 resonant Raman scattering from La metal with a final 4p hole: Calculations with 4p-4d-4f configuration interaction in the final state and comparison to experiments

    We consider the x-ray resonant Raman scattering (RRS) in La in the whole M4,5 region ending with a state with a 4p hole, along the sequence 3d104f0->3d94f1->3d104p54f1. The final state configuration mixes with that with two 4d holes, i.e., 3d104d84fn+2 having almost the same energy. Thus RRS must be described by introducing final-state configuration interaction (CI) between states with one 4p hole and with two 4d holes. This approach allows detailed experimental data on La metal to be interpreted on the basis of a purely ionic approach. It is shown that the inclusion of CI is crucial and has very clear effects. The calculations with the Kramers-Heisenberg formula describe all measured spectral features appearing in the strict Raman regime, i.e., dispersing with the incident photon energy. In the experiment also a nondispersive component is present when the excitation energy is greater than about 2 eV above the M5 peak. The shape and position of this component is well accounted for by a model based on all possible partitions of the excitation energy between localized and extended states. However the intensity of the nondispersive component is greater in the measurements, suggesting a rearrangement in the intermediate excited state. The comparison of ionic calculations with the metal measurements is legitimate, as shown by the comparison between the measurements on La metal and on LaF3 with M5 excitation giving the same spectrum within the experimental accuracy. Moreover the experiment shows that the final lifetime broadening is much greater in the final states corresponding to lower outgoing photon energies than in the states corresponding to higher outgoing photon energies

  20. Evidence for Jahn-Teller coupling and Fano-resonance of lower Hg modes in K3C60 and Rb3C60 films from Raman scattering

    The Raman scattering study of superconducting thin film of A3C60 (A = K,Rb) carried out upon laser excitations at 1.16 and 2.41 eV have revealed the significant broadening and Fano-lineshapes of several low energy Hg intramolecular modes with relative intensities and widths depending om excitation energies. The most interesting feature of the 1.16 eV excited spectrum is the wide asymmetric band at 400 cm-1 which can be assigned by Fano-shape fitting to enormously broadened Hg(2) mode red shifted compared to its bare frequency of 408 cm-1. The narrowing of all lower Hg modes in insulating A6C60 phase indicates strong electron-phonon coupling of this Jahn-Teller modes in x=3 phase and suggests that this low energy vibrations are contributing to superconducting pairing. However, the possibility to interpret the wide band at 400 cm-1 as the maximum of electronic background can not be ruled out yet and is supported by our preliminary observations of its disappearance at low temperature below Tc. (author). 31 refs, 3 figs

  1. High purity efficient first Stokes Raman laser

    Liu, Xiaomeng; Liu, Qinyong; Li, Daijun; Du, Keming

    2015-02-01

    The subject of the solid-state Raman frequency conversion to the yellow frequency spectra has been an active topic since the mid 1990's, because of its application in bio-medical and astronomy fields. However, the yellow laser performance is often limited because of the cascade conversion to second or higher Stokes. This cascade conversion not only limits the conversion efficiency and the output power of the first Stokes, but also degrades the pulse and the beam profile of the first Stokes. We present a type of polarization coupled Raman resonator, in which the higher order ( the second Stokes and higher ) laser output can be dramatically suppressed. Our Raman resonator is pumped by a Q-switched and frequency doubled slab laser, and we can get an almost pure (P559/(P559 +P532)>99%) 559 nm yellow light output with an efficiency over 39% from 532 nm to 559 nm. The resonator includes a high reflection rear mirror, a KGW crystal, a polarization coupled input/output element, and a high reflection output coupler of 559 nm (R559 nm = 0.6). Furthermore, we have proposed an improvement of this polarization coupled Raman resonator. The theoretical calculations of the temporal and spatial dependent Raman conversion equations show that the conversion efficiency of the first order Stokes is greatly enhanced with an additionalλ/2 waveplate for 589 nm and the BBO crystal.

  2. Transient Impulsive Giant Electronic Raman Redistribution

    Miyabe, S

    2014-01-01

    Resonant Raman excitation by ultrafast vacuum ultraviolet laser pulses is a powerful means to study electron dynamics in molecules, but experiments must contend with linear background ionization: frequencies high enough to reach resonant core-valence transitions will usually ionize all occupied orbitals as well, and the ionization cross sections are usually dominant. Here we show that attosecond pulses can induce a new process, transient impulsive stimulated Raman scattering, which can overwhelm valence ionization. Calculations are performed for atomic sodium, but the principal is valid for many molecular systems. This approach opens the path for high fidelity multidimensional spectroscopy with attosecond pulses.

  3. Spectral interferometric polarised coherent anti-Stokes Raman spectroscopy

    Littleton, Brad; Festy, Frederic; Richards, David

    2013-01-01

    We have developed an interferometric implementation of coherent anti-Stokes Raman scattering (CARS) which enables broadband coherent Raman spectroscopy free from non-resonant background (NRB), with a signal strength proportional to concentration. Spectra encode mode symmetry information into the amplitude response which can be directly compared to polarised spontaneous Raman spectra. The method requires only passive polarisation optics and is suitable for a wide range of laser linewidths and pulse durations

  4. Magnetic Circular Dichroism in Resonant Raman Scattering in the Perpendicular Geometry at the L edge of 3d Transition Metal Systems

    We measured circular dichroism in resonant x-ray scattering 3dn→2p53dn+1→3s13dn+1 with incidence perpendicular to the magnetization where the absorption dichroism vanishes. The advantages of photon scattering over other techniques make it possible to study a wide range of materials. The Ni L3 dichroism in NiFe2O 4 is (28±5)% in agreement with a localized model. In the metal Co the dichroism is reduced to (10.4±1)% (L3) and (6.8±1.5)% (7.5 eV above L3 ), indicating a large sensitivity to the nature of the valence states despite the fact that this spectroscopy is based on inner shell transitions. copyright 1999 The American Physical Society

  5. On-Line Multichannel Raman Spectroscopic Detection System For Capillary Zone Electrophoresis

    2001-01-01

    An on-line multichannel Raman spectroscopic detection system for capillary electrophoresis was established by using an Ar+ laser and a cryogenically cooled ICCD. Resonant excitation Raman spectra of methyl red and methyl orange were employed to test the system. The result shows that it could yield on-line electrophoretogram and time series of Raman spectra.

  6. Surface-Enhanced Raman Scattering and Biophysics

    Kneipp, Katrin

    2001-03-01

    Surface-enhanced Raman scattering (SERS) is a phenomenon resulting in strongly increased Raman signals from molecules which have been attached to metallic nanostructures such as colloidal silver or gold particles. The effect combines the structural information content of a vibrational spectroscopy with extremely high sensitivity and in some cases, it showes promise in overcoming the low-sensitivity problems inherent in Raman spectroscopy. Cross sections effective in SERS can reach 10 16 to 10 15 cm2 per molecule corresponding to enhancement factors of about fourteen orders of magnitude compared with “normal” non-resonant Raman scattering. Such extremely large cross sections are sufficient for single molecule Raman spectroscopy. The high sensitivity and particularly the single molecule capabilities open up exciting perspectives for SERS as tool for basic research in biophysics, biochemistry and in laboratory medicine, where it allows to study extremely small amounts of biolomedically relevant molecules in order to understand development of diseases, treatment and therapy control based on molecular structural information at the single molecule level. The most spectacular applications might appear in rapidly spectroscopic characterization of specific DNA fragments down to structurally sensitive detection of single bases in order to elucidate the human genome sequence without any labeling technology. I will briefly introduce the SERS effect and report experiments with Raman scattering of single molecules. Potential and limitations of surface-enhanced Raman techniques as a tool in biophysics and biomedical spectroscopy will be considered.

  7. Collective spectral properties of Raman scattering

    The theory of collective Raman scattering has been developed by using the quantum-mechanical master-equation approach and secular approximation. The influence of the frequency detuning of resonance and other parameters on the collective spectral properties of scattered light is investigated

  8. Raman Spectroscopy of Ocular Tissue

    Ermakov, Igor V.; Sharifzadeh, Mohsen; Gellermann, Warner

    excised tissue samples and synthetic preparations and thus to identify potential biomarkers for the onset of this disease. Using resonance Raman detection techniques, the concentration and spatial distribution of macular pigment, a protective compound, can be detected in the living human retina Useable in clinical settings for patient screening, the technology is suitable to investigate correlations between pigment concentration levels and risk for macular degeneration and to monitor increases in pigment levels occurring as a result of dietary intervention strategies.

  9. Coherently controlling Raman-induced grating in atomic media

    Arkhipkin, V G; Timofeev, I V

    2015-01-01

    We consider dynamically controllable periodic structures, called Raman induced gratings, in three- and four-level atomic media, resulting from Raman interaction in a standing-wave pump. These gratings are due to periodic spatial modulation of the Raman nonlinearity and fundamentally differ from the ones based on electromagnetically induced transparency. The transmission and reflection spectra of such gratings can be simultaneously amplified and controlled by varying the pump field intensity. It is shown that a transparent medium with periodic spatial modulation of the Raman gain can be opaque near the Raman resonance and yet at the same time it can be a non-linear amplifying mirror. We also show that spectral properties of the Raman induced grating can be controlled with the help of an additional weak control field.

  10. Polarizability corrections in stimulated Raman propagation

    Traditional descriptions of stimulated Raman scattering relate the various Stokes and anti-Stokes fields to the incident pump field by means of a polarizability (tensor). This description is usable for pulsed radiation but it fails when the pump carrier frequency coincides with a resonant frequency of the medium. We here describe a simple procedure for correcting the traditional polarizability approximation for pulse envelopes so as to account for effects of finite pump bandwidth. The correction amounts to the introduction of an auxiliary field envelope that incorporates pump dispersion. We apply this procedure to the equations for a degenerate, Doppler broadened ensemble of three-level atoms, in which the uppermost (virtual) level is close to resonance with the pump carrier frequency. This system becomes a two-level Raman system, but with a correction to the Raman Hamiltonian and the propagation equation. The plane-wave propagation equations presented include dispersive as well as Raman effects, and allow arbitrary combinations of field polarizations. We comment on several incidental aspects of Raman propagation, including dynamic Stark shifts, sublevel averages and fluence equations

  11. Coherent Raman spectroscopy

    Eesley, G L

    1981-01-01

    Coherent Raman Spectroscopy provides a unified and general account of the fundamental aspects of nonlinear Raman spectroscopy, also known as coherent Raman spectroscopy. The theoretical basis from which coherent Raman spectroscopy developed is described, along with its applications, utility, and implementation as well as advantages and disadvantages. Experimental data which typifies each technique is presented. This book is comprised of four chapters and opens with an overview of nonlinear optics and coherent Raman spectroscopy, followed by a discussion on nonlinear transfer function of matter

  12. In situ cell cycle phase determination using Raman spectroscopy

    Oshima, Yusuke; Takenaka, Tatsuji; Sato, Hidetoshi; Furihata, Chie

    2010-02-01

    Raman spectroscopy is a powerful tool for analysis of the chemical composition in living tissue and cells without destructive processes such as fixation, immunostaining, and fluorescence labeling. Raman microspectroscopic technique enables us to obtain a high quality spectrum from a single living cell. We demonstrated in situ cell cycle analysis with Raman microspectroscopy with the excitation wavelength of 532 nm. Cell cycle phases, G0/G1 and G2/M were able to be identified in the present study. The result of in situ Raman analysis was evaluated with flow cytometry analysis. Although the Raman spectra of living cells showed complex patterns during cell cycle, several Raman bands could be useful as markers for the cell cycle identification. A single cell analysis using Raman microspectroscopy predicted a possibility to observe directly molecular dynamics intracellular molecules of proteins, lipids and nucleic acids. Our current study focused on cytoplasm region and resonant Raman signals of cytochrome c in mitochondrion, and discussed how the Raman signals from cellular components contribute to the Raman spectral changes in cell cycle change in the human living cell (lung cancer cell).

  13. Raman spectra of carotenoids in natural products

    Withnall, Robert; Chowdhry, Babur Z.; Silver, Jack; Edwards, Howell G. M.; de Oliveira, Luiz F. C.

    2003-08-01

    Resonance Raman spectra of naturally occurring carotenoids have been obtained from nautilus, periwinkle ( Littorina littorea) and clam shells under 514.5 nm excitation and these spectra are compared with the resonance Raman spectra obtained in situ from tomatoes, carrots, red peppers and saffron. The tomatoes, carrots and red peppers gave rise to resonance Raman spectra exhibiting a ν1 band at ca. 1520 cm -1, in keeping with its assignment to carotenoids with ca. nine conjugated carboncarbon double bonds in their main chains, whereas the resonance Raman spectrum of saffron showed a ν1 band at 1537 cm -1 which can be assigned to crocetin, having seven conjugated carboncarbon double bonds. A correlation between ν1 wavenumber location and effective conjugated chain length has been used to interpret the data obtained from the shells, and the wavenumber position (1522 cm -1) of the ν1 band of the carotenoid in the orange clam shell suggests that it contains nine conjugated double bonds in the main chain. However, the black periwinkle and nautilus shells exhibit ν1 bands at 1504 and 1496 cm -1, respectively. On the basis of the correlation between ν1 wavenumber location and effective conjugated chain length, this indicates that they contain carotenoids with longer conjugated chains, the former having ca. 11 double bonds and the latter ca. 13 or even more. Raman spectra of the nautilus, periwinkle and clam shells also exhibited a strong band at 1085 cm -1 and a doublet with components at 701 and 705 cm -1, which can be assigned to biogenic calcium carbonate in the aragonite crystallographic form.

  14. Confocal Raman Microscopy

    Dieing, Thomas; Toporski, Jan

    2011-01-01

    Confocal Raman Microscopy is a relatively new technique that allows chemical imaging without specific sample preparation. By integrating a sensitive Raman spectrometer within a state-of-the-art microscope, Raman microscopy with a spatial resolution down to 200nm laterally and 500nm vertically can be achieved using visible light excitation. Recent developments in detector and computer technology as well as optimized instrument design have reduced integration times of Raman spectra by orders of magnitude, so that complete images consisting of tens of thousands of Raman spectra can be acquired in seconds or minutes rather than hours, which used to be standard just one decade ago. The purpose of this book is to provide the reader a comprehensive overview of the rapidly developing field of Confocal Raman Microscopy and its applications.

  15. Enhancing the efficiency of silicon Raman converters

    Vermeulen, Nathalie; Sipe, John E.; Thienpont, Hugo

    2010-05-01

    We propose a silicon ring Raman converter in which the spatial variation of the Raman gain along the ring for TE polarization is used to quasi-phase-match the CARS process. If in addition the pump, Stokes, and anti-Stokes waves involved in the CARS interaction are resonantly enhanced by the ring structure, the Stokes-to-anti-Stokes conversion efficiency can be increased by at least four orders of magnitude over that of one-dimensional perfectly phase-matched silicon Raman converters, and can reach values larger than unity with relatively low input pump intensities. These improvements in conversion performance could substantially expand the practical applicability of the CARS process for optical wavelength conversion.

  16. Photodissociation and continuum resonance Raman cross sections and general Franck--Condon intensities from S-matrix Kohn scattering calculations with application to the photoelectron spectrum of H2F-+hν→H2+F, HF+H + e-

    It is shown how the S-matrix version of the Kohn variational method for quantum scattering can be readily adapted to compute matrix elements involving the scattering wave function and also matrix elements of the scattering Green's function. The former of these quantities is what is involved in computing photodissociation cross sections, photodetachment intensities from a bound negative ion to a neutral scattering state, or the intensity of any Franck--Condon transition from a bound state to a scattering state. The latter quantity (i.e., a matrix element of the scattering Green's function between two bound states) gives the resonance Raman cross section for the case that the intermediate state in the Raman process is a scattering state. Once the basic S-matrix Kohn scattering calculation has been performed, it is shown that little additional effort is required to determine these quantities. Application of this methodology is made to determine the electron energy distribution for photodetachment of H2F- to F+H2, HF+H. Resonance structure in the J=0 reaction probabilities is seen to appear in the electron energy distribution

  17. Novel Raman instrumentation for characterizing 2D nanomaterials

    Hight Walker, Angela

    2015-03-01

    We have designed and constructed a unique Raman microscope system to enable diffraction limited measurements of graphene and two-dimensional transition-metal dichalcogenides (TMD). The design enables low frequency phonon measurements down to ten wavenumbers through a triple grating Raman spectrometer, as well as resonance Raman spectroscopy through multiple laser excitation lines throughout the visible region. Through coupling to a cryogen-free magnet system, Raman spectra can be collected while the sample is in fields up 9 Tesla and at temperatures from 4 K to 400 K. Uniquely, both Farady and Voight geometries are accessible. Furthermore, multiple electronic feedthroughs permit collecting Raman scatter from devices at varying voltages. Proof of concept measurements on TMDs will highlight the full capabilities of the instrumentation. Collaborations are sought to demonstrate the utility of the new instrumentation.

  18. On-Chip Diamond Raman Laser

    Latawiec, Pawel; Burek, Michael J; Hausmann, Birgit J M; Bulu, Irfan; Loncar, Marko

    2015-01-01

    Synthetic single-crystal diamond has recently emerged as a promising platform for Raman lasers at exotic wavelengths due to its giant Raman shift, large transparency window and excellent thermal properties yielding a greatly enhanced figure-of-merit compared to conventional materials. To date, diamond Raman lasers have been realized using bulk plates placed inside macroscopic cavities, requiring careful alignment and resulting in high threshold powers (~W-kW). Here we demonstrate an on-chip Raman laser based on fully-integrated, high quality-factor, diamond racetrack micro-resonators embedded in silica. Pumping at telecom wavelengths, we show Stokes output discretely tunable over a ~100nm bandwidth around 2-{\\mu}m with output powers >250 {\\mu}W, extending the functionality of diamond Raman lasers to an interesting wavelength range at the edge of the mid-infrared spectrum. Continuous-wave operation with only ~85 mW pump threshold power in the feeding waveguide is demonstrated along with continuous, mode-hop-fr...

  19. Portable raman explosives detection

    Moore, David Steven [Los Alamos National Laboratory; Scharff, Robert J [Los Alamos National Laboratory

    2008-01-01

    Recent advances in portable Raman instruments have dramatically increased their application to emergency response and forensics, as well as homeland defense. This paper reviews the relevant attributes and disadvantages of portable Raman spectroscopy, both essentially and instrumentally, to the task of explosives detection in the field.

  20. Enhanced Raman scattering of graphene on Ag nanoislands

    HU Wei; HUANG ZhiYi; ZHOU YingHui; CAI WeiWei; KANG JunYong

    2014-01-01

    The effect of Ag nanoislands on the Raman of graphene was investigated in this work.Compared with that on the bare silicon wafer,Raman enhancement was observed in the graphene film that covered on Ag/Si surface with nanoscale Ag islands,which would be induced by the localized plasmon resonance in Ag nanostructures.The interaction between the graphene sheet and Ag/Si substrate was further studied.The peak shift and line shape of Raman spectroscopy indicated a nonuniform strain distribution in the Ag/Si supported graphene film.

  1. Raman modes in transferred bilayer CVD graphene

    Niilisk Ahti

    2015-01-01

    Full Text Available A systematic experimental Raman spectroscopic study of twisted bilayer graphene (tBLG domains localized inside wide-area single layer graphene (SLG produced by low-pressure CVD on Cu foil and transferred onto SiO2/Si substrate has been performed. According to the Raman characterization the tBLG domains had a great variety of twisting angles θ between the bottom and top graphene layers (6° < θ < 25°. The twisting angle θ was estimated from the spectral position of the rotating R and R' modes in the Raman spectrum.Under G band resonance conditions the breathing mode ZO' with a frequency of 95- 97 cm−1 was detected, and a breathing mode ZO was found in the spectra between 804 cm−1 and 836 cm−1, its position depending on the twisting angle θ. An almost linear relationship was found between the frequencies ωZO and ωR. Also a few other spectral peculiarities were found, e.g. a high-energy excitation of the G band resonance, the 2G overtone appearing at 3170-3180 cm−1 by the G band resonance, revealing a linear dispersion of 80 cm−1/eV of the 2D band in tBLG

  2. Citrate-reduced silver hydrosol modified with omega-mercaptoalkanoic acids self-assembled monolayers as a substrate for surface-enhanced resonance Raman scattering. A study with cytochrome c

    Bonifacio, A.; Sneppen, van der L.; Gooijer, C.; Zwan, van der G.

    2004-01-01

    A new citrate-reduced silver hydrosol coated with omega-mercaptoalkanoic acids (mercaptopropionic and mercaptoundecanoic acids) self-assembled monolayers was prepared and characterized with surface-enhanced Raman spectroscopy. The structure and the quality of the coating monolayers are discussed and

  3. Raman spectroscopic analysis of isomers of biliverdin dimethyl ester.

    Matysik, J; Hildebrandt, P; Smit, K; Mark, F; Gärtner, W; Braslavsky, S E; Schaffner, K; Schrader, B

    1997-06-01

    The constitutional isomers of biliverdin dimethyl ester, IX alpha and XIII alpha, were studied by resonance Raman spectroscopy. The far-reaching spectral similarities suggest that despite the different substitution patterns, the compositions of the normal modes are closely related. This conclusion does not hold only for the parent state (ZZZ, sss configuration) but also for the configurational isomers which were obtained upon double-bond photoisomerization. Based on a comparison of the resonance Raman spectra, a EZZ configuration is proposed for one of the two photoisomers of biliverdin dimethyl ester IX alpha, while a ZZE, ssa configuration has been assigned previously to the second isomer. PMID:9226559

  4. Raman scattering in crystals

    Edwards, D.F.

    1988-09-30

    A tutorial presentation is given of Raman scattering in crystals. The physical concepts are emphasized rather than the detailed mathematical formalism. Starting with an introduction to the concepts of phonons and conservation laws, the effects of photon-phonon interactions are presented. This interaction concept is shown for a simple cubic crystal and is extended to a uniaxial crystal. The correlation table method is used for determining the number and symmetry of the Raman active modes. Finally, examples are given to illustrate the relative ease of using this group theoretical method and the predictions are compared with measured Raman spectra. 37 refs., 17 figs., 6 tabs.

  5. Raman scattering in crystals

    A tutorial presentation is given of Raman scattering in crystals. The physical concepts are emphasized rather than the detailed mathematical formalism. Starting with an introduction to the concepts of phonons and conservation laws, the effects of photon-phonon interactions are presented. This interaction concept is shown for a simple cubic crystal and is extended to a uniaxial crystal. The correlation table method is used for determining the number and symmetry of the Raman active modes. Finally, examples are given to illustrate the relative ease of using this group theoretical method and the predictions are compared with measured Raman spectra. 37 refs., 17 figs., 6 tabs

  6. New Insight into Erythrocyte through In Vivo Surface-Enhanced Raman Spectroscopy

    Brazhe, Nadezda A.; Abdali, Salim; Brazhe, Alexey R.; Luneva, Oksana G.; Bryzgalova, Nadezda Y.; Parshina, Eugenia Y.; Sosnovtseva, Olga V.; Maksimov, Georgy V.

    2009-01-01

    The article presents a noninvasive approach to the study of erythrocyte properties by means of a comparative analysis of signals obtained by surface-enhanced Raman spectroscopy (SERS) and resonance Raman spectroscopy (RS). We report step-by-step the procedure for preparing experimental samples...

  7. Construction of coherent antistokes Raman spectroscopy (CARS)

    Coherent Antistokes Raman Spectroscopy (CARS) has been built. It consists of a Raman cell, which is filled with CO2 gas at 5 atm pressure and a frequency doubled Nd-YAG laser pumped dye laser. The two beams are focused by means of a bi-convex lens into Raman cell. The Antistokes signals (CARS signals) are generated due to Four-wave mixing process. The antistokes signals were directed to monochrometer entrance slit by prism . The signals are detected by photomultiplier detector which is fixed on the exit slit and connected to data acquisition card located inside the computed case. The dye laser frequency has to be tuned to satisfy the energy difference between the ν1 beam (Nd- YAG laser beam) and the ν2 beam (the stokes beam or the dye laser beam) exactly corresponds to a vibrational - rotational Raman resonance (ν2 - ν1 = νM) in the 12CO2 or 13CO2 molecule, then the antistokes signals (ν3) will be generated. The spectra of the CARS signals have been recorded to determine the isotope shift of 12CO2, 13CO2, which is 18.3 cm-1. (author)

  8. Synthesis, electronic structure, and Raman scattering of phosphorus-doped single-wall carbon nanotubes

    Substitutional phosphorus doping in single-wall carbon nanotubes (SWNTs) is investigated by density functional theory and resonance Raman spectroscopy. Electronic structure calculations predict charge localization on the phosphorus atom, which is also responsible of generating non-dispersive valence and conduction bands close to the Fermi level. Analysis of electron and phonon renormalization in the double-resonance Raman process confirms the different nature of the phosphorus donor doping (localized) when compared to nitrogen substitutional doping (non-localized) in SWNTs

  9. A High Efficiency Architecture for Cascaded Raman Fiber Lasers

    Supradeepa, V R; Headley, Clifford E; Yan, Man F; Palsdottir, Bera; Jakobsen, Dan

    2013-01-01

    We demonstrate a new high efficiency architecture for cascaded Raman fiber lasers based on a single pass cascaded amplifier configuration. Conversion is seeded at all intermediate Stokes wavelengths using a multi-wavelength seed source. A lower power Raman laser based on the conventional cascaded Raman resonator architecture provides a convenient seed source providing all the necessary wavelengths simultaneously. In this work we demonstrate a 1480nm laser pumped by an 1117nm Yb-doped fiber laser with maximum output power of 204W and conversion efficiency of 65% (quantum-limited efficiency is ~75%). We believe both the output power and conversion efficiency (relative to quantum-limited efficiency) are the highest reported for Raman fiber lasers.

  10. Measurement of spin coherence using Raman scattering

    Sun, Z.; Delteil, A.; Faelt, S.; Imamoǧlu, A.

    2016-06-01

    Ramsey interferometry provides a natural way to determine the coherence time of most qubit systems. Recent experiments on quantum dots, however, demonstrated that dynamical nuclear spin polarization can strongly influence the measurement process, making it difficult to extract the T2* coherence time using standard optical Ramsey pulses. Here, we demonstrate an alternative method for spin coherence measurement that is based on first-order coherence of photons generated in spin-flip Raman scattering. We show that if a quantum emitter is driven by a weak monochromatic laser, Raman coherence is determined exclusively by spin coherence, allowing for a direct determination of spin T2* time. When combined with coherence measurements on Rayleigh scattered photons, our technique enables us to identify coherent and incoherent contributions to resonance fluorescence, and to minimize the latter. We verify the validity of our technique by comparing our results to those determined from Ramsey interferometry for electron and heavy-hole spins.

  11. Rotational Raman scattering in sup 127 I

    Mondry, G.; Wissmann, F.; Mueller, G.; Schroeder, F.; Rullhusen, P.; Smend, F.; Schumacher, M. (2. Physikalisches Inst., Univ. Goettingen (Germany)); Fettweis, P.; Carchon, R. (Studiecentrum voor Kernenergie, Centre de l' Etudes de l' Energie Nucleaire, Mol (Belgium))

    1991-09-02

    Elastic and Raman scattering of photons by {sup 181}Ta and {sup 127}I are studied using the 11.4 MeV mono-energetic photon beam installed at the Mol BR2 reactor. For the strongly deformed prolate nucleus {sup 181}Ta the simple rotator model is re-investigated and found to be valid. The intrinsic quadrupole moment Q{sub 0} derived from spectroscopic data by assuming a strong particle-surface coupling was found to be in agreement with the splitting of the giant dipole resonance, thus removing previous inconsistencies. When applying the same model to the oblate nucleus {sup 127}I a severe discrepancy between experimental and predicted Raman cross sections was observed; this discrepancy is discussed in terms of nuclear-structure properties. (orig.).

  12. Raman and surface enhanced Raman spectroscopic investigation on Lamiaceae plants

    Rösch, P.; Popp, J.; Kiefer, W.

    1999-05-01

    The essential oils of Thymus vulgaris and Origanum vulgaris are studied by means of micro-Raman spectroscopy. The containing monoterpenes can be identified by their Raman spectra. Further the essential oils are investigated in their natural environment, the so-called oil cells of these Lamiaceae plants, with surface enhanced Raman spectroscopy (SERS). This method has the advantage to enhance Raman signals and furthermore the SERS effect leads to fluorescence quenching.

  13. ABSOLUTE CROSS SECTIONS FOR ONE-PHONON RAMAN SCATTERING FROM SEVERAL INSULATORS AND SEMICONDUCTORS

    Calleja, J; H. Vogt; Cardona, M.

    1981-01-01

    Using the Brillouin-Raman method we have measured the Raman scattering efficiencies for the Ɖ phonons of GaP, ZnTe, ZnSe, ZnS as well as CaF2, SrF2, BaF2. The results for the zincblende-type materials allow us to calibrate in absolute scattering efficiency units the resonance Raman curves found in the literature. From the calibrated resonances the deformation potential do is deduced on the basis of a parabolic band model. For the fluorides the scattering efficiency is attributed to the adge e...

  14. Raman spectrum of asphaltene

    Abdallah, Wael A.

    2012-11-05

    Asphaltenes extracted from seven different crude oils representing different geological formations from around the globe were analyzed using the Raman spectroscopic technique. Each spectrum is fitted with four main peaks using the Gaussian function. On the basis of D1 and G bands of the Raman spectrum, asphaltene indicated an ordered structure with the presence of boundary defected edges. The average aromatic sheet size of the asphaltene molecules is estimated within the range of 1.52-1.88 nm, which represents approximately seven to eight aromatic fused rings. This estimation is based on the integrated intensity of D1 and G bands, as proposed by Tunistra and Koenig. The results here are in perfect agreement with so many other used techniques and indicate the potential applicability of Raman measurements to determine the average aromatic ring size and its boundary. © 2012 American Chemical Society.

  15. Development of Raman spectrophotometer

    In this work, the Raman spectrophotometer HG.2S Jobin Yvon rebuilt and developed, the Raman setup provided as a gift for Neelian University from Amsterdam University. The main parts, which were replaced, include monochromator, an air-cooled photomultiplier tube RCA IP 28, log amplifier, hand scanning lab VIEW card for computer interfacing. The components assembled and the whole device was tested successfully. The developed setup was checked using some standard solutions, which showed perfect consistency with literature in the references and published papers. Solutions included hexane, cyclohexane, carbon tetrachloride, benzene and sodium sulfate.(Author)

  16. Raman scattering in a two-layer antiferromagnet

    Morr, Dirk K.; Chubukov, Andrey V.; Kampf, Arno P.; Blumberg, G.

    1996-08-01

    Two-magnon Raman scattering is a useful tool to verify recent suggestions concerning the value of the interplanar exchange constant in antiferromagnetic two-layer systems, such as YBa2Cu3O6+x. We present a theory for Raman scattering in a two-layer antiferromagnet. We study the spectra for the electronic and magnetic excitations across the charge transfer gap within the one-band Hubbard model and derive the matrix elements for the Raman scattering cross section in a diagrammatic formalism. We analyze the effect of the interlayer exchange coupling J2 for the Raman spectra in A1g and B1g scattering geometries both in the nonresonant regime (when the Loudon-Fleury model is valid) and at resonance. We show that within the Loudon-Fleury approximation, a nonzero J2 gives rise to a finite signal in A1g scattering geometry. Both in this approximation and at resonance the intensity in the A1g channel has a peak at small transferred frequency equal to twice the gap in the spin-wave spectrum. We compare our results with experiments in YBa2Cu3O6.1 and Sr2CuO2Cl2 compounds and argue that the large value of J2 suggested in a number of recent studies is incompatible with Raman experiments in A1g geometry.

  17. Timing jitter of Raman solitons.

    Zhou, Gengji; Xin, Ming; Kaertner, Franz X; Chang, Guoqing

    2015-11-01

    We study the relative intensity noise (RIN) and timing jitter of a Raman soliton. We demonstrate that the RIN of an excitation pulse causes center-wavelength fluctuations of the resulting Raman soliton which translates by fiber dispersion into relative timing jitter (RTJ) between the Raman soliton and the excitation pulse. The Raman soliton's absolute timing jitter is dominated by the excitation pulse's timing jitter at low frequency and by the RTJ at high frequency. The experimental study reveals that RTJ can be significantly reduced by reducing the accumulated fiber dispersion (e.g., using less dispersive fibers with shorter length) experienced by the Raman soliton. PMID:26512530

  18. Raman Imaging Techniques and Applications

    2012-01-01

    Raman imaging has long been used to probe the chemical nature of a sample, providing information on molecular orientation, symmetry and structure with sub-micron spatial resolution. Recent technical developments have pushed the limits of micro-Raman microscopy, enabling the acquisition of Raman spectra with unprecedented speed, and opening a pathway to fast chemical imaging for many applications from material science and semiconductors to pharmaceutical drug development and cell biology, and even art and forensic science. The promise of tip-enhanced raman spectroscopy (TERS) and near-field techniques is pushing the envelope even further by breaking the limit of diffraction and enabling nano-Raman microscopy.

  19. The Discovery of Raman Scattering in HII Regions

    Dopita, Michael A; Sutherland, Ralph S; Kewley, Lisa J; Groves, Brent A

    2016-01-01

    We report here on the discovery of faint extended wings of H\\alpha\\ observed out to an apparent velocity of ~ 7600 km/s in the Orion Nebula (M42) and in five HII regions in the Large and the Small Magellanic Clouds. We show that, these wings are caused by Raman scattering of both the O I and Si II resonance lines and stellar continuum UV photons with H I followed by radiative decay to the H I n=2 level. The broad wings also seen in H\\beta\\ and in H\\gamma\\ result from Raman scattering of the UV continuum in the H I n=4 and n=5 levels respectively.The Raman scattering fluorescence is correlated with the intensity of the narrow permitted lines of O I and Si II. In the case of Si II, this is explained by radiative pumping of the same 1023.7\\AA\\ resonance line involved in the Raman scattering by the Ly\\beta\\ radiation field. The subsequent radiative cascade produces enhanced Si II 5978.9, 6347.1$ and 6371.4\\AA\\ permitted transitions. Finally we show that in O I, radiative pumping of the 1025.76\\AA\\ resonance line ...

  20. Resonances and resonance widths

    Two-dimensional betatron resonances are much more important than their simple one-dimensional counterparts and exhibit a strong dependence on the betatron phase advance per cell. A practical definition of ''width'' is expanded upon in order to display these relations in tables. A primarily pedagogical introduction is given to explain the tables, and also to encourage a wider capability for deriving resonance behavior and wider use of ''designer'' resonances

  1. Theory of coherent Raman superradiance imaging of condensed Bose gases

    We describe theoretically the dynamics of the off-resonant superradiant Raman scattering of light in a prolate atomic Bose-Einstein condensate, from the initial stages governed by quantum fluctuations to the subsequent semiclassical regime, and within a multimode theory that fully accounts for propagation effects. Our results are in good agreement with recent experimental results that exploit Raman superradiance as an imaging technique to probe the long-range coherence of condensates, including the observed time-dependent spatial features, and account properly for the macroscopic shot-to-shot fluctuations resulting from the quantum noise that initiates the superradiance process

  2. Theory of coherent Raman superradiance imaging of condensed Bose gases

    Uys, H.; Meystre, P.

    2007-03-01

    We describe theoretically the dynamics of the off-resonant superradiant Raman scattering of light in a prolate atomic Bose-Einstein condensate, from the initial stages governed by quantum fluctuations to the subsequent semiclassical regime, and within a multimode theory that fully accounts for propagation effects. Our results are in good agreement with recent experimental results that exploit Raman superradiance as an imaging technique to probe the long-range coherence of condensates, including the observed time-dependent spatial features, and account properly for the macroscopic shot-to-shot fluctuations resulting from the quantum noise that initiates the superradiance process.

  3. Graphene-Enhanced Raman Scattering from the Adenine Molecules.

    Dolgov, Leonid; Pidhirnyi, Denys; Dovbeshko, Galyna; Lebedieva, Tetiana; Kiisk, Valter; Heinsalu, Siim; Lange, Sven; Jaaniso, Raivo; Sildos, Ilmo

    2016-12-01

    An enhanced Raman scattering from a thin layer of adenine molecules deposited on graphene substrate was detected. The value of enhancement depends on the photon energy of the exciting light. The benzene ring in the structure of adenine molecule suggests π-stacking of adenine molecule on top of graphene. So, it is proposed that the enhancement in the adenine Raman signal is explained by the resonance electron transfer from the Fermi level of graphene to the lowest unoccupied molecular orbital (LUMO) level of adenine. PMID:27075339

  4. Theory for the Acoustic Raman Modes of Proteins

    DeWolf, Timothy

    2016-01-01

    We present a theoretical analysis that associates the resonances of extraordinary acoustic Raman (EAR) spectroscopy [Wheaton et al., Nat Photon 9, 68 (2015)] with the collective modes of proteins. The theory uses the anisotropic elastic network model to find the protein acoustic modes, and calculates Raman intensity by treating the protein as a polarizable ellipsoid. Reasonable agreement is found between EAR spectra and our theory. Protein acoustic modes have been extensively studied theoretically to assess the role they play in protein function; this result suggests EAR as a new experimental tool for studies of protein acoustic modes.

  5. Graphene-Enhanced Raman Scattering from the Adenine Molecules

    Dolgov, Leonid; Pidhirnyi, Denys; Dovbeshko, Galyna; Lebedieva, Tetiana; Kiisk, Valter; Heinsalu, Siim; Lange, Sven; Jaaniso, Raivo; Sildos, Ilmo

    2016-04-01

    An enhanced Raman scattering from a thin layer of adenine molecules deposited on graphene substrate was detected. The value of enhancement depends on the photon energy of the exciting light. The benzene ring in the structure of adenine molecule suggests π-stacking of adenine molecule on top of graphene. So, it is proposed that the enhancement in the adenine Raman signal is explained by the resonance electron transfer from the Fermi level of graphene to the lowest unoccupied molecular orbital (LUMO) level of adenine.

  6. Equations describing coherent and partially coherent multilevel molecular excitation induced by pulsed Raman transitions: III

    This memo discusses the equations of motion used to describe multilevel molecular excitation induced by Raman transitions. These equations are based upon the time-dependent Schroedinger equation expressed in a basis of molecular energy states. A partition of these states is made into two sets, those that are far from resonance (and hence unpopulated) and those that are close to resonance, either by one-photon transition or two-photon (Raman) processes. By adiabatic elimination an effective Schroedinger equation is obtained for the resonance states alone. The effective Hamiltonian is expressible in terms of a polarizibility operator

  7. Raman spectroscopy of small-diameter nanotubes

    Results based on Raman measurements of small-diameter nanotubes (NTs) are presented and discussed in this paper. The NTs with diameters from 1 nm down to 0.4 nm were produced either as the inner tubes in the double-wall carbon NTs (DWCNTs) or as tubes embedded in the channels of the zeolite crystals. While analysing the Raman spectra attention was paid to the radial breathing mode (RBM), the D line and the G band. For both NT systems the RBM frequency was found to follow the same functional diameter dependence as the tubes with larger diameters. However, in contrast to the latter, the diameters of the thin tubes obtained from density functional theory calculations must be taken into account to explain satisfactorily the observed line positions. The resonance behaviour of the RBM intensities was recorded for the tubes in zeolites. It allows us to ascribe a position of the RBM to a particular NT. This result also demonstrates the breakdown of a simple tight-binding approach to the electronic structure but agrees with predictions from ab initio calculations. The D line of the outer tubes in DWCNTs is dispersive, similar to the single-wall carbon NTs. However, the rate of dispersion is reduced for the inner tubes in DWCNTs. This is attributed to the fact that the inner and outer tubes are probed with the same laser excitation. The linear shift due to the increasing laser energy is compensated by the negative shift due to the NT diameter. The latter is smaller for the inner NTs which leads to a stronger compensation of their dispersive behaviour. This effect is even stronger for the NTs in zeolites. In the extreme case, the strong Raman lines are not dispersive at all. This unexpected behaviour was explained by the detailed ab initio calculation of the phonon structure. The G bands of the inner semiconducting tubes were observed as new features in the Raman spectra of DWCNTs. On the other hand, no lines of metallic inner tubes were found. G bands of semiconducting as

  8. Raman spectroscopy of magnetoliposomes

    In this study Raman spectroscopy was used to investigate monolayer and bilayer magnetite-based magnetoliposomes (MLs). The Raman probe is the hydroxyl (OH) group chemisorbed at the magnetite nanoparticle surface. Measurements were performed at room temperature in the typical OH stretching region. The data gathered for both samples are compared to each other and with those obtained for pure water. In comparison to liquid water (2.74 kcal/mol), it was found that the hydrogen bond strength between the chemisorbed OH-group and the polar headgroup of the inner phospholipid layer was reduced in both the monolayer (2.22 kcal/mol) and the bilayer (1.83 kcal/mol) ML samples

  9. Surface enhanced Raman scattering

    Furtak, Thomas

    1982-01-01

    In the course of the development of surface science, advances have been identified with the introduction of new diagnostic probes for analytical characterization of the adsorbates and microscopic structure of surfaces and interfaces. Among the most recently de­ veloped techniques, and one around which a storm of controversy has developed, is what has now been earmarked as surface enhanced Raman scattering (SERS). Within this phenomenon, molecules adsorbed onto metal surfaces under certain conditions exhibit an anomalously large interaction cross section for the Raman effect. This makes it possible to observe the detailed vibrational signature of the adsorbate in the ambient phase with an energy resolution much higher than that which is presently available in electron energy loss spectroscopy and when the surface is in contact with a much larger amount of material than that which can be tolerated in infrared absorption experiments. The ability to perform vibrational spectroscopy under these conditions would l...

  10. Comparative study of the two-phonon Raman bands of silicene and graphene

    Popov, Valentin N.; Lambin, Philippe

    2016-06-01

    We present a computational study of the two-phonon Raman spectra of silicene and graphene within a density-functional non-orthogonal tight-binding model. Due to the presence of linear bands close to the Fermi energy in the electronic structure of both structures, the Raman scattering by phonons is resonant. We find that the Raman spectra exhibit a crossover behavior for laser excitation close to the π-plasmon energy. This phenomenon is explained by the disappearance of certain paths for resonant Raman scattering and the appearance of other paths beyond this energy. Besides that, the electronic joint density of states (DOS) is divergent at this energy, which is reflected on the behavior of the Raman bands of the two structures in a qualitatively different way. Additionally, a number of Raman bands, originating from divergent phonon DOS at the M point and at points, inside the Brillouin zone, is also predicted. The calculated spectra for graphene are in excellent agreement with available experimental data. The obtained Raman bands can be used for structural characterization of silicene and graphene samples by Raman spectroscopy.

  11. Amplifying the SERS signal of DNA bases via the chemical resonance

    Freeman, Lindsay M.; Pang, Lin; Fainman, Yeshaiahu

    2015-03-01

    Label-free detection methods of DNA bases using surface-enhanced Raman spectroscopy (SERS) have yet to be successfully utilized due to inconsistent signal readouts. We have identified the primary reason for the discrepancies in the SERS signals of nucleic acids as being caused by the charge-transfer chemical resonance of the base silver system which is dependent on excitation wavelength. Time-dependent density functional theory (TD-DFT) methods to calculate the electronic transitions and resonance Raman spectra of base silver complexes are performed, and the optimal excitation wavelength for the charge-transfer electronic transition is found for each base silver complex. The enhancement caused by the chemical resonance is then experimentally measured for adenine, cytosine, guanine and thymine at multiple excitation wavelengths. The dependence of the Raman intensity on excitation wavelength shows good agreement with the TD-DFT calculations. In order to fully achieve the maximum Raman intensity, both the electromagnetic and chemical resonance must be enhanced by the appropriate wavelength selection. Based on the optimal chemical resonance Raman wavelength, we design a SERS substrate which has an electromagnetic maximum wavelength that matches the chemical resonance wavelength. By aligning both resonances, the highest Raman intensity can be found for each base silver system. We have proven that the variance in DNA bases' Raman intensities are caused by chemical enhancement. By incorporating the chemical resonance and optimizing both the chemical and electromagnetic resonance, we believe a label-free DNA SERS based detection method can be realized.

  12. Enhancement of Raman light scattering in dye-labeled cell membrane on metal-containing conducting polymer film

    Grushevskaya, H. V.; Krylova, N. G.; Lipnevich, I. V.; Orekhovskaja, T. I.; Egorova, V. P.; Shulitski, B. G.

    2016-03-01

    An enhanced Raman spectroscopy method based on a plasmon resonance in ultrathin metal-containing LB-film deposited on nanoporous anodic alumina supports has been proposed. This material has been utilized to enhance Raman scattering of light in fluorescent-labeled subcellular membrane structures. It has been shown that the plasmon resonance between vibrational modes of the organometallic complexes monolayers and dye-labeled subcellular structures happens. It makes possible to detect interactions between living cell monolayers and an extracellular matrix.

  13. Electronic Raman scattering in cuprate superconductors and parent insulating phases

    Raman scattering from charge and spin excitations in cuprates is reviewed. The two-magnon resonance Raman profile is used to determine the most probable energy for photon-assisted charge transfer leading to exchange between two spins. The difference between this energy and that for absorption is attributed to spin relaxation (spin polaron) effects. Two-magnon spectra in superconducting cuprates are presented. It is argued that their presence is evidence that the antiferromagnetic correlation length is equal to or greater than three lattice constants. The recently-discovered Raman-active excitons are described and possible assignments of them are discussed. It is pointed out that in highly correlated metals and insulators, the mechanisms for fight scattering that are familiar for doped semiconductors or conventional metals are not necessarily the only ones that are operative

  14. Cavity-Enhanced Room-Temperature Broadband Raman Memory

    Saunders, D. J.; Munns, J. H. D.; Champion, T. F. M.; Qiu, C.; Kaczmarek, K. T.; Poem, E.; Ledingham, P. M.; Walmsley, I. A.; Nunn, J.

    2016-03-01

    Broadband quantum memories hold great promise as multiplexing elements in future photonic quantum information protocols. Alkali-vapor Raman memories combine high-bandwidth storage, on-demand readout, and operation at room temperature without collisional fluorescence noise. However, previous implementations have required large control pulse energies and have suffered from four-wave-mixing noise. Here, we present a Raman memory where the storage interaction is enhanced by a low-finesse birefringent cavity tuned into simultaneous resonance with the signal and control fields, dramatically reducing the energy required to drive the memory. By engineering antiresonance for the anti-Stokes field, we also suppress the four-wave-mixing noise and report the lowest unconditional noise floor yet achieved in a Raman-type warm vapor memory, (15 ±2 )×10-3 photons per pulse, with a total efficiency of (9.5 ±0.5 )%.

  15. Kontrollierte Erzeugung einzelner Photonen in einem optischen Resonator hoher Finesse

    Hennrich, Markus

    2007-01-01

    Zur kontrollierten Erzeugung einzelner Photonen in einem optischen Resonator hoher Finesse werden einzelne Drei-Niveau Atome eingesetzt. Ein von außen eingestrahlter Laserpuls pumpt einen Zweig eines Ramanübergangs im Atom, während das Vakuumfeld des umgebenden Resonators eine Emission entlang des anderen Zweigs stimuliert. Dabei strahlt das Atom ein einzelnes Photon in den Resonator ab. Dieses wird durch den Auskoppelspiegel des Resonators gerichtet in den freien Raum emittiert. Über einen H...

  16. Raman spectra of ordinary and deuterated liquid ammonias

    The three deuterated ammonia molecules, as well as ordinary ammonia, have been examined in the liquid state by Raman spectroscopy using a high-pressure cell described elsewhere. This work thus completes the infrared spectrometry studies. We have examined the NH and ND valency absorption regions. The polarization measurements and isotope effect considerations make it possible to confirm most of the attributions recently proposed for interpreting the infrared spectra of the four isotopic molecules: the apparent disagreement between the NH3 and ND3 spectra obtained in this region by infrared and Raman spectroscopy is discussed: by the first technique the number of bands in the spectra corresponds well to the theoretically expected number, and the relative intensities conform more or less to expectations; the Raman spectra however have a strong supplementary band in the same region, produced by a Fermi resonance; it is possible to explain, from theoretical considerations, why this resonance appears so easily in the Raman spectrum, whereas it is detected in the infrared only by a very detailed analysis of the effects of solvents on the ammonia. (authors)

  17. Femtosecond stimulated Raman spectroscopy as a tool to detect molecular vibrations in ground and excited electronic states

    Gelin, Maxim F.; Domcke, Wolfgang; Rao, B. Jayachander

    2016-05-01

    We give a detailed theoretical analysis of the simplest variant of femtosecond stimulated Raman spectroscopy, where a picosecond Raman pump pulse and a femtosecond Raman probe pulse are applied resonantly to a chromophore in thermal equilibrium in the ground electronic state. We demonstrate that this technique is capable of the detection of dephasing-free Raman-like lines revealing vibrational modes not only in the electronic ground state but also in the excited electronic state of the chromophore. The analytical results obtained with simplifying assumptions for the shape of the laser pulses are substantiated by numerical simulations with realistic laser pulses, employing the equation-of-motion phase-matching approach.

  18. [Research Progress of Raman Spectroscopy on Dyestuff Identification of Ancient Relics and Artifacts].

    He, Qiu-ju; Wang, Li-qin

    2016-02-01

    As the birthplace of Silk Road, China has a long dyeing history. The valuable information about the production time, the source of dyeing material, dyeing process and preservation status were existed in organic dyestuff deriving from cultural relics and artifacts. However, because of the low contents, complex compositions and easily degraded of dyestuff, it is always a challenging task to identify the dyestuff in relics analyzing field. As a finger-print spectrum, Raman spectroscopy owns unique superiorities in dyestuff identification. Thus, the principle, characteristic, limitation, progress and development direction of micro-Raman spectroscopy (MRS/µ-Raman), near infrared reflection and Fourier transform Raman spectroscopy (NIR-FT-Raman), surface-enhanced Raman spectroscopy (SERS) and resonance raman spectroscopy (RRS) have been introduced in this paper. Furthermore, the features of Raman spectra of gardenia, curcumin and other natural dyestuffs were classified by MRS technology, and then the fluorescence phenomena of purpurin excitated with different wavelength laser was compared and analyzed. At last, gray green silver colloidal particles were made as the base, then the colorant of madder was identified combining with thin layer chromatography (TLC) separation technology and SERS, the result showed that the surface enhancement effect of silver colloidal particles could significantly reduce fluorescence background of the Raman spectra. It is pointed out that Raman spectroscopy is a rapid and convenient molecular structure qualitative methodology, which has broad application prospect in dyestuff analysis of cultural relics and artifacts. We propose that the combination of multi-Raman spectroscopy, separation technology and long distance transmission technology are the development trends of Raman spectroscopy. PMID:27209739

  19. Time-dependent micro-Raman scattering studies of polyvinyl alcohol and silver nitrate thin films

    K Shadak Alee; D Narayana Rao

    2014-02-01

    In-situ monitoring of silver nanoparticle formation was studied in thin films of polyvinyl alcohol and silver nitrate. We proposed the observation of surface-enhanced Raman spectroscopy (SERS) as a novel and simple technique to record the growth of silver nanoparticles in polyvinyl alcohol thin films. Observed enhancement in the Raman bands of polyvinyl alcohol is explained through the localized surface plasmon resonance of silver nanoparticles. Influence of temperature generated by silver nanoparticles on the formation of nanoparticles is also discussed.

  20. Theory of Raman Superradiance Imaging of Condensed Bose Gases

    Uys, Hermann; Meystre, Pierre

    2006-05-01

    We investigate superradiant off-resonant Raman scattering of light from an elongated Bose-condensate of atoms. Absorption imaging of superradiant systems yields stronger image contrast than imaging of systems scattering light incoherently. However, the spatial structure of the recoiling atomic fields is not simply proportional to the initial state density. We present a multi-mode theory that reproduces the time evolving spatial features observed in absorption images and accounts for shot-to-shot fluctuations.

  1. Efficient Raman Sideband Generation in a Coherent Atomic Medium

    Huss, A. F.; Peer, N.; Lammegger, R.; Korsunsky, E. A.; Windholz, L.

    2000-01-01

    We demonstrate the efficient generation of Raman sidebands in a medium coherently prepared in a dark state by continuous-wave low-intensity laser radiation. Our experiment is performed in sodium vapor excited in $\\Lambda $ configuration on the D$_{1}$ line by two laser fields of resonant frequencies $\\omega_{1}$ and $\\omega_{2}$, and probed by a third field $% \\omega_{3}$. First-order sidebands for frequencies $\\omega_{1}$, $\\omega_{2}$ and up to the third-order sidebands for frequency $\\omeg...

  2. Diffusion measurements by Raman spectroscopy

    Hansen, Susanne Brunsgaard; Shapiro, Alexander; Berg, Rolf W.;

    Poster "Diffusion measurements by Raman spectroscopy", See poster at http://www.kemi.dtu.dk/~ajo/rolf/petroday2004.ppt......Poster "Diffusion measurements by Raman spectroscopy", See poster at http://www.kemi.dtu.dk/~ajo/rolf/petroday2004.ppt...

  3. Raman Spectroscopy of Cocrystals

    Rooney, Frank; Reardon, Paul; Ochoa, Romulo; Abourahma, Heba; Marti, Marcus; Dimeo, Rachel

    2010-02-01

    Cocrystals are a class of compounds that consist of two or more molecules that are held together by hydrogen bonding. Pharmaceutical cocrystals are those that contain an active pharmaceutical ingredient (API) as one of the components. Pharmaceutical cocrystals are of particular interest and have gained a lot of attention in recent years because they offer the ability to modify the physical properties of the API, like solubility and bioavailability, without altering the chemical structure of the API. The APIs that we targeted for our studies are theophylline (Tp) and indomethacin (Ind). These compounds have been mixed with complementary coformers (cocrystal former) that include acetamide (AcONH2), melamine (MLM), nicotinic acid (Nic-COOH), 4-cyanopyridine (4-CNPy) and 4-aminopyridine (4-NH2Py). Raman spectroscopy has been used to characterize these cocrystals. Spectra of the cocrystals were compared to those of the coformers to analyze for peak shifts, specifically those corresponding to hydrogen bonding. A 0.5 m CCD Spex spectrometer was used, in a micro-Raman setup, for spectral analysis. An Argon ion Coherent laser at 514.5 nm was used as the excitation source. )

  4. Aharonov–Bohm oscillation of Raman scattering in a quantum ring

    An electron Raman scattering process in a semiconductor quantum ring with a repulsive scattering center is investigated in the presence of an external magnetic field. The differential cross section is calculated as a function of the diffusion photon energy. The scattering spectra are discussed for the different magnetic field strengths and ring radii. The calculated results show that the electron Raman scattering of quantum rings is strongly affected by the external magnetic field, the ring radius and the impurity. Also we find that the resonant peak of the differential cross section of electron Raman scattering shows the optical Aharonov–Bohm oscillation upon changing the magnetic field and the ring radius.

  5. Aharonov–Bohm oscillation of Raman scattering in a quantum ring

    Xie, Wenfang, E-mail: xiewf@vip.163.com

    2014-04-01

    An electron Raman scattering process in a semiconductor quantum ring with a repulsive scattering center is investigated in the presence of an external magnetic field. The differential cross section is calculated as a function of the diffusion photon energy. The scattering spectra are discussed for the different magnetic field strengths and ring radii. The calculated results show that the electron Raman scattering of quantum rings is strongly affected by the external magnetic field, the ring radius and the impurity. Also we find that the resonant peak of the differential cross section of electron Raman scattering shows the optical Aharonov–Bohm oscillation upon changing the magnetic field and the ring radius.

  6. Two-magnon Raman scattering in cuprate superconductors: Evolution of magnetic fluctuations with doping

    We report observation and resonance Raman studies of spin-pair excitations in YBa2Cu3O6+x (0.372Cu4O8 superconductors. These excitations at energy ∼3J (2700±150 cm-1), similar to two-magnon excitations in insulators, are evidence that antiferromagnetic fluctuations with spatial extent of at least three lattice constants are not overdamped in the underdoped superconductors. With optimal hole dopings, where Tc>80 K, the two-magnon peak can no longer be seen above the flat Raman continuum. Photoluminescence and the origin of the broad-spectrum Raman continuum are also discussed

  7. Noninvasive laser Raman detection of carotenoid antioxidants in living human skin

    Gellermann, Werner; Ermakov, Igor V.; Ermakova, Maia R.; McClane, Robert W.

    2001-05-01

    We have used resonance Raman scattering as a novel non- invasive optical technology to measure carotenoid antioxidants in human skin of healthy volunteers. Using blue-green laser excitation, clearly distinguishable carotenoid Raman spectra are obtained which are superimposed on a large skin autofluorescence background. The Raman spectra are obtained rapidly, i.e. within about 30 seconds, and the required laser light exposure levels are well within safety standards. Our technique can be used for rapid screening of carotenoid antioxidant levels in large populations and may have applications for assessing the risk for cutaneous diseases.

  8. Spatial resolution of tip-enhanced Raman spectroscopy - DFT assessment of the chemical effect.

    Latorre, Federico; Kupfer, Stephan; Bocklitz, Thomas; Kinzel, Daniel; Trautmann, Steffen; Gräfe, Stefanie; Deckert, Volker

    2016-05-21

    Experimental evidence of extremely high spatial resolution of tip-enhanced Raman scattering (TERS) has been recently demonstrated. Here, we present a full quantum chemical description (at the density functional level of theory) of the non-resonant chemical effects on the Raman spectrum of an adenine molecule mapped by a tip, modeled as a single silver atom or a small silver cluster. We show pronounced changes in the Raman pattern and its intensities depending on the conformation of the nanoparticle-substrate system, concluding that the spatial resolution of the chemical contribution of TERS can be in the sub-nm range. PMID:27123952

  9. Experimental and ab initio DFT calculated Raman Spectrum of Sudan I, a Red Dye

    Kunov-Kruse, Andreas Jonas; Kristensen, Steffen Buus; Liu, Chuan;

    2011-01-01

    . Comparison was made with other azo dyes in the literature on natural, abundant plant pigments. The results show that there is a possibility in foodstuff analysis to distinguish Sudan I from other dyes by using Raman spectroscopy with more than one laser wavelength for resonance enhancement of the different......The red dye Sudan I was investigated by Raman spectroscopy using different excitation wavelengths (1064, 532 and 244 nm). A calculation of the Raman spectrum based on quantum mechanical ab initio density functional theory (DFT) was made using the RB3LYP method with the 3-21G and 6-311+G(d,p) basis...

  10. Can surface-enhanced Raman scattering serve as a channel for strong optical pumping?

    Haslett, T. L.; Tay, L.; Moskovits, M.

    2000-07-01

    The surface-enhanced Raman scattering spectra of a number of dye and colorless molecules adsorbed on deposited coloidal silver films were systematically studied as a function of power and position using a Raman microscope. The anti-Stokes portions of the spectra of the dyes reproducibly show line intensities much greater than what is expected on the basis of the equilibrium population of the excited vibrational states, even at the lowest incident light intensities used. This behavior was observed previously and attributed to optical pumping of vibrationally excited states of the molecules by unusually intense surface-enhanced Raman transitions, [Phys. Rev. Lett. 76, 2444 (1996)] suggesting either uncommonly large Raman cross-sections or very intense local field strengths exceeding those encountered in the most powerful currently available lasers. Based on this work, however, we ascribe the apparently large anti-Stokes intensities primarily to a difference in the Stokes and anti-Stokes Raman cross-sections resulting from resonance or pre-resonance Raman processes in the adsorbate-surface complex rather than to strongly nonequilibrium populations in the molecular vibrational states. Finally, we observed no significant inhomogeneity in the Raman enhancement in the images of the deposited silver coloid samples down to spatial resolutions of ˜1 μm.

  11. Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals

    Guc, Maxim; Levcenko, Sergiu; Bodnar, Ivan V.; Izquierdo-Roca, Victor; Fontane, Xavier; Volkova, Larisa V.; Arushanov, Ernest; Pérez-Rodríguez, Alejandro

    2016-01-01

    A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone-center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm-1 on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis.

  12. Probing non-adiabatic conical intersections using absorption, spontaneous Raman, and femtosecond stimulated Raman spectroscopy

    We present the time-frame calculated photoabsorption spectrum (ABS), spontaneous Raman excitation profile (REP), femtosecond stimulated Raman spectroscopy (FSRS) spectrum, and femtosecond stimulated Raman excitation profile (FSREP) results of a two-mode and three-mode, three-electronic-states model Hamiltonians containing conical intersections (CIs) along its two upper diabatic electronic states, e1 (dark) and e2 (bright), with and without coupling (nonadiabatic dynamics) along an asymmetric mode. For every electronic state in each model, there is one coupling mode and the rest of the modes are symmetric tuning modes. The CI appears in the Hamiltonian as off-diagonal entries to the potential term that couple the two upper states, in the form of a linear function of the coupling mode. We show that: (a) the ABS, REP, and FSREP for Stokes and anti-Stokes lines contain similar information about the e1 and e2 vibrational bands, (b) the FSRS spectra feature narrow stationary peaks and broader moving peaks contributed by the different resonant components of the third-order polarization terms from perturbation theory, and (c) a relatively strong and narrow stationary band of the allowed first overtone of the asymmetric coupling mode is observed in the Stokes FSREP in the e1 energy region with coupling to e2

  13. All-Fiber Raman Probe

    Brunetti, Anna Chiara

    perform real-time measurements with little or no sample preparation, Raman spectroscopy is now considered an invaluable analytical tool, finding application in several fields including medicine, defense and process control. When combined with fiber optics technology, Raman spectroscopy allows for the......The design and development of an all-in-fiber probe for Raman spectroscopy are presented in this Thesis. Raman spectroscopy is an optical technique able to probe a sample based on the inelastic scattering of monochromatic light. Due to its high specificity and reliability and to the possibility to...... means of fiber components. Assuming the possibility to use a fiber laser with a fundamental radiation at 1064nm, in-fiber efficient second harmonic generation is achieved by optically poling the core of the waveguide delivering the excitation light to the sample. In this way, Raman spectroscopy in the...

  14. Raman Spectroscopy for Clinical Oncology

    Michael B. Fenn

    2011-01-01

    Full Text Available Cancer is one of the leading causes of death throughout the world. Advancements in early and improved diagnosis could help prevent a significant number of these deaths. Raman spectroscopy is a vibrational spectroscopic technique which has received considerable attention recently with regards to applications in clinical oncology. Raman spectroscopy has the potential not only to improve diagnosis of cancer but also to advance the treatment of cancer. A number of studies have investigated Raman spectroscopy for its potential to improve diagnosis and treatment of a wide variety of cancers. In this paper the most recent advances in dispersive Raman spectroscopy, which have demonstrated promising leads to real world application for clinical oncology are reviewed. The application of Raman spectroscopy to breast, brain, skin, cervical, gastrointestinal, oral, and lung cancers is reviewed as well as a special focus on the data analysis techniques, which have been employed in the studies.

  15. Anomalous lattice vibrations of monolayer MoS 2 probed by ultraviolet Raman scattering

    Liu, Hsiang Lin

    2015-01-01

    We present a comprehensive Raman scattering study of monolayer MoS2 with increasing laser excitation energies ranging from the near-infrared to the deep-ultraviolet. The Raman scattering intensities from the second-order phonon modes are revealed to be enhanced anomalously by only the ultraviolet excitation wavelength 354 nm. We demonstrate theoretically that such resonant behavior arises from a strong optical absorption that forms near the Γ point and of the band structure and an inter-valley resonant electronic scattering by the M-point phonons. These results advance our understanding of the double resonance Raman scattering process in low-dimensional semiconducting nanomaterials and provide a foundation for the technological development of monolayer MoS2 in the ultraviolet frequency range. © the Owner Societies 2015.

  16. Surface plasmon near-field back-action and displacement of enhanced Raman scattering spectrum in graphene

    Ghamsari, Behnood G.; Berini, Pierre

    2016-07-01

    It has been recently observed that plasmonic nanoantennas tuned to the Stokes wavelengths associated with the G and 2D Raman bands of graphene, rather than the laser pump, not only enhance Raman scattering in graphene but also displace and broaden the Raman spectra Ghamsari et al (2015 Phys. Rev. B 91 201408(R)). This paper presents a model to explain the frequency pulling and lineshape broadening effects based on the back-action of surface plasmons near-field on the induced microscopic Raman dipoles in graphene. The model provides the relation among Raman enhancement factor, Raman frequency displacement, and broadening caused by Stokes-tuned resonant nanoantennas and compares the results to the previously reported experimental data.

  17. Anharmonic Effects on Vibrational Spectra Intensities: Infrared, Raman, Vibrational Circular Dichroism, and Raman Optical Activity.

    Bloino, Julien; Biczysko, Malgorzata; Barone, Vincenzo

    2015-12-10

    The aim of this paper is 2-fold. First, we want to report the extension of our virtual multifrequency spectrometer (VMS) to anharmonic intensities for Raman optical activity (ROA) with the full inclusion of first- and second-order resonances for both frequencies and intensities in the framework of the generalized second-order vibrational perturbation theory (GVPT2) for all kinds of vibrational spectroscopies. Then, from a more general point of view, we want to present and validate the performance of VMS for the parallel analysis of different vibrational spectra for medium-sized molecules (IR, Raman, VCD, ROA) including both mechanical and electric/magnetic anharmonicity. For the well-known methyloxirane benchmark, careful selection of density functional, basis set, and resonance thresholds permitted us to reach qualitative and quantitative agreement between experimental and computed band positions and shapes. Next, the whole series of halogenated azetidinones is analyzed, showing that it is now possible to interpret different spectra in terms of mass, electronegativity, polarizability, and hindrance variation between closely related substituents, chiral spectroscopies being particular effective in this connection. PMID:26580121

  18. Raman Lidar (RL) Handbook

    Newsom, RK

    2009-03-01

    The Raman lidar at the ARM Climate Research Facility (ACRF) Southern Great Plains (SGP) Central Facility (SGPRL) is an active, ground-based laser remote sensing instrument that measures height and time resolved profiles of water vapor mixing ratio and several cloud- and aerosol-related quantities. The system is a non-commercial custom-built instrument developed by Sandia National Laboratories specifically for the ARM Program. It is fully computer automated, and will run unattended for many days following a brief (~5-minute) startup period. The self-contained system (requiring only external electrical power) is housed in a climate-controlled 8’x8’x20’ standard shipping container.

  19. Femtosecond Stimulated Raman Spectroscopy.

    Dietze, Daniel R; Mathies, Richard A

    2016-05-01

    Femtosecond stimulated Raman spectroscopy (FSRS) is an ultrafast nonlinear optical technique that provides vibrational structural information with high temporal (sub-50 fs) precision and high spectral (10 cm(-1) ) resolution. Since the first full demonstration of its capabilities ≈15 years ago, FSRS has evolved into a mature technique, giving deep insights into chemical and biochemical reaction dynamics that would be inaccessible with any other technique. It is now being routinely applied to virtually all possible photochemical reactions and systems spanning from single molecules in solution to thin films, bulk crystals and macromolecular proteins. This review starts with an historic overview and discusses the theoretical and experimental concepts behind this technology. Emphasis is put on the current state-of-the-art experimental realization and several variations of FSRS that have been developed. The unique capabilities of FSRS are illustrated through a comprehensive presentation of experiments to date followed by prospects. PMID:26919612

  20. The polarization field for pulsed Raman transitions

    This memo discusses the induced polarization field that occurs in the presence of Raman processes, and the propagation equations that result from this field. First the paper summarizes the relationship between the macroscopic polarization field and the microscopic dipole-moment expectation value. It summarizes expressions for the induced dipole moment that result from the adiabatic elimination of non-resonant molecular transitions, to produce an effective two-photon (Raman) Hamiltonian. Then it shows that the polarization field has a similar mode expansion to the electric field. Using this result the equations for pulse propagation of the electric field are described. These equations involve a generalized gain matrix and mode velocity, as well as a refractive index, each of which depends upon position and time. Finally the paper summarizes these results and exhibits succinctly the pulse propagation equations in the plane-wave slowly-varying envelope approximation. The equations presented here must be supplemented with excitation equations (or by steady-state results) for the molecules. The material presented here is a portion of a more extensive treatment of propagation to be presented separately

  1. Enhanced coherent Raman emission from uniform plasmas

    A mechanism for the coherent emission of radio and microwaves from a warm uniform plasma is proposed. The output power from this mechanism appears to have the characteristics of a classical parametric amplification process. An earlier kinetic theory model for radiation by the scattering of plasma waves in a homogeneous plasma is revamped and modified to incorporate the dominant role of longitudinal Rayleigh scattered waves which stimulate the emission of transverse combination radiation (sum and difference of impressed and natural frequencies) by the resonant Raman scattering process in the plasma. This results in intense radio or microwave radiation at approximately twice the plasma frequency, the intensity depending upon plasma parameters. This intensity, its angular pattern, and the threshold condition for its enhanced emission are calculated. Comparisons of the computed results with the laboratory observation of the radiation output from dc discharges in argon gas, and from a helium theta-pinch plasma are made. Both qualitative and quantitative agreement are found

  2. Scanning angle Raman spectroscopy: Investigation of Raman scatter enhancement techniques for chemical analysis

    Meyer, Matthew W. [Iowa State Univ., Ames, IA (United States)

    2013-01-01

    This thesis outlines advancements in Raman scatter enhancement techniques by applying evanescent fields, standing-waves (waveguides) and surface enhancements to increase the generated mean square electric field, which is directly related to the intensity of Raman scattering. These techniques are accomplished by employing scanning angle Raman spectroscopy and surface enhanced Raman spectroscopy. A 1064 nm multichannel Raman spectrometer is discussed for chemical analysis of lignin. Extending dispersive multichannel Raman spectroscopy to 1064 nm reduces the fluorescence interference that can mask the weaker Raman scattering. Overall, these techniques help address the major obstacles in Raman spectroscopy for chemical analysis, which include the inherently weak Raman cross section and susceptibility to fluorescence interference.

  3. [Raman active vibrations of aluminosilicates].

    Pan, Feng; Yu, Xue-hui; Mo, Xuan-xue; You, Jing-lin; Wang, Chen; Chen, Hui; Jiang, Guo-chang

    2006-10-01

    Raman spectra of aluminosilicate minerals, namely kyanite, andalusite, and sillimanite and K2O-Al2O3-SiO2 glasses were recorded. Four alumino-silicon tetrahedral model clusters were calculated by self-consistent (SCF) molecular orbital ab-ini-tio calculation of the quantum chem (QC) method. The result shows a decrease tendency in Raman frequencies in the 800-1200 cm(-1) frequency region with increase in four-coordinated Al content, which is assigned to the Si--Onb symmetry stretching vibrations. The Raman spectra in the 700-800 cm(-1) frequency region is attributed to Al-Onb symmetry stretching vibrations. PMID:17205741

  4. Stimulated Raman scattering in an optical parametric oscillator based on periodically poled MgO-doped stoichiometric LiTaO3

    My, T-H; Mhibik, O; Drag, C; Bretenaker, F

    2009-01-01

    The evolution versus pump power of the spectrum of a singly resonant optical parametric oscillator based on an MgO-doped periodically poled stoichiometric lithium tantalate crystal is observed. The onset of cascade Raman lasing due to stimulated Raman scattering in the nonlinear crystal is analyzed. Spurious frequency doubling and sum-frequency generation phenomena are observed and understood. A strong reduction of the intracavity Raman scattering is obtained by a careful adjustment of the cavity losses.

  5. Topological Raman band in the carbon nanohorn.

    Sasaki, Ken-ichi; Sekine, Yoshiaki; Tateno, Kouta; Gotoh, Hideki

    2013-09-13

    Raman spectroscopy has been used in chemistry and physics to investigate the fundamental process involving light and phonons. The carbon nanohorn introduces a new subject to Raman spectroscopy, namely topology. We show theoretically that a photoexcited carrier with a nonzero winding number activates a topological D Raman band through the Aharonov-Bohm effect. The topology-induced D Raman band can be distinguished from the ordinary D Raman band for a graphene edge by its peak position. PMID:24074113

  6. Femtosecond stimulated Raman spectroscopy by six-wave mixing

    Molesky, Brian P.; Guo, Zhenkun; Moran, Andrew M.

    2015-06-01

    Femtosecond Stimulated Raman Spectroscopy (FSRS) is motivated by the knowledge of the molecular geometry changes that accompany sub-picosecond chemical reactions. The detection of vibrational resonances throughout the entire fingerprint region of the spectrum with sub-100-fs delay precision is fairly straightforward to accomplish with the FSRS technique. Despite its utility, FSRS must contend with substantial technical challenges that stem from a large background of residual laser light and lower-order nonlinearities when all laser pulses are electronically resonant with the equilibrium system. In this work, a geometry based on five incident laser beams is used to eliminate much of this undesired background in experiments conducted on metmyoglobin. Compared to a three-beam FSRS geometry with all electronically resonant laser pulses, the five-beam approach described here offers major improvements in the data acquisition rate, sensitivity, and background suppression. The susceptibility of the five-beam geometry to experimental artifacts is investigated using control experiments and model calculations. Of particular concern are undesired cascades of third-order nonlinearities, which are known to challenge FSRS measurements carried out on electronically off-resonant systems. It is generally understood that "forbidden" steps in the desired nonlinear optical processes are the origin of the problems encountered under off-resonant conditions. In contrast, the present experiments are carried out under electronically resonant conditions, where such unfortunate selection rules do not apply. Nonetheless, control experiments based on spectroscopic line shapes, signal phases, and sample concentrations are conducted to rule out significant contributions from cascades of third-order processes. Theoretical calculations are further used to estimate the relative intensities of the direct and cascaded responses. Overall, the control experiments and model calculations presented in this

  7. Femtosecond stimulated Raman spectroscopy by six-wave mixing

    Molesky, Brian P.; Guo, Zhenkun; Moran, Andrew M., E-mail: ammoran@email.unc.edu [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599 (United States)

    2015-06-07

    Femtosecond Stimulated Raman Spectroscopy (FSRS) is motivated by the knowledge of the molecular geometry changes that accompany sub-picosecond chemical reactions. The detection of vibrational resonances throughout the entire fingerprint region of the spectrum with sub-100-fs delay precision is fairly straightforward to accomplish with the FSRS technique. Despite its utility, FSRS must contend with substantial technical challenges that stem from a large background of residual laser light and lower-order nonlinearities when all laser pulses are electronically resonant with the equilibrium system. In this work, a geometry based on five incident laser beams is used to eliminate much of this undesired background in experiments conducted on metmyoglobin. Compared to a three-beam FSRS geometry with all electronically resonant laser pulses, the five-beam approach described here offers major improvements in the data acquisition rate, sensitivity, and background suppression. The susceptibility of the five-beam geometry to experimental artifacts is investigated using control experiments and model calculations. Of particular concern are undesired cascades of third-order nonlinearities, which are known to challenge FSRS measurements carried out on electronically off-resonant systems. It is generally understood that “forbidden” steps in the desired nonlinear optical processes are the origin of the problems encountered under off-resonant conditions. In contrast, the present experiments are carried out under electronically resonant conditions, where such unfortunate selection rules do not apply. Nonetheless, control experiments based on spectroscopic line shapes, signal phases, and sample concentrations are conducted to rule out significant contributions from cascades of third-order processes. Theoretical calculations are further used to estimate the relative intensities of the direct and cascaded responses. Overall, the control experiments and model calculations presented in

  8. The Raman Fingerprint of Graphene

    Ferrari, A. C.; Meyer, J. C.; Scardaci, V.; Casiraghi, C.; Lazzeri, Michele; Mauri, Francesco; Piscanec, S.; Jiang, Da; Novoselov, K. S.; Roth, S; Geim, A. K.

    2006-01-01

    Graphene is the two-dimensional (2d) building block for carbon allotropes of every other dimensionality. It can be stacked into 3d graphite, rolled into 1d nanotubes, or wrapped into 0d fullerenes. Its recent discovery in free state has finally provided the possibility to study experimentally its electronic and phonon properties. Here we show that graphene's electronic structure is uniquely captured in its Raman spectrum that clearly evolves with increasing number of layers. Raman fingerprint...

  9. Validation model for Raman based skin carotenoid detection.

    Ermakov, Igor V; Gellermann, Werner

    2010-12-01

    Raman spectroscopy holds promise as a rapid objective non-invasive optical method for the detection of carotenoid compounds in human tissue in vivo. Carotenoids are of interest due to their functions as antioxidants and/or optical absorbers of phototoxic light at deep blue and near UV wavelengths. In the macular region of the human retina, carotenoids may prevent or delay the onset of age-related tissue degeneration. In human skin, they may help prevent premature skin aging, and are possibly involved in the prevention of certain skin cancers. Furthermore, since carotenoids exist in high concentrations in a wide variety of fruits and vegetables, and are routinely taken up by the human body through the diet, skin carotenoid levels may serve as an objective biomarker for fruit and vegetable intake. Before the Raman method can be accepted as a widespread optical alternative for carotenoid measurements, direct validation studies are needed to compare it with the gold standard of high performance liquid chromatography. This is because the tissue Raman response is in general accompanied by a host of other optical processes which have to be taken into account. In skin, the most prominent is strongly diffusive, non-Raman scattering, leading to relatively shallow light penetration of the blue/green excitation light required for resonant Raman detection of carotenoids. Also, sizable light attenuation exists due to the combined absorption from collagen, porphyrin, hemoglobin, and melanin chromophores, and additional fluorescence is generated by collagen and porphyrins. In this study, we investigate for the first time the direct correlation of in vivo skin tissue carotenoid Raman measurements with subsequent chromatography derived carotenoid concentrations. As tissue site we use heel skin, in which the stratum corneum layer thickness exceeds the light penetration depth, which is free of optically confounding chromophores, which can be easily optically accessed for in vivo RRS

  10. Controlling metamaterial resonances with light

    We investigate the use of coherent optical fields as a means of dynamically controlling the resonant behavior of a variety of composite metamaterials, wherein the metamaterial structures are embedded in a dispersive dielectric medium. Control and switching are implemented by coherently driving the resonant permittivity of the embedding medium with applied optical radiation. The effect of embedding split ring resonators in a frequency-dispersive medium with Lorentz-like dispersion or with dispersion engineered by electromagnetically induced transparency (EIT) is manifested in the splitting of the negative-permeability band, the modified (frequency-dependent) filling fractions, and the dissipation factors. The modified material parameters are strongly linked to the resonant frequencies of the medium, and for an embedding medium exhibiting EIT also to the strength and detuning of the control field. The robustness of control against the deleterious influence of dissipation associated with the metallic structures as well as the inhomogeneous broadening due to structural imperfections is demonstrated. Studies on plasmonic metamaterials that consist of metallic nanorods arranged in loops and exhibit a collective magnetic response at optical frequencies are presented. Control and switching in this class of plasmonic nanorod metamaterials is shown to be possible, for example, by embedding these arrays in a Raman-active liquid like CS2 and utilizing the inverse Raman effect.

  11. Laser Raman Spectroscopy in studies of corrosion and electrocatalysis

    Laser Raman Spectroscopy (LRS) has become an important tool for the in-situ structural study of electrochemical systems and processes in recent years. Following a brief introduction of the experimental techniques involved in applying LRS to electrochemical systems, we survey the literature for examples of studies in the inhibition of electrode reactions by surface films (e.g., corrosion and passivation phenomena) as well as the acceleration of reactions by electro-sorbates (electrocatalysis). We deal mostly with both normal and resonance Raman effects on fairly thick surface films in contrast to surface-enhanced Raman investigations of monolayer adsorbates, which is covered in another lecture. Laser Raman spectroelectrochemical studies of corrosion and film formation on such metals as Pb, Ag, Fe, Ni, Co, Cr, Au, stainless steel, etc. in various solution conditions are discussed. Further extension of the technique to studies in high-temperature and high-pressure aqueous environments is demonstrated. Results of studies of the structure of corrosion inhibitors are also presented. As applications of the LRS technique in the area of electrocatalysis, we cite studies of the structure of transition metal macrocyclic compounds, i.e., phthalocyanines and porphyrins, used for catalysis of the oxygen reduction reaction. 104 refs., 20 figs

  12. Raman measurement of carotenoid composition in human skin

    Ermakov, Igor V.; Ermakova, Maia R.; Gellermann, Werner

    2004-07-01

    The carotenoids lycopene and beta-carotene are powerful antioxidants in skin and are thought to act as scavengers for free radicals and singlet oxygen. The role of carotenoid species in skin health is of strong current interest. We demonstrate the possibility to use Resonance Raman spectroscopy for fast, non-invasive, highly specific, and quantitative detection of beta-carotene and lycopene in human skin. Analyzing Raman signals originating from the carbon-carbon double bond stretch vibrations of the carotenoid molecules under blue and green laser excitation, we were able to characterize quantitatively the relative concentrations of each carotenoid species in-vivo. In the selective detection, we take advantage of different Raman cross-section spectral profiles for beta-carotene and lycopene molecules, and obtain a quantitative assessment of individual long-chain carotenoid species in the skin rather than their cumulative levels. Preliminary dual-wavelength Raman measurements reveal significant differences in the carotenoid composition of different subjects. The technique holds promise for rapid screening of carotenoid compositions in human skin in large populations and may be suitable in clinical studies for assessing the risk for cutaneous diseases.

  13. Tip enhanced Raman scattering: plasmonic enhancements for nanoscale chemical analysis

    Schultz, Zachary D.; Marr, James M.; Wang, Hao

    2014-04-01

    Tip enhanced Raman scattering (TERS) is an emerging technique that uses a metalized scanning probe microscope tip to spatially localize electric fields that enhances Raman scattering enabling chemical imaging on nanometer dimensions. Arising from the same principles as surface enhanced Raman scattering (SERS), TERS offers unique advantages associated with controling the size, shape, and location of the enhancing nanostructure. In this article we discuss the correlations between current understanding of SERS and how this relates to TERS, as well as how TERS provides new understanding and insights. The relationship between plasmon resonances and Raman enhancements is emphasized as the key to obtaining optimal TERS results. Applications of TERS, including chemical analysis of carbon nanotubes, organic molecules, inorganic crystals, nucleic acids, proteins, cells and organisms, are used to illustrate the information that can be gained. Under ideal conditions TERS is capable of single molecule sensitivity and sub-nanometer spatial resolution. The ability to control plasmonic enhancements for chemical analysis suggests new experiments and opportunities to understand molecular composition and interactions on the nanoscale.

  14. Spatial resolution of tip-enhanced Raman spectroscopy - DFT assessment of the chemical effect

    Latorre, Federico; Kupfer, Stephan; Bocklitz, Thomas; Kinzel, Daniel; Trautmann, Steffen; Gräfe, Stefanie; Deckert, Volker

    2016-05-01

    Experimental evidence of extremely high spatial resolution of tip-enhanced Raman scattering (TERS) has been recently demonstrated. Here, we present a full quantum chemical description (at the density functional level of theory) of the non-resonant chemical effects on the Raman spectrum of an adenine molecule mapped by a tip, modeled as a single silver atom or a small silver cluster. We show pronounced changes in the Raman pattern and its intensities depending on the conformation of the nanoparticle-substrate system, concluding that the spatial resolution of the chemical contribution of TERS can be in the sub-nm range.Experimental evidence of extremely high spatial resolution of tip-enhanced Raman scattering (TERS) has been recently demonstrated. Here, we present a full quantum chemical description (at the density functional level of theory) of the non-resonant chemical effects on the Raman spectrum of an adenine molecule mapped by a tip, modeled as a single silver atom or a small silver cluster. We show pronounced changes in the Raman pattern and its intensities depending on the conformation of the nanoparticle-substrate system, concluding that the spatial resolution of the chemical contribution of TERS can be in the sub-nm range. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00093b

  15. Nanopillars array for surface enhanced Raman scattering

    S.P. Chang, A; Bora, M; Nguyen, H T; Behymer, E M; Larson, C C; Britten, J A; Carter, J C; Bond, T C

    2011-04-14

    The authors present a new class of surface-enhanced Raman scattering (SERS) substrates based on lithographically-defined two-dimensional rectangular array of nanopillars. Two types of nanopillars within this class are discussed: vertical pillars and tapered pillars. For the vertical pillars, the gap between each pair of nanopillars is small enough (< 50 nm) such that highly confined plasmonic cavity resonances are supported between the pillars when light is incident upon them, and the anti-nodes of these resonances act as three-dimensional hotspots for SERS. For the tapered pillars, SERS enhancement arises from the nanofocusing effect due to the sharp tip on top. SERS experiments were carried out on these substrates using various concentrations of 1,2 bis-(4-pyridyl)-ethylene (BPE), benzenethiol (BT) monolayer and toluene vapor. The results show that SERS enhancement factor of over 0.5 x 10{sup 9} can be achieved, and BPE can be detected down to femto-molar concentration level. The results also show promising potential for the use of these substrates in environmental monitoring of gases and vapors such as volatile organic compounds.

  16. Chirality Changes in Carbon Nanotubes Studied with Near-Field Raman Spectroscopy

    Anderson, Neil; Hartschuh, Achim; Novotny, Lukas

    2007-01-01

    We report on the direct visualization of chirality changes in carbon nanotubes by mapping local changes in resonant RBM phonon frequencies with an optical resolution of 40 nm using near-field Raman spectroscopy. We observe the transition from semiconducting-to-metal and metal-to-metal chiralities at the single nanotube level. Our experimental findings, based on detecting changes in resonant RBM frequencies, are complemented by measuring changes in the G-band frequency and line shape. In addit...

  17. Revisiting the Young's double slit experiment for background-free nonlinear Raman spectroscopy and microscopy.

    Gachet, David; Brustlein, Sophie; Rigneault, Hervé

    2010-05-28

    In the Young's double slit experiment, the spatial shift of the interference pattern projected onto a screen is directly related to the phase difference between the fields diffracted by the two slits. We apply this property to fields emitted by nonlinear processes and thus demonstrate background-free coherent anti-Stokes Raman scattering microscopy near an axial interface between a resonant and a nonresonant medium. This method is relevant to remove the nonresonant background in other coherent resonant processes. PMID:20867103

  18. Gold Nanoparticles as Probes for Nano-Raman Spectroscopy: Preliminary Experimental Results and Modeling

    V. Le Nader

    2012-01-01

    Full Text Available This paper presents an effective Tip-Enhanced Raman Spectrometer (TERS in backscattering reflection configuration. It combines a tip-probe nanopositioning system with Raman spectroscope. Specific tips were processed by anchoring gold nanoparticles on the apex of tapered optical fibers, prepared by an improved chemical etching method. Hence, it is possible to expose a very small area of the sample (~20 nm2 to the very strong local electromagnetic field generated by the lightning rod effect. This experimental configuration was modelled and optimised using the finite element method, which takes into account electromagnetic effects as well as the plasmon resonance. Finally, TERS measurements on single-wall carbon nanotubes were successfully performed. These results confirm the high Raman scattering enhancement predicted by the modelling, induced by our new nano-Raman device.

  19. Raman imaging and spectroscopy of individual single-wall carbon nanotubes

    Zhang, Li

    Single-wall carbon nanotubes (SWNT) are unique one-dimensional materials that are promising for many potential applications in various important areas. Their vibrational properties reflect the electron and phonon confinement as well as the structures of the tubes. Resonant Raman spectroscopy has been proven to be an exceedingly powerful tool for the characterization of the vibrational and electronic properties of SWNTs. This thesis focuses on the study of Raman spectroscopy of individual single carbon nanotubes. Single tube spectroscopy allows probing the structure dependent properties of SWNTs. A beam-scanning confocal Raman microscope system capable of large-area Raman imaging is first developed for characterizing SWNTs at the single tube level. Raman images and first-order Raman spectra of nanotubes, consisting of both semicoducting and metallic nanotubes, are systemically studied at room temperature in ambient air. The diameter of the nanotubes is determined from their radial breathing mode (RBM) frequency. A broad diameter distribution is observed for nanotubes synthesized by chemical vapor deposition. The tangential G mode Raman spectra of individual metallic nanotubes are found to exhibit a broad distribution of line shapes, which is attributed to shift of the Fermi level due to O2 adsorption. The doping dependence of Raman spectra of metallic tubes is further studied by both electrostatic gating and electrochemical gating. Significant changes in the G band Raman spectra of nanotubes are observed, suggesting the effect of doping on electron-phonon interaction. The observation of a gradual evolution of G band spectrum from a semiconducting type to the broad BWF type reveals evidence of phonon interaction between two G band modes. Raman imaging and Raman spectra of isolated SWNTs and single-layer graphenen are investigated at both room temperature and low temperature. The temperature-induced Raman spectral change of individual nanotubes is observed to be tube

  20. Sum-Frequency-Generation-Based Laser Sidebands for Tunable Femtosecond Raman Spectroscopy in the Ultraviolet

    Liangdong Zhu

    2015-04-01

    Full Text Available Femtosecond stimulated Raman spectroscopy (FSRS is an emerging molecular structural dynamics technique for functional materials characterization typically in the visible to near-IR range. To expand its applications we have developed a versatile FSRS setup in the ultraviolet region. We use the combination of a narrowband, ~400 nm Raman pump from a home-built second harmonic bandwidth compressor and a tunable broadband probe pulse from sum-frequency-generation-based cascaded four-wave mixing (SFG-CFWM laser sidebands in a thin BBO crystal. The ground state Raman spectrum of a laser dye Quinolon 390 in methanol that strongly absorbs at ~355 nm is systematically studied as a standard sample to provide previously unavailable spectroscopic characterization in the vibrational domain. Both the Stokes and anti-Stokes Raman spectra can be collected by selecting different orders of SFG-CFWM sidebands as the probe pulse. The stimulated Raman gain with the 402 nm Raman pump is >21 times larger than that with the 550 nm Raman pump when measured at the 1317 cm−1 peak for the aromatic ring deformation and ring-H rocking mode of the dye molecule, demonstrating that pre-resonance enhancement is effectively achieved in the unique UV-FSRS setup. This added tunability in the versatile and compact optical setup enables FSRS to better capture transient conformational snapshots of photosensitive molecules that absorb in the UV range.

  1. Raman sideband cooling of a 138Ba+ ion using a Zeeman interval

    Seck, Christopher M; Dietrich, Matthew R; Odom, Brian C

    2016-01-01

    Motional ground state cooling and internal state preparation are important elements for quantum logic spectroscopy (QLS), a class of quantum information processing. Since QLS does not require the high gate fidelities usually associated with quantum computation and quantum simulation, it is possible to make simplifying choices in ion species and quantum protocols at the expense of some fidelity. Here, we report sideband cooling and motional state detection protocols for $^{138}$Ba$^+$ of sufficient fidelity for QLS without an extremely narrowband laser or the use of a species with hyperfine structure. We use the two S$_{1/2}$ Zeeman sublevels of $^{138}$Ba$^+$ to Raman sideband cool a single ion to the motional ground state. Because of the small Zeeman splitting, near-resonant Raman sideband cooling of $^{138}$Ba$^+$ requires only the Doppler cooling lasers and two additional AOMs. Observing the near-resonant Raman optical pumping fluorescence, we estimate a final average motional quantum number $\\bar{n}\\appro...

  2. Surface-enhanced Raman scattering from finite arrays of gold nano-patches

    We experimentally investigate the surface-enhanced Raman scattering (SERS) response of a 2D-periodic array of square gold nano-patches, functionalized by means of a conjugated, rigid thiol. We measure a Raman signal enhancement up to 200 times more intense compared to other plasmon-based nanostructures functionalized with the same molecule, and show that the enhancement is not strictly correlated to the presence of plasmonic resonances. The agreement between experimental and theoretical results reveals the importance of a full-wave analysis based on the inclusion of the actual scattering cross section of the molecule. The proposed numerical approach may serve not only as a tool to predict the enhancement of Raman signal scattered from strongly resonant nanostructure but also as an effective instrument to engineer SERS platforms that target specific molecules.

  3. Gold Nanostructures for Surface-Enhanced Raman Spectroscopy, Prepared by Electrodeposition in Porous Silicon

    Yukio H. Ogata

    2011-04-01

    Full Text Available Electrodeposition of gold into porous silicon was investigated. In the present study, porous silicon with ~100 nm in pore diameter, so-called medium-sized pores, was used as template electrode for gold electrodeposition. The growth behavior of gold deposits was studied by scanning electron microscope observation of the gold deposited porous silicon. Gold nanorod arrays with different rod lengths were prepared, and their surface-enhanced Raman scattering properties were investigated. We found that the absorption peak due to the surface plasmon resonance can be tuned by changing the length of the nanorods. The optimum length of the gold nanorods was ~600 nm for surface-enhanced Raman spectroscopy using a He-Ne laser. The reason why the optimum length of the gold nanorods was 600 nm was discussed by considering the relationship between the absorption peak of surface plasmon resonance and the wavelength of the incident laser for Raman scattering.

  4. Raman and Surface-enhanced Raman Scattering of Chlorophenols

    SONG Wei; SHANG Xiao-hong; LU Yong; LIU Bing-bing; WANG Xu

    2011-01-01

    Raman spectrum is a powerful analytical tool for determining the chemical information of compounds.In this study,we obtained analytical results of chlorophenols(CPs) molecules including 4-chlorophenol(4-CP),2,6-dichlorophenol(2,6-DCP) and 2,4,6-trichlorophenol(2,4,6-TCP) on the surface of Ag dendrites by surface-enhanced Raman scattering(SERS) spectra.SEM images indicate that the SERS substrate of Ag dendrites is composed of a large number of polygonal nanocrystallites,which self-assembled into a 3D hierarchical structure.It was found that there were distinct differences for those three molecules from Raman and SERS spectra.This indicates that SERS could be a new tool of detection technique regarding trace amounts of CPs.

  5. Stochastic Liouville equations for femtosecond stimulated Raman spectroscopy

    Agarwalla, Bijay Kumar; Ando, Hideo; Dorfman, Konstantin E.; Mukamel, Shaul [Department of Chemistry, University of California, Irvine, California 92617 (United States)

    2015-01-14

    Electron and vibrational dynamics of molecules are commonly studied by subjecting them to two interactions with a fast actinic pulse that prepares them in a nonstationary state and after a variable delay period T, probing them with a Raman process induced by a combination of a broadband and a narrowband pulse. This technique, known as femtosecond stimulated Raman spectroscopy (FSRS), can effectively probe time resolved vibrational resonances. We show how FSRS signals can be modeled and interpreted using the stochastic Liouville equations (SLE), originally developed for NMR lineshapes. The SLE provide a convenient simulation protocol that can describe complex dynamics caused by coupling to collective bath coordinates at much lower cost than a full dynamical simulation. The origin of the dispersive features that appear when there is no separation of timescales between vibrational variations and the dephasing time is clarified.

  6. Superconductive B-doped nanocrystalline diamond thin films: Electrical transport and Raman spectra

    Nesládek, M.; Tromson, D.; Mer, Ch.; Bergonzo, P.; Hubík, Pavel; Mareš, Jiří J.

    2006-01-01

    Roč. 88, č. 23 (2006), 232111/1-232111/3. ISSN 0003-6951 R&D Projects: GA ČR(CZ) GA202/06/0040 Institutional research plan: CEZ:AV0Z10100521 Keywords : nanocrystalline diamond * superconductivity * magnetoresistance * Raman spectroscopy * Fano resonance Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.977, year: 2006

  7. Barium Nitrate Raman Laser Development for Remote Sensing of Ozone

    McCray, Christopher L.; Chyba, Thomas H.

    1997-01-01

    In order to understand the impact of anthropogenic emissions upon the earth's environment, scientists require remote sensing techniques which are capable of providing range-resolved measurements of clouds, aerosols, and the concentrations of several chemical constituents of the atmosphere. The differential absorption lidar (DIAL) technique is a very promising method to measure concentration profiles of chemical species such as ozone and water vapor as well as detect the presence of aerosols and clouds. If a suitable DIAL system could be deployed in space, it would provide a global data set of tremendous value. Such systems, however, need to be compact, reliable, and very efficient. In order to measure atmospheric gases with the DIAL technique, the laser transmitter must generate suitable on-line and off-line wavelength pulse pairs. The on-line pulse is resonant with an absorption feature of the species of interest. The off-line pulse is tuned so that it encounters significantly less absorption. The relative backscattered power for the two pulses enables the range-resolved concentration to be computed. Preliminary experiments at NASA LaRC suggested that the solid state Raman shifting material, Ba(NO3)2, could be utilized to produce these pulse pairs. A Raman oscillator pumped at 532 nm by a frequency-doubled Nd:YAG laser can create first Stokes laser output at 563 nm and second Stokes output at 599 nm. With frequency doublers, UV output at 281 nm and 299 nm can be subsequently obtained. This all-solid state system has the potential to be very efficient, compact, and reliable. Raman shifting in Ba(NO3)2, has previously been performed in both the visible and the infrared. The first Raman oscillator in the visible region was investigated in 1986 with the configurations of plane-plane and unstable telescopic resonators. However, most of the recent research has focused on the development of infrared sources for eye-safe lidar applications.

  8. Resonance Raman detection of carotenoid antioxidants in living human tissue

    Ermakov, Igor V.; M Sharifzadeh; Ermakova, Maia; Gellermann, W.

    2005-01-01

    Increasing evidence points to the beneficial effects of carotenoid antioxidants in the human body. Several studies, for example, support the protective role of lutein and zeaxanthin in the prevention of age-related eye diseases. If present in high concentrations in the macular region of the retina, lutein and zeaxanthin provide pigmentation in this most light sensitive retinal spot, and as a result of light filtering and/or antioxidant action, delay the onset of macular degeneration with incr...

  9. Raman and Photoluminescence Spectroscopy in Mineral Identification

    Kuehn, J. W.

    2014-06-01

    Raman spectroscopy is particularly useful for rapid identification of minerals and gemstones. Raman spectrometers also allow PL studies for authentication of samples and geological provenance, diamond type screening and detection of HPHT treatments.

  10. Field Raman spectrograph for environmental analysis

    The use of Raman Spectroscopy in the screening of soils, ground water, and surface waters for pollutants is described. A probe accessory for conducting surface enhanced Raman Spectroscopy is undergoing testing for dilute chlorinated solvents

  11. High gain/broadband oxide glasses for next generation Raman amplifiers

    Rivero, Clara A.

    aware when conducting these measurements near the absorption band edge of the material. This led to the detection of an inherent frequency-dispersion in the Raman susceptibility and a resonant enhancement phenomenon when measurements were conducted near the absorption edge of the material.

  12. Raman Spectroscopy and Related Techniques in Biomedicine

    Alistair Elfick; Andrew Downes

    2010-01-01

    In this review we describe label-free optical spectroscopy techniques which are able to non-invasively measure the (bio)chemistry in biological systems. Raman spectroscopy uses visible or near-infrared light to measure a spectrum of vibrational bonds in seconds. Coherent anti-Stokes Raman (CARS) microscopy and stimulated Raman loss (SRL) microscopy are orders of magnitude more efficient than Raman spectroscopy, and are able to acquire high quality chemically-specific images in seconds. We dis...

  13. Multi-scale nonlinear effects in whispering-gallery mode resonators

    Lin, Guoping; Diallo, Souleymane; Chembo, Yanne K.

    2016-03-01

    Whispering gallery mode resonators have been the focus of many research works in recent years. They allow to study the light-matter interactions induced by the confinement of photons in nonlinear media. In particular, Brillouin Raman and Kerr nonlinearities excite the resonator at the lattice, molecular and electronic scale. This difference in spatial scales give to whispering gallery-mode resonators the potential to be central photonic components in microwave photonics, quantum optics and optoelectronics. We discuss in this communication some of the key challenges that have to be met for the understanding of Kerr, Raman and Brillouin interactions that can take place in these resonators.

  14. Nanoparticle Based Surface-Enhanced Raman Spectroscopy

    Talley, C E; Huser, T R; Hollars, C W; Jusinski, L; Laurence, T; Lane, S M

    2005-01-03

    Surface-enhanced Raman scattering is a powerful tool for the investigation of biological samples. Following a brief introduction to Raman and surface-enhanced Raman scattering, several examples of biophotonic applications of SERS are discussed. The concept of nanoparticle based sensors using SERS is introduced and the development of these sensors is discussed.

  15. Theory of polariton-mediated Raman scattering in microcavities.

    León Hilario, L M; Bruchhausen, A; Lobos, A M; Aligia, A A

    2007-04-30

    We calculate the intensity of the polariton-mediated inelastic light scattering in semiconductor microcavities. We treat the exciton-photon coupling nonperturbatively and incorporate lifetime effects in both excitons and photons, and a coupling of the photons to the electron-hole continuum. Taking the matrix elements as fitting parameters, the results are in excellent agreement with measured Raman intensities due to optical phonons that are resonant with the upper polariton branches in II-VI microcavities with embedded CdTe quantum wells. PMID:21690956

  16. Raman spectroscopy for nanomaterials characterization

    2012-01-01

    First volume of a 40-volume series on nanoscience and nanotechnology, edited by the renowned scientist Challa S.S.R. Kumar. This handbook gives a comprehensive overview about Raman spectroscopy for the characterization of nanomaterials. Modern applications and state-of-the-art techniques are covered and make this volume essential reading for research scientists in academia and industry.

  17. Electronic Raman Scattering in Graphene

    LU Hong-Yan; WANG Qiang-Hua

    2008-01-01

    Linear dispersion near the Dirac points in the band structure of graphenes can give rise to novel physical properties.We calculate the electronic contribution to the Raman spectra in graphenes, which also shows novel features.In the clean limit, the Raman spectrum in the undoped graphene is linear (with a universal slope against impurity scattering) at low energy due to the linear dispersion near the Dirac points, and it peaks at a position corresponding to the van Hove singularity in the band structure. In a doped graphene, the electronic Raman absorption is forbidden up to a vertical inter-band particle-hole gap. Beyond the gap the spectrum follows the undoped case. In the presence of impurities, absorption within the gap (in the otherwise clean case) is induced, which is identified as the intra-band contribution. The Drude-like intra-band contribution is seen to be comparable to the higher energy inter-band Raman peak. The results are discussed in connection to experiments.

  18. Simulations of the polarisation-dependent Raman intensity of β-carotene in photosystem II crystals

    Highlights: • First polarisation-dependent Raman spectroscopy on photosystem II crystals. • Orientation-dependent Raman intensity simulations for di- and monomeric crystals. • Simulations account for all β-carotenes (β-Car) in the unit cell for the first time. • Prediction for identificationy of the β-Car cation in side-path electron transport. - Abstract: In order to clarify possibilities to identify the β-carotene (β-Car) radicals in secondary electron transfer (ET) reactions in the photosystem II core complex (PSIIcc), Raman intensities of all 96 β-Car cofactors in the unit cell of PSIIcc-dimer crystals as a function of polarisation and crystal orientation were simulated based on the 2.9 Å resolution structure. The Raman-active symmetry Ag in the C2h group is assigned to the β-Car modes ν66 and ν67. Simulations are in agreement with experiment for off-resonant excitation at 1064 nm. Resonant measurements at 476 and 532 nm excitation can not be explained, which is attributed to mode mixing in the excited state and the existence of different spectral pools. The identity of the β-Car oxidised in secondary ET can not be resolved by Raman measurements on PSIIcc-dimer crystals. Additional simulations show that similar measurements on PSIIcc-monomer crystals could provide a possible route to solve this issue

  19. Simulations of the polarisation-dependent Raman intensity of β-carotene in photosystem II crystals

    Brose, K., E-mail: katharina.brose@gmx.net [Institut für Festkörperphysik, Technische Universität Berlin, Hardenbergstraße 36, 10623 Berlin (Germany); Zouni, A. [Institut für Chemie, Max-Volmer-Laboratorium, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany); Müh, F. [Institut für Theoretische Physik, Johannes Kepler Universität Linz, Altenberger Straße 69, 4040 Linz (Austria); Mroginski, M.A. [Institut für Chemie, Max-Volmer-Laboratorium, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany); Maultzsch, J. [Institut für Festkörperphysik, Technische Universität Berlin, Hardenbergstraße 36, 10623 Berlin (Germany)

    2013-06-03

    Highlights: • First polarisation-dependent Raman spectroscopy on photosystem II crystals. • Orientation-dependent Raman intensity simulations for di- and monomeric crystals. • Simulations account for all β-carotenes (β-Car) in the unit cell for the first time. • Prediction for identificationy of the β-Car cation in side-path electron transport. - Abstract: In order to clarify possibilities to identify the β-carotene (β-Car) radicals in secondary electron transfer (ET) reactions in the photosystem II core complex (PSIIcc), Raman intensities of all 96 β-Car cofactors in the unit cell of PSIIcc-dimer crystals as a function of polarisation and crystal orientation were simulated based on the 2.9 Å resolution structure. The Raman-active symmetry A{sub g} in the C{sub 2h} group is assigned to the β-Car modes ν{sub 66} and ν{sub 67}. Simulations are in agreement with experiment for off-resonant excitation at 1064 nm. Resonant measurements at 476 and 532 nm excitation can not be explained, which is attributed to mode mixing in the excited state and the existence of different spectral pools. The identity of the β-Car oxidised in secondary ET can not be resolved by Raman measurements on PSIIcc-dimer crystals. Additional simulations show that similar measurements on PSIIcc-monomer crystals could provide a possible route to solve this issue.

  20. Raman spectroscopy of bone metastasis

    Esmonde-White, Karen A.; Sottnik, Joseph; Morris, Michael; Keller, Evan

    2012-02-01

    Raman spectroscopy of bone has been used to characterize chemical changes occurring in diseases such as osteoporosis, osteoarthritis and osteomyelitis. Metastasis of cancer into bone causes changes to bone quality that are similar to those observed in osteoporosis, such as decreased bone strength, but with an accelerated timeframe. In particular, osteolytic (bone degrading) lesions in bone metastasis have a marked effect on patient quality of life because of increased risk of fractures, pain, and hypercalcemia. We use Raman spectroscopy to examine bone from two different mouse models of osteolytic bone metastasis. Raman spectroscopy measures physicochemical information which cannot be obtained through standard biochemical and histological measurements. This study was reviewed and approved by the University of Michigan University Committee on the Care and Use of Animals. Two mouse models of prostate cancer bone metastasis, RM1 (n=3) and PC3-luc (n=4) were examined. Tibiae were injected with RM1 or PC3-luc cancer cells, while the contralateral tibiae received a placebo injection for use as controls. After 2 weeks of incubation, the mice were sacrificed and the tibiae were examined by Raman microspectroscopy (λ=785 nm). Spectroscopic markers corresponding to mineral stoichiometry, bone mineralization, and mineral crystallinity were compared in spectra from the cancerous and control tibiae. X-ray imaging of the tibia confirmed extensive osteolysis in the RM1 mice, with tumor invasion into adjoining soft tissue and moderate osteolysis in the PC3-luc mice. Raman spectroscopic markers indicate that osteolytic lesions are less mineralized than normal bone tissue, with an altered mineral stoichiometry and crystallinity.

  1. Raman spectroscopy as a tool for the characterization and classification of pollen; Raman-Spektroskopie als Werkzeug fuer die Charakterisierung und Klassifizierung von Pollen

    Schulte, Franziska

    2010-09-20

    The chemical composition of pollen, the physiological containers that produce the male gametophytes of seed plants, has been a subject of research of plant physiologists, biochemists, and lately even material scientists for various reasons. The aim of this work was the analysis of whole pollen grains and pollen components by Raman Spectroscopy. These experiments were complemented by other techniques such as Enviromental Scanning Electron Microscopy (ESEM), High-Performance- Thin-Layer-Chromatography (HPTLC), Infrared Spectroscopy (IR) and Nuclear-Magnetic-Resonance Spectroscopy (NMR). As reported here, individual fresh pollen grains and their morphological constituents can be characterized and also classified in situ without prior preparation. Classification of pollen is based on their biochemical fingerprint revealed in their Raman spectrum. Raman spectroscopy is nondestructive and can be carried out with single pollen grains or fragments. It could be shown that the biochemical makeup of the pollen (as a part of the recognition/mating system) is altered during formation of a new biological species and that the species-specific chemical similarities and dissimilarities indeed reflect in the Raman spectral fingerprint. On the basis of the chemical information, unsupervised multivariate analysis consisting of hierarchical clustering revealed in most cases chemical similarities between species that were indicative of both phylogenetic relationship and matin behavior. Therefore experiments were conducted that gave the in situ Raman spectroscopic signatures ot the carotenoid molecules. As the data indicates, the in situ Raman spectra of the carotenoid molecules measured in single intact pollen grains provide in situ evidence of interspecies variations in pollen carotenoid content, structure, and/or assembly without prior purification. Results from HPTLC confirmed that carotenoid composition varied greatly between species and that the different in situ spectral

  2. Inverse Raman effect: applications and detection techniques

    The processes underlying the inverse Raman effect are qualitatively described by comparing it to the more familiar phenomena of conventional and stimulated Raman scattering. An experession is derived for the inverse Raman absorption coefficient, and its relationship to the stimulated Raman gain is obtained. The power requirements of the two fields are examined qualitatively and quantitatively. The assumption that the inverse Raman absorption coefficient is constant over the interaction length is examined. Advantages of the technique are discussed and a brief survey of reported studies is presented

  3. Nanoscale Analysis of Interwall Interaction in a Multiwalled Carbon Nanotube by Tip-Enhanced Raman Spectroscopy

    Chaunchaiyakul, Songpol; Yano, Takeshi; Khoklang, Kamonchanok; Krukowski, Pawel; Akai-Kasaya, Megumi; Saito, Akira; Kuwahara, Yuji

    Raman spectroscopy is a useful tool for the study of carbon materials, but its spatial resolution is limited by the optical diffraction limit. Recently, we constructed a scanning tunneling microscope-based tip-enhanced Raman spectroscopy (STM-TERS) system in ultrahigh vacuum, which overcomes the optical diffraction limit, and enables the investigation of single-molecular Raman spectra simultaneously with topographic imaging. We have investigated position-sensitive Raman spectra along the tube axis of an isolated multiwalled carbon nanotube, which is a result of the different number of nanotube walls at each location. We found that the intensity ratio between the 2D to the G band increases with the number of walls. This indicates that the quantum interference between Raman scattering pathways affects each Raman mode differently. The interaction between nanotube walls induces splitting of the π and π* bands which increases the number of the 2D band scattering pathways owing to double resonance, eventually increasing the probability of scattering for the 2D band relative to the G band. These results provide a deeper understanding of the single-molecule interaction of carbon materials in the nanoscale.

  4. Raman spectroscopy of transition metal dichalcogenides.

    Saito, R; Tatsumi, Y; Huang, S; Ling, X; Dresselhaus, M S

    2016-09-01

    Raman spectroscopy of transition metal dichalcogenides (TMDs) is reviewed based on our recent theoretical and experimental works. First, we discuss the semi-classical and quantum mechanical description for the polarization dependence of Raman spectra of TMDs in which the optical dipole transition matrix elements as a function of laser excitation energy are important for understanding the polarization dependence of the Raman intensity and Raman tensor. Overviewing the symmetry of TMDs, we discuss the dependence of the Raman spectra of TMDs on layer thickness, polarization, laser energy and the structural phase. Furthermore, we discuss the Raman spectra of twisted bilayer and heterostructures of TMDs. Finally, we give our perspectives on the Raman spectroscopy of TMDs. PMID:27388703

  5. From molecular fragments to crystals: a UV Raman spectroscopic study on the mechanism of Fe-ZSM-5 synthesis.

    Fan, Fengtao; Sun, Keju; Feng, Zhaochi; Xia, Haian; Han, Bo; Lian, Yuxiang; Ying, Pinliang; Li, Can

    2009-01-01

    The nucleation process of iron-exchanged zeolite Fe-ZSM-5, from the assembly of distorted tetrahedrally coordinated iron species and silicate rings in the precursor to the final Fe-ZSM-5 crystals, as well as variations in the coordination environment of iron, were studied by UV resonance Raman spectroscopy and complementary techniques.The entire sequence of crystallization events of Fe-ZSM-5 was monitored by UV Raman spectroscopy in combination with HRTEM, UV/Vis spectroscopy, X-ray diffraction patterns, and periodic DFT calculations. Fe-ZSM-5 was synthesized by an organic-free method to avoid signal interference from the organic template in Raman spectra. Framework iron atoms with resonance Raman bands at 516, 1115, and 1165 cm(-1), and a Raman band at 1016 cm(-1) are detected for Fe-ZSM-5. In the early stage of Fe-ZSM-5 synthesis, the precursor contains iron atoms in distorted tetrahedral coordination and five- and six-membered silicate rings. Nucleation by aggregation of the precursor species was monitored by UV Raman spectroscopy based on the resonance Raman effect, and confirmed by periodic DFT calculations. Evolution of iron species on the surface and in the bulk phase was monitored by UV Raman spectroscopy with excitation at 244 and 325 nm, as well as HRTEM. Nucleation takes place first in the core of the amorphous particles, and crystalline nuclei with Fe-ZSM-5 structure are formed in the core by consuming the amorphous shell. Finally the amorphous particles are completely transformed into Fe-ZSM-5 crystals. PMID:19197930

  6. Regime for a Self-ionizing Raman Laser Amplifier

    Backward Raman amplification and compression at high power might occur if a long pumping laser pulse is passed through a plasma to interact resonantly with a counter-propagating short seed pulse [V.M. Malkin, et al., Phys. Rev. Lett. 82 (1999) 4448-4451]. One critical issue, however, is that the pump may be unacceptably depleted due to spontaneous Raman backscatter from intrinsic fluctuations in the amplifying plasma medium prior to its useful interaction with the seed. Premature backscatter may be avoided, however, by employing a gaseous medium with pump intensities too low to ionize the medium, and using the intense seed to produce the plasma by rapid photoionization as it is being amplified [V.M. Malkin, et al., Phys. Plasmas (2001)]. In addition to allowing that only rather low power pumps be used, photoionization introduces a damping of the short pulse which must be overcome by the Raman growth rate for net amplification to occur. The parameter space of gas densities, laser wavelengths, and laser intensities is surveyed to identify favorable regimes for this effect. Output laser intensities of 10(superscript ''17'') W/cm(superscript ''2'') for 0.5 mm radiation are found to be feasible for such a scheme using a pump of 10(superscript ''13'') W/cm(superscript ''2'') and an initial seed of 5 x 10(superscript ''14'') W/cm(superscript ''2'') over an amplification length of 5.6 cm in hydrogen gas

  7. Regime for a self-ionizing Raman laser amplifier

    Backward Raman amplification and compression at high power might occur if a long pumping laser pulse is passed through a plasma to interact resonantly with a counter-propagating short seed pulse [V. M. Malkin et al., Phys. Rev. Lett. 82, 4448-4451 (1999)]. One critical issue, however, is that the pump may be unacceptably depleted due to spontaneous Raman backscatter from intrinsic fluctuations in the amplifying plasma medium prior to its useful interaction with the seed. Premature backscatter may be avoided, however, by employing a gaseous medium with pump intensities too low to ionize the medium and using the intense seed to produce the plasma by rapid photoionization as it is being amplified [V. M. Malkin et al., Phys. Plasmas 8, 4698-4699 (2001)]. In addition to allowing that only rather low power pumps be used, photoionization introduces a damping of the short pulse which must be overcome by the Raman growth rate for net amplification to occur. The parameter space of gas densities, laser wavelengths, and laser intensities is surveyed to identify favorable regimes for this effect. Output laser intensities of 2x1017 W/cm2 for 0.5 μm radiation are found to be feasible for such a scheme using a pump of 1x1013 W/cm2 and an initial seed of 5x1014 W/cm2 over an amplification length of 5.6 cm in hydrogen gas

  8. Raman scattering of few-layers MoTe2

    Grzeszczyk, M.; Gołasa, K.; Zinkiewicz, M.; Nogajewski, K.; Molas, M. R.; Potemski, M.; Wysmołek, A.; Babiński, A.

    2016-06-01

    We report on room-temperature Raman scattering measurements in few-layer crystals of exfoliated molybdenum ditelluride (MoTe2) performed with the use of 632.8 nm (1.96 eV) laser light excitation. In agreement with a recent study reported by Froehlicher et al (2015 Nano Lett. 15 6481) we observe a complex structure of the out-of-plane vibrational modes ({{{A}}}1{{g}}{/{{A}}}1\\prime ), which can be explained in terms of interlayer interactions between single atomic planes of MoTe2. In the case of low-energy shear and breathing modes of rigid interlayer vibrations, it is shown that their energy evolution with the number of layers can be well reproduced within a linear chain model with only the nearest neighbor interaction taken into account. Based on this model the corresponding in-plane and out-of-plane force constants are determined. We also show that the Raman scattering in MoTe2 measured using 514.5 nm (2.41 eV) laser light excitation results in much simpler spectra. We argue that the rich structure of the out-of-plane vibrational modes observed in Raman scattering spectra excited with the use of 632.8 nm laser light results from its resonance with the electronic transition at the M point of the MoTe2 first Brillouin zone.

  9. Raman characteristics of hydrocarbon and hydrocarbon inclusions

    ZHANG Nai; TIAN ZuoJi; LENG YingYing; WANG HuiTong; SONG FuQing; MENG JianHua

    2007-01-01

    The Raman spectrograms of hydrocarbon standard samples show that: (1) the Raman spectrogram of normal paraffin has very strong peaks of methyl and methylene (from 2700 cm-1 to 2970 cm-1); (2)branch methyl has the particular peak of 748 cm-1±; (3) six cyclic has the particular peak of 804 cm-1±; (4)phenyl has two particular peaks of 988 cm-1± and 3058 cm-1± and the 988 cm-1± peak is stronger than the 3058 cm-1± peak; and (5) hexene has three alkenyl spectrum peaks of 1294 cm-1±, 1635 cm-1± and 2996 cm-1±, with the 1635 cm-1± peak being the strongest, showing that the number of carbon in hydrocarbon does not affect its Raman spectrogram, and the hydrocarbon molecular structure and base groups affect its Raman spectrogram, the same hydrocarbons (such as normal paraffin) have the same Raman spectrogram; the types (such as CH4, C2H6, C3H8) and the content of hydrocarbon in oil inclusions are not estimated by their characteristic Raman peaks. According to the Raman spectrograms of hydrocarbon compositions, the Raman spectrogram of hydrocarbon inclusion can be divided into five types: saturated hydrocarbon Raman spectrogram, fluoresce Raman spectrogram, saturated hydrocarbon bitumen Raman spectrogram, bitumen Raman spectrogram, and ethane Raman spectrogram.And according to the characteristics of Raman spectrogram, hydrocarbon inclusions can be divided into five types: saturated hydrocarbon inclusion, less saturated hydrocarbon (oil or gas) inclusion,saturated hydrocarbon bitumen inclusion, bitumen inclusion, and methane water inclusion.

  10. Raman characteristics of hydrocarbon and hydrocarbon inclusions

    2007-01-01

    The Raman spectrograms of hydrocarbon standard samples show that: (1) the Raman spectrogram of normal paraffin has very strong peaks of methyl and methylene (from 2700 cm-1 to 2970 cm-1); (2) branch methyl has the particular peak of 748 cm-1±; (3) six cyclic has the particular peak of 804 cm-1±; (4) phenyl has two particular peaks of 988 cm-1± and 3058 cm-1± and the 988 cm-1± peak is stronger than the 3058 cm-1± peak; and (5) hexene has three alkenyl spectrum peaks of 1294 cm-1±, 1635 cm-1± and 2996 cm-1±, with the 1635 cm-1± peak being the strongest, showing that the number of carbon in hy-drocarbon does not affect its Raman spectrogram, and the hydrocarbon molecular structure and base groups affect its Raman spectrogram, the same hydrocarbons (such as normal paraffin) have the same Raman spectrogram; the types (such as CH4, C2H6, C3H8) and the content of hydrocarbon in oil inclu-sions are not estimated by their characteristic Raman peaks. According to the Raman spectrograms of hydrocarbon compositions, the Raman spectrogram of hydrocarbon inclusion can be divided into five types: saturated hydrocarbon Raman spectrogram, fluoresce Raman spectrogram, saturated hydro-carbon bitumen Raman spectrogram, bitumen Raman spectrogram, and ethane Raman spectrogram. And according to the characteristics of Raman spectrogram, hydrocarbon inclusions can be divided into five types: saturated hydrocarbon inclusion, less saturated hydrocarbon (oil or gas) inclusion, saturated hydrocarbon bitumen inclusion, bitumen inclusion, and methane water inclusion.

  11. Raman lasing and Fano lineshapes in a packaged fiber-coupled whispering-gallerymode microresonator

    Zhao, Guangming; Wang, Tao; Xu, Linhua; Long, Gui-lu; Yang, Lan

    2016-01-01

    We report Raman lasing and the optical analog of electromagnetically-induced-transparency (EIT) in a whispering-gallerymode (WGM) microtoroid resonator embedded in a low refractive index polymer matrix together with a tapered fiber coupler. The Raman laser supports both single and multimode operation with low power thresholds. Observations of Fano and EIT-like pheonomena in a packaged microresonator will enable high resolution sensors and can be used in networks where slow light process is needed. These results open the way for portable, robust, and stable WGM microlasers and laserbased sensors for applications in various environments.

  12. RAMAN SCATTERING AND EXCITATION SPECTROSCOPY IN CdTe/CdMnTe SUPERLATTICES

    Viña, L.; Chang, L; J. Yoshino

    1987-01-01

    We have observed oscillatory structure in the excitation spectra of CdTe/CdxMN1-xTe superlattices. A comparison of these spectra with conventional Raman spectra shows that the structures correspond to first and higher order LO-phonons of the CdTe wells and the CdTe/CdxMn1-xTe barriers, as well as combination of them. A strong enhancement in Resonance Raman scattering of both the CdTe and the CdMnTe phonons, at the energy of the heavy-hole exciton of the superlattice, suggests a small valence-...

  13. Nonlinear resonances

    Rajasekar, Shanmuganathan

    2016-01-01

    This introductory text presents the basic aspects and most important features of various types of resonances and anti-resonances in dynamical systems. In particular, for each resonance, it covers the theoretical concepts, illustrates them with case studies, and reviews the available information on mechanisms, characterization, numerical simulations, experimental realizations, possible quantum analogues, applications and significant advances made over the years. Resonances are one of the most fundamental phenomena exhibited by nonlinear systems and refer to specific realizations of maximum response of a system due to the ability of that system to store and transfer energy received from an external forcing source. Resonances are of particular importance in physical, engineering and biological systems - they can prove to be advantageous in many applications, while leading to instability and even disasters in others. The book is self-contained, providing the details of mathematical derivations and techniques invo...

  14. CuO-chain Raman scattering and photoinduced metastability in YBa2Cu3Ox

    Käll, M.; Osada, M.; Kakihana, M.;

    1998-01-01

    Raman measurements in YBa2Cu3Ox (x=6.72-6.82) high-T-c superconductors reveal intense phonon scattering due to an electronic resonance localized near oxygen vacancies on the CuO chains. Below room temperature the resonance can be photobleached in a manner similar to reported persistent photoinduced...

  15. 瞬态吸收和共振拉曼光谱研究硝基对联苯氮宾、氮宾离子反应活性的影响%Investigation of the Influence of Nitro-Substitution on the Reaction of Biphenyl-Nitrene and Nitrenium Ion by Transient Absorption and Resonance Raman Spectroscopic Techniques

    李亚芳; 程博文; 沈超; 郑旭明; 薛佳丹; 杜勇; 汤文建

    2016-01-01

    利用光解芳基叠氮化合物得到单重态氮宾,运用纳秒瞬态吸收光谱、瞬态共振拉曼光谱实验手段,辅以密度泛函理论(DFT)计算,研究了4′-硝基-4-联苯氮宾在乙腈和水溶液中的光化学反应中间体。实验结果表明,在非质子溶剂中,4′-硝基-4-联苯氮宾发生系间窜越反应生成三线态氮宾;在质子溶剂中,单重态氮宾可被质子化产生氮宾离子。与4-联苯氮宾和氮宾离子相比,硝基对单重态氮宾系间窜越反应路径影响很小;降低了氮宾离子与水和叠氮阴离子的反应活性,却提高了其与鸟苷的反应活性。%Arylnitrenes and arylnitrenium ions are both short-lived intermediates that are highly reactive. In this work, nanosecond transient absorption and transient resonance Raman spectroscopic measurements were used to detect and identify the intermediates generated from the singlet 4′-nitro-4-biphenylnitrene after photolysis of the corresponding aryl azide in acetonitrile and aqueous solution. Combined with the density functional theory (DFT) simulation results, the structural and electronic characteristics of the above experimental intermediates were specified. The spectral results indicate that in aprotic solvents (such as acetonitrile), the singlet 4′-nitro-4-biphenylnitrene undergoes intersystem crossing (ISC) to the triplet nitrene. In contrast, in a protic solvent (such as the mixed aqueous solution used in this work), the singlet 4′-nitro-4-biphenylnitrene can be protonated to produce the nitrenium ion. Compared with its un-substituted counterpart, the nitro substitution has little influence on the ISC reaction pathway of the singlet 4-biphenylnitrene. With regard to the un-substituted nitrenium ion, the nitro group decreases its reactivity towards water and azide anion, while accelerating its reaction rate towards 2′-deoxyguanosine based on the different quench reaction rates between the nitrenium ion and

  16. Plasmonic nanostructures for surface-enhanced Raman spectroscopy

    Jiang, Ruiqian

    In the last three decades, a large number of different plasmonic nanostructures have attracted much attention due to their unique optical properties. Those plasmonic nanostructures include nanoparticles, nanoholes and metal nanovoids. They have been widely utilized in optical devices and sensors. When the plasmonic nanostructures interact with the electromagnetic wave and their surface plasmon frequency match with the light frequency, the electrons in plasmonic nanostructures will resonate with the same oscillation as incident light. In this case, the plasmonic nanostructures can absorb light and enhance the light scattering. Therefore, the plasmonic nanostructures can be used as substrate for surface-enhanced Raman spectroscopy to enhance the Raman signal. Using plasmonic nanostructures can significantly enhance Raman scattering of molecules with very low concentrations. In this thesis, two different plasmonic nanostructures Ag dendrites and Au/Ag core-shell nanoparticles are investigated. Simple methods were used to produce these two plasmonic nanostructures. Then, their applications in surface enhanced Raman scattering have been explored. Ag dendrites were produced by galvanic replacement reaction, which was conducted using Ag nitrate aqueous solution and copper metal. Metal copper layer was deposited at the bottom side of anodic aluminum oxide (AAO) membrane. Silver wires formed inside AAO channels connected Ag nitrate on the top of AAO membrane and copper layer at the bottom side of AAO. Silver dendrites were formed on the top side of AAO. The second plasmonic nanostructure is Au/Ag core-shell nanoparticles. They were fabricated by electroless plating (galvanic replacement) reaction in a silver plating solution. First, electrochemically evolved hydrogen bubbles were used as template through electroless deposition to produce hollow Au nanoparticles. Then, the Au nanoparticles were coated with Cu shells in a Cu plating solution. In the following step, a Ag

  17. Rashba realization: Raman with RF

    Campbell, D. L.; Spielman, I. B.

    2016-03-01

    We theoretically explore a Rashba spin–orbit coupling scheme which operates entirely in the absolute ground state manifold of an alkali atom, thereby minimizing all inelastic processes. An energy gap between ground eigenstates of the proposed coupling can be continuously opened or closed by modifying laser polarizations. Our technique uses far-detuned ‘Raman’ laser coupling to create the Rashba potential, which has the benefit of low spontaneous emission rates. At these detunings, the Raman matrix elements that link m F magnetic sublevel quantum numbers separated by two are also suppressed. These matrix elements are necessary to produce the Rashba Hamiltonian within a single total angular momentum f manifold. However, the far-detuned Raman couplings can link the three XYZ states familiar to quantum chemistry, which possess the necessary connectivity to realize the Rashba potential. We show that these XYZ states are essentially the hyperfine spin eigenstates of {}87{Rb} dressed by a strong radio-frequency magnetic field.

  18. Raman spectroscopy peer review report

    The Hanford Site in eastern Washington includes 177 underground storage tanks (UST), which contain waste materials produced during the production of nuclear fuels. The materials in the tanks must be characterized to support the retrieval, processing, and final disposition of the waste. Characterization is currently performed by removing waste samples for analyses in a hot cell or laboratory. A review of the Hanford Raman Spectroscopy Program was held in Richland on March 23 and 24, 1994. A team of principal investigators and researchers made presentations that covered both technical and programmatic aspects of the Hanford Site Raman work. After these presentations and discussions, the review panel met in a closed session to formalize a list of findings. The reviewers agreed that Raman spectroscopy is an excellent method to attack the tank waste characterization and screening problems that were presented. They agreed that there was a good chance that the method would be successful as presently envisioned. The reviewers provided the following primary recommendations: evaluation a laser with wavelength in the near infrared; provide optical filters at or near the sampling end of the fiber-optic probe; develop and implement a strategy for frequent calibration of the system; do not try to further increase Raman resolution at the expense of wavelength range; clearly identify and differentiate between requirements for providing a short-term operational system and requirements for optimizing a system for long-term field use; and determine the best optical configuration, which may include reduced fiber-optic diameter and/or short focal length and low F-number spectrographs

  19. Novel systems of resonant wave interactions

    A matrix Riemann–Hilbert problem (RHP) is constructed using the dressing method starting from two uncoupled, one-directional linear wave equations; the RHP thus obtained is then used to derive a novel integrable matrix non-local system of equations describing resonant wave interactions, together with its Lax pair. This system is shown to be a matrix generalization of the equations for resonant three-wave interactions and stimulated Raman scattering. Several compatible reductions admitted by this system are also discussed. (paper)

  20. Raman spectroscopic studies on bacteria

    Maquelin, Kees; Choo-Smith, Lin-P'ing; Endtz, Hubert P.; Bruining, Hajo A.; Puppels, Gerwin J.

    2000-11-01

    Routine clinical microbiological identification of pathogenic micro-organisms is largely based on nutritional and biochemical tests. Laboratory results can be presented to a clinician after 2 - 3 days for most clinically relevant micro- organisms. Most of this time is required to obtain pure cultures and enough biomass for the tests to be performed. In the case of severely ill patients, this unavoidable time delay associated with such identification procedures can be fatal. A novel identification method based on confocal Raman microspectroscopy will be presented. With this method it is possible to obtain Raman spectra directly from microbial microcolonies on the solid culture medium, which have developed after only 6 hours of culturing for most commonly encountered organisms. Not only does this technique enable rapid (same day) identifications, but also preserves the sample allowing it to be double-checked with traditional tests. This, combined with the speed and minimal sample handling indicate that confocal Raman microspectroscopy has much potential as a powerful new tool in clinical diagnostic microbiology.

  1. Difference Raman spectroscopy of DNA molecules

    In this paper the micro-Raman spectra of calf DNA for different points of DNA sample have been recorded. The Raman spectra were made with help of difference Raman spectroscopy technique. Raman spectra were recorded with high spatial resolution from different points of the wet and dry samples in different spectral range (100÷4000cm−1) using two lasers: argon (514.5 nm) and helium -neon (632.8 nm). The significant differences in the Raman spectra for dry and wet DNA and for different points of DNA molecules were observed. The obtained data on difference Raman scattering spectra of DNA molecules may be used for identification of DNA types and for analysis of genetic information associated with the molecular structure of this molecule

  2. Raman technique application for rubber blends characterization

    Smitthipong, W.

    2007-11-01

    Full Text Available Raman spectroscopy has been employed in a number of studies to examine the morphological changes in a variety of materials. It is a non-destructive analysis method and an equally useful method for the investigation of material structure. Recently, Raman spectroscopy has been developed to employ as an imaging instrumentation. Sample surface scanning in X- and Y-axis and sample depth (Z-axis can be carried out by modifying the focus of the laser beam from the Raman microscope. Therefore, three-dimensional images can be thus built by using special software. The surface and bulk properties of immiscible rubber blend were investigated by Raman spectroscopy. The results obtained by Raman spectroscopy were in good agreement with those of Scanning Electron Microscope (SEM. The combination of Raman spectrometry and SEM clearly elucidates the identification of phases between the dispersed phase and the matrix (continuous phase of the immiscible rubber blends.

  3. Stimulated Raman scattering in large plasmas

    Stimulated Raman scattering is of concern to laser fusion since it can create a hot electron environment which can increase the difficulty of achieving high final fuel densities. In earlier experiments with one micron laser light, the energy measured in Raman-scattered light has been insignificant. But these experiments were done with, at most, about 100 joules of laser energy. The Raman instability has a high threshold which also requires a large plasma to be irradiated with a large diameter spot. Only with a long interaction length can the Raman-scattered light wave convectively grow to a large amplitude, and only in recent long pulse, high energy experiments (4000 joules in 2 ns) at the Shiva laser facility have we observed as much as several percent of the laser light to be Raman-scattered. We find that the Raman instability has a much lower intensity threshold for longer laser pulselength and larger laser spot size on a solid target

  4. Design of an 1800nm Raman amplifier

    Svane, Ask Sebastian; Rottwitt, Karsten

    2013-01-01

    We present the experimental results for a Raman amplifier that operates at 1810 nm and is pumped by a Raman fiber laser at 1680 nm. Both the pump laser and the Raman amplifier is polarization maintaining. A challenge when scaling Raman amplifiers to longer wavelengths is the increase in...... transmission loss, but also the reduction in the Raman gain coefficient as the amplifier wavelength is increased. Both polarization components of the Raman gain is characterized, initially for linearly co-polarized signal and pump, subsequently linearly polarized orthogonal signal and pump. The noise...... performance of the amplifier is also investigated for both configurations. Our results show an on/off gain exceeding 20 dB at 1810 nm for which the obtained effective noise figure is below 3 dB....

  5. Increased wavelength options in the visible and ultraviolet for Raman lasers operating on dual Raman modes.

    Mildren, R P; Piper, J A

    2008-03-01

    We report increased wavelength options from Raman lasers for Raman media having two Raman modes of similar gain coefficient. For an external-cavity potassium gadolinium tungstate Raman laser pumped at 532 nm, we show that two sets of Stokes orders are generated simultaneously by appropriate orientation of the Raman crystal, and also wavelengths that correspond to sums of the two Raman modes. Up to 14 visible Stokes lines were observed in the wavelength range 555-675 nm. The increase in Stokes wavelengths also enables a much greater selection of wavelengths to be accessed via intracavity nonlinear sum frequency and difference frequency mixing. For example, we demonstrate 30 output wavelength options for a wavelength-selectable 271-321 nm Raman laser with intracavity sum frequency mixing in BBO. We also present a theoretical analysis that enables prediction of wavelength options for dual Raman mode systems. PMID:18542414

  6. Surface Plasmons and Surface Enhanced Raman Spectra of Aggregated and Alloyed Gold-Silver Nanoparticles

    Y. Fleger

    2009-01-01

    Full Text Available Effects of size, morphology, and composition of gold and silver nanoparticles on surface plasmon resonance (SPR and surface enhanced Raman spectroscopy (SERS are studied with the purpose of optimizing SERS substrates. Various gold and silver films made by evaporation and subsequent annealing give different morphologies and compositions of nanoparticles and thus different position of the SPR peak. SERS measurements of 4-mercaptobenzoic acid obtained from these films reveal that the proximity of the SPR peak to the exciting laser wavelength is not the only factor leading to the highest Raman enhancement. Silver nanoparticles evaporated on top of larger gold nanoparticles show higher SERS than gold-silver alloyed nanoparticles, in spite of the fact that the SPR peak of alloyed nanoparticles is narrower and closer to the excitation wavelength. The highest Raman enhancement was obtained for substrates with a two-peak particle size distribution for excitation wavelengths close to the SPR.

  7. Raman spectroscopy in pharmaceutical product design

    Paudel, Amrit; Raijada, Dhara; Rantanen, Jukka

    2015-01-01

    molecular-based drug discovery, design of innovative drug delivery systems and quality control of finished products. This review presents concise accounts of various conventional and emerging Raman instrumentations including associated hyphenated tools of pharmaceutical interest. Moreover, relevant...... application cases of Raman spectroscopy in early and late phase pharmaceutical development, process analysis and micro-structural analysis of drug delivery systems are introduced. Finally, potential areas of future advancement and application of Raman spectroscopic techniques are discussed....

  8. Raman LIDAR Detection of Cloud Base

    Demoz, Belay; Starr, David; Whiteman, David; Evans, Keith; Hlavka, Dennis; Peravali, Ravindra

    1999-01-01

    Advantages introduced by Raman lidar systems for cloud base determination during precipitating periods are explored using two case studies of light rain and virga conditions. A combination of the Raman lidar derived profiles of water vapor mixing ratio and aerosol scattering ratio, together with the Raman scattered signals from liquid drops, can minimize or even eliminate some of the problems associated with cloud boundary detection using elastic backscatter lidars.

  9. Fluorocarbon Fiber-Optic Raman Probe for Non-Invasive Raman Spectroscopy

    Okagbare, Paul I.; Morris, Michael D.

    2012-01-01

    We report the development of a novel fiber-optic Raman probe using a graded index fluorocarbon optical fiber. The fluorocarbon fiber has a simple Raman spectrum, a low fluorescence background, and generates a Raman signal that in turbid media serves as an intense reference Raman signal that corrects for albedo. The intensity of the reference signal can easily be varied as needed by scaling the length of the excitation fiber. Additionally, the fluorocarbon probe eliminates the broad silica Ram...

  10. Femtosecond stimulated Raman spectroscopy as a tool to detect molecular vibrations in ground and excited electronic states.

    Gelin, Maxim F; Domcke, Wolfgang; Rao, B Jayachander

    2016-05-14

    We give a detailed theoretical analysis of the simplest variant of femtosecond stimulated Raman spectroscopy, where a picosecond Raman pump pulse and a femtosecond Raman probe pulse are applied resonantly to a chromophore in thermal equilibrium in the ground electronic state. We demonstrate that this technique is capable of the detection of dephasing-free Raman-like lines revealing vibrational modes not only in the electronic ground state but also in the excited electronic state of the chromophore. The analytical results obtained with simplifying assumptions for the shape of the laser pulses are substantiated by numerical simulations with realistic laser pulses, employing the equation-of-motion phase-matching approach. PMID:27179484

  11. Occlusal caries detection using polarized Raman spectroscopy

    Ionita, I.; Bulou, A.

    2008-02-01

    The tooth enamel, because of its hydroxyapatite composition, must present a Raman spectrum with strong polarization anisotropy. Carious lesions of the enamel will produce an alteration of local symmetry and will increase much more scattering of light. This will reduce the anisotropy of the Raman spectra. Because of the difference between high sensitivity to polarization of the 959 cm -1 Raman peak in sound enamel and low sensitivity in carried enamel, Raman polarized spectroscopy could be a useful method to early detect teeth caries.

  12. Titanium-enhanced Raman microcavity laser.

    Deka, Nishita; Maker, Ashley J; Armani, Andrea M

    2014-03-15

    Whispering gallery mode microcavities are ideally suited to form microlaser devices because the high circulating intensity within the cavity results in ultralow lasing thresholds. However, to achieve low-threshold Raman lasing in silica devices, it is necessary to have quality factors above 100 million. One approach to circumvent this restriction is to intercalate a sensitizer into the silica, which increases the Raman gain. In the present work, we demonstrate a Raman laser based on a titanium sensitized silica solgel coated toroidal microcavity. By tuning the concentration of the Ti, the Raman efficiency improves over 3× while maintaining sub-mW thresholds. PMID:24690786

  13. Raman Spectroscopy and its Application in Nanostructures

    Zhang, Shu-Lin

    2012-01-01

    Raman Spectroscopy and its Application in Nanostructures is an original and timely contribution to a very active area of physics and materials science research. This book presents the theoretical and experimental phenomena of Raman spectroscopy, with specialized discussions on the physical fundamentals, new developments and main features in low-dimensional systems of Raman spectroscopy. In recent years physicists, materials scientists and chemists have devoted increasing attention to low-dimensional systems and as Raman spectroscopy can be used to study and analyse such materials as carbon nan

  14. Raman gain induced mode evolution and on-demand coupling control in whispering-gallery-mode microcavities.

    Yang, Xu; Özdemir, Şahin Kaya; Peng, Bo; Yilmaz, Huzeyfe; Lei, Fu-Chuan; Long, Gui-Lu; Yang, Lan

    2015-11-16

    Waveguide-coupled optical resonators have played an important role in a wide range of applications including optical communication, sensing, nonlinear optics, slow/fast light, and cavity QED. In such a system, the coupling regimes strongly affect the resonance feature in the light transmission spectra, and hence the performance and outcomes of the applications. Therefore it is crucial to control the coupling between the waveguide and the microresonator. In this work, we investigated a fiber-taper coupled whispering-gallery-mode microresonator system, in which the coupling regime is traditionally controlled by adjusting the distance between the resonator and the fiber-taper mechanically. We propose and experimentally demonstrate that by utilizing Raman gain one can achieve on-demand control of the coupling regime without any mechanical movement in the resonator system. Particularly, the application of Raman gain is accompanied by Q enhancement. We also show that with the help of Raman gain control, the transitions between various coupling regimes can affect the light transmission spectra so as to provide better resolvability and signal amplification. This all-optical approach is also suitable for monolithically integrated and packaged waveguide-resonator systems, whose coupling regime is fixed at the time of manufacturing. It provides an effective route to control the light transmission in a waveguide-couple resonator system without mechanically moving individual optical components. PMID:26698440

  15. Four-fold Raman enhancement of 2D band in twisted bilayer graphene: evidence for a doubly degenerate Dirac band and quantum interference

    We report the observation of a strong 2D band Raman in twisted bilayer graphene (tBLG) with large rotation angles under 638 nm and 532 nm visible laser excitations. The 2D band Raman intensity increased four-fold as opposed to the two-fold increase observed in single-layer graphene. The same tBLG samples also exhibited rotation-dependent G-line resonances and folded phonons under 364 nm UV laser excitation. We attribute this 2D band Raman enhancement to the constructive interference between two double-resonance Raman pathways, which were enabled by a nearly degenerate Dirac band in the tBLG Moiré superlattices. (paper)

  16. Self-assembled microtubes and rhodamine 6G functionalized Raman-active gold microrods from 1-hydroxybenzotriazole

    Ravula Thirupathi; Erode N Prabhakaran

    2011-05-01

    1-Hydroxybenzotriazole spontaneously self-assembles to form hollow, linear microtubes initiated by controlled evaporation from water. The tube cavities act as thermo-labile micromoulds for the synthesis of linear gold microrods. Rhodamine 6G-labelled gold microrods, exhibiting surface enhanced resonance Raman activity, have been synthesized using the HOBT microtubes.

  17. Chirality changes in carbon nanotubes studied with near-field Raman spectroscopy.

    Anderson, Neil; Hartschuh, Achim; Novotny, Lukas

    2007-03-01

    We report on the direct visualization of chirality changes in carbon nanotubes by mapping local changes in resonant RBM phonon frequencies with an optical resolution of 40 nm using near-field Raman spectroscopy. We observe the transition from semiconducting-to-metal and metal-to-metal chiralities at the single nanotube level. Our experimental findings, based on detecting changes in resonant RBM frequencies, are complemented by measuring changes in the G-band frequency and line shape. In addition, we observe increased Raman scattering due to local defects associated with the structural transition. From our results, we determine the spatial extent of the transition region to be Ltrans approximately 40-100 nm. PMID:17324000

  18. Single-pulse coherent anti-Stokes Raman spectroscopy via fiber Bragg grating

    Oh, Seung Ryeol; Park, Joo Hyun; Kwon, Won Sik; Kim, Jin Hwan; Kim, Kyung-Soo; Lee, Jae Yong; Kim, Soohyun

    2016-03-01

    Fiber Bragg grating is used in a variety of applications. In this study, we suggest compact, cost-effective coherent anti- Stokes Raman spectroscopy which is based on the pulse shaping methods via commercialized fiber Bragg grating. The experiment is performed incorporating a commercialized femtosecond pulse laser system (MICRA, Coherent) with a 100 mm length of 780-HP fiber which is inscribed 50 mm of Bragg grating. The pump laser for coherent anti-Stokes Raman spectroscopy has a bandwidth of 90 nm and central wavelength of 815 nm with a notch shaped at 785 nm. The positive chirped pulse is compensated by chirped mirror set. We compensate almost 14000 fs2 of positive group delay dispersion for the transform-limited pulse at the sample position. The pulse duration was 15 fs with average power of 50 mW, and showed an adequate notch shape. Finally, coherent anti-Stokes Raman signals are observed using a spectrometer (Jobin Yvon Triax320 and TE-cooled Andor Newton EMCCD). We obtained coherent anti-Stokes Raman signal of acetone sample which have Raman peak at the spectral finger-print region. In conclusion, the proposed method is more simple and cost-effective than the methods of previous research which use grating pairs and resonant photonic crystal slab. Furthermore, the proposed method can be used as endoscope application.

  19. Coherent Raman scattering in high-pressure/high-temperature fluids: An overview

    The present understanding of high-pressure/high-temperature dense-fluid behavior is derived almost exclusively from hydrodynamic and thermodynamic measurements. Such results average over the microscopic aspects of the materials and are, therefore, insufficient for a complete understanding of fluid behavior. At the present, dense-fluid models can be verified only to the extend that they agree with the macroscopic measurements. Recently, using stimulated Raman scattering, Raman induced Kerr effect scattering, and coherent anti-Stokes Raman scattering, we have been able to probe some of the microscopic phenomenology of these dense fluids. In this paper, we discuss primarily the use of CARS in conjunction with a two-stage light-gas gun to obtain vibrational spectra of shock-compressed liquid N2, O2, CO, their mixtures, CH3NO2, and N2O. These experimental spectra are compared to synthetic spectra calculated using a semiclassical model for CARS intensities and best fit vibrational frequencies, peak Raman susceptibilities, and Raman linewidths. For O2, the possibility of resonance enhancement from collision-induced absorption is addressed. Shifts in the vibrational frequencies reflect the influence of increased density and temperature on the intramolecular motion. The derived parameters suggest thermal equilibrium of the vibrational levels is established less than a few nanoseconds after shock passage. Vibrational temperatures are obtained that agree with those derived from equation-of-state calculations. Measured linewidths suggest that vibrational dephasing times have decreased to subpicosecond values at the highest shock pressures

  20. Neuroaesthetic Resonance

    Brooks, Anthony Lewis

    2013-01-01

    the unencumbered motion-to-computer-generated activities - ‘Music Making’, ‘Painting’, ‘Robotic’ and ‘Video Game’ control. A focus of this position paper is to highlight how Aesthetic Resonance, in this context, relates to the growing body of research on Neuroaesthetics to evolve Neuroaesthetic Resonance.......Neuroaesthetic Resonance emerged from a mature body of patient- centered gesture-control research investigating non-formal rehabilitation via ICT-enhanced-Art to question ‘Aesthetic Resonance’. Motivating participation, ludic engagement, and augmenting physical motion in non-formal (fun) treatment...... tailored channeling of sensory stimulus aligned as ‘art-making’ and ‘game playing’ core experiences. Thus, affecting brain plasticity and human motoric-performance via the adaptability (plasticity) of digital medias result in closure of the human afferent-efferent neural feedback loop closure through...

  1. Phase Matching of Diverse Modes in a WGM Resonator

    Savchenkov, Anatoliy; Strekalov, Dmitry; Yu, Nan; Matsko, Andrey; Mohageg, Makan; Maleki, Lute

    2008-01-01

    Phase matching of diverse electromagnetic modes (specifically, coexisting optical and microwave modes) in a whispering-gallery-mode (WGM) resonator has been predicted theoretically and verified experimentally. Such phase matching is necessary for storage of microwave/terahertz and optical electromagnetic energy in the same resonator, as needed for exploitation of nonlinear optical phenomena. WGM resonators are used in research on nonlinear optical phenomena at low optical intensities and as a basis for design and fabrication of novel optical devices. Examples of nonlinear optical phenomena recently demonstrated in WGM resonators include low-threshold Raman lasing, optomechanical oscillations, frequency doubling, and hyperparametric oscillations. The present findings regarding phase matching were made in research on low-threshold, strongly nondegenerate parametric oscillations in lithium niobate WGM resonators. The principle of operation of such an oscillator is rooted in two previously observed phenomena: (1) stimulated Raman scattering by polaritons in lithium niobate and (2) phase matching of nonlinear optical processes via geometrical confinement of light. The oscillator is partly similar to terahertz oscillators based on lithium niobate crystals, the key difference being that a novel geometrical configuration of this oscillator supports oscillation in the regime. The high resonance quality factors (Q values) typical of WGM resonators make it possible to achieve oscillation at a threshold signal level much lower than that in a non-WGM-resonator lithium niobate crystal.

  2. Raman scattering determination of strain in CdTe/ZnTe superlattices

    Jackson, M K; Miles, R. H.; McGill, T. C.; Faurie, J. P.

    1989-01-01

    The strain configuration in CdTe/ZnTe strained-layer superlattices has been measured by Raman scattering near resonance. The ZnTe-like longitudinal optical phonon energy in the superlattice is significantly shifted from the bulk value to lower energies and the shift increases with increasing superlattice CdTe fraction. The observed shifts agree with calculations of strain shifts based on a free-standing strain distribution.

  3. Entangled valence electron-hole dynamics revealed by stimulated attosecond x-ray Raman scattering

    Healion, Daniel; Zhang, Yu; Biggs, Jason D.; Govind, Niranjan; Mukamel, Shaul

    2012-09-06

    We show that broadband x-ray pulses can create wavepackets of valence electrons and holes localized in the vicinity of a selected atom (nitrogen, oxygen or sulfur in cysteine) by resonant stimulated Raman scattering. The subsequent dynamics reveals highly correlated motions of entangled electrons and hole quasiparticles. This information goes beyond the time-dependent total charge density derived from x-ray diffraction.

  4. Q-switched Raman laser system

    George, E.V.

    Method and apparatus for use of a Raman or Brillouin switch together with a conventional laser and a saturable absorber that is rapidly bleached at a predeterimined frequency nu = nu/sub O/, to ultimately produce a Raman or Brillouin pulse at frequency nu = nu/sub O/ +- nu /sub Stokes/.

  5. Self-pulsation in Raman fiber amplifiers

    Pedersen, Martin Erland Vestergaard; Ott, Johan Raunkjær; Rottwitt, Karsten

    2009-01-01

    Dynamic behavior caused by Brillouin scattering in Raman fiber amplifiers is studied. Modes of self-pulsation steady state oscillations are found. Their dependence on amplification scheme is demonstrated.......Dynamic behavior caused by Brillouin scattering in Raman fiber amplifiers is studied. Modes of self-pulsation steady state oscillations are found. Their dependence on amplification scheme is demonstrated....

  6. Applications of Raman spectroscopy in life science

    Martin, Airton A.; T. Soto, Cláudio A.; Ali, Syed M.; Neto, Lázaro P. M.; Canevari, Renata A.; Pereira, Liliane; Fávero, Priscila P.

    2015-06-01

    Raman spectroscopy has been applied to the analysis of biological samples for the last 12 years providing detection of changes occurring at the molecular level during the pathological transformation of the tissue. The potential use of this technology in cancer diagnosis has shown encouraging results for the in vivo, real-time and minimally invasive diagnosis. Confocal Raman technics has also been successfully applied in the analysis of skin aging process providing new insights in this field. In this paper it is presented the latest biomedical applications of Raman spectroscopy in our laboratory. It is shown that Raman spectroscopy (RS) has been used for biochemical and molecular characterization of thyroid tissue by micro-Raman spectroscopy and gene expression analysis. This study aimed to improve the discrimination between different thyroid pathologies by Raman analysis. A total of 35 thyroid tissues samples including normal tissue (n=10), goiter (n=10), papillary (n=10) and follicular carcinomas (n=5) were analyzed. The confocal Raman spectroscopy allowed a maximum discrimination of 91.1% between normal and tumor tissues, 84.8% between benign and malignant pathologies and 84.6% among carcinomas analyzed. It will be also report the application of in vivo confocal Raman spectroscopy as an important sensor for detecting advanced glycation products (AGEs) on human skin.

  7. Energy Scavenging in Silicon Raman Amplifiers

    Fathpour, S; Jalali, B

    2006-01-01

    Continuous-wave Raman amplification in silicon waveguides with negative electrical power dissipation is reported. It is shown that a p-n junction can simultaneously achieve carrier sweep-out leading to net continuous-wave gain, and electrical power generation. The approach is also applicable to silicon Raman lasers and other third-order nonlinear optical devices.

  8. Development of a Raman spectrometer to study surface-enhanced Raman scattering

    Raman spectroscopy is an important tool, which provides enormous information on the vibrational and structural details of materials. This understanding is not only interesting due to its fundamental importance, but also of considerable importance in optoelectronics and device applications of these materials in nanotechnology. In this report, we begin with a brief introduction on the Raman effect and various Raman scattering techniques, followed by a detailed discussion on the development of an instrument with home-built collection optics attachment. This Raman system consists of a pulsed laser excitation source, a sample compartment, collection optics to collect the scattered light, a notch filter to reject the intense laser light, a monochromator to disperse the scattered light and a detector to detect the Raman signal. After calibrating the Raman spectrometer with standard solvents, we present our results on Surface-Enhanced Raman Scattering (SERS) investigations on three different kinds of chemical systems. (author)

  9. Raman barometry of diamond formation

    Izraeli, E. S.; Harris, J. W.; Navon, O.

    1999-11-01

    Pressures and temperatures of the diamond source region are commonly estimated using chemical equilibria between coexisting mineral inclusions. Here we present another type of geobarometer, based on determination of the internal pressure in olivine inclusions and the stresses in the surrounding diamond. Using Raman spectroscopy, pressures of 0.13 to 0.65 GPa were measured inside olivine inclusions in three diamonds from the Udachnaya mine in Siberia. Stresses in the diamond surrounding the inclusions indicated similar pressures (0.11-0.41 GPa). Nitrogen concentration and aggregation state in two of the diamonds yielded mantle residence temperatures of ˜1200°C. Using this temperature and the bulk moduli and thermal expansion of olivine and diamond, we calculated source pressures of 4.4-5.2 GPa. We also derived a linear approximation for the general dependence of the source pressure ( P0, GPa) on source temperature ( T0, °C) and the measured internal pressure in the inclusion ( Pi): P0=(3.259×10 -4Pi+3.285×10 -3) T0+0.9246 Pi+0.319. Raman barometry may be applied to other inclusions in diamonds or other inclusion-host systems. If combined with IR determination of the mantle residence temperature of the diamond, it allows estimation of the pressure at the source based on a non-destructive examination of a single diamond containing a single inclusion.

  10. Rashba realization: Raman with RF

    Campbell, D L; Spielman, I B

    2016-01-01

    We theoretically explore a Rashba spin–orbit coupling scheme which operates entirely in the absolute ground state manifold of an alkali atom, thereby minimizing all inelastic processes. An energy gap between ground eigenstates of the proposed coupling can be continuously opened or closed by modifying laser polarizations. Our technique uses far-detuned ‘Raman’ laser coupling to create the Rashba potential, which has the benefit of low spontaneous emission rates. At these detunings, the Raman matrix elements that link mF magnetic sublevel quantum numbers separated by two are also suppressed. These matrix elements are necessary to produce the Rashba Hamiltonian within a single total angular momentum f manifold. However, the far-detuned Raman couplings can link the three XYZ states familiar to quantum chemistry, which possess the necessary connectivity to realize the Rashba potential. We show that these XYZ states are essentially the hyperfine spin eigenstates of 87Rb dressed by a strong radio-frequency magnetic field.

  11. Local structures of polar wurtzites Zn_{1-x}Mg_{x}O studied by Raman and {67}Zn/{25}Mg NMR spectroscopies and by total neutron scattering

    Kim, Young-Il; Cadars, Sylvian; Shayib, Ramzy; Proffen, Thomas; Feigerle, Charles S.; Chmelka, Bradley F.; Seshadri, Ram

    2008-01-01

    Local compositions and structures of Zn_{1-x}Mg_{x}O alloys have been investigated by Raman and solid-state {67}Zn/{25}Mg nuclear magnetic resonance (NMR) spectroscopies, and by neutron pair-distribution-function (PDF) analyses. The E2(low) and E2(high) Raman modes of Zn_{1-x}Mg_{x}O display Gaussian- and Lorentzian-type profiles, respectively. At higher Mg substitutions, both modes become broader, while their peak positions shift in opposite directions. The evolution of Raman spectra from Zn...

  12. Applications of Raman spectroscopy to gemology.

    Bersani, Danilo; Lottici, Pier Paolo

    2010-08-01

    Being nondestructive and requiring short measurement times, a low amount of material, and no sample preparation, Raman spectroscopy is used for routine investigation in the study of gemstone inclusions and treatments and for the characterization of mounted gems. In this work, a review of the use of laboratory Raman and micro-Raman spectrometers and of portable Raman systems in the gemology field is given, focusing on gem identification and on the evaluation of the composition, provenance, and genesis of gems. Many examples are shown of the use of Raman spectroscopy as a tool for the identification of imitations, synthetic gems, and enhancement treatments in natural gemstones. Some recent developments are described, with particular attention being given to the semiprecious stone jade and to two important organic materials used in jewelry, i.e., pearls and corals. PMID:20419294

  13. Strongly enhanced Raman scattering of graphene by a single gold nanorod

    He, Yingbo; Shen, Hongming; Cheng, Yuqing [State Key Laboratory for Mesoscopic Physics, Department of Physics, Peking University, Beijing 100871 (China); Lu, Guowei, E-mail: guowei.lu@pku.edu.cn; Gong, Qihuang [State Key Laboratory for Mesoscopic Physics, Department of Physics, Peking University, Beijing 100871 (China); Collaborative Innovation Center of Quantum Matter, Beijing 100871 (China)

    2015-08-03

    Individual gold nanorods (AuNRs) and monolayer graphene hybrid system is investigated experimentally. Surface enhanced Raman scattering (SERS) signal of the graphene is observed due to a single AuNR with enhancement factor up to ∼1000-fold. The SERS intensity is strongly polarization dependent and the enhancement effect varies with the detuning between the excitation laser and the AuNR resonance. The SERS effect is highest when the resonant wavelength of the AuNRs matches well with the excitation light. By correlating the scattering and photoluminescence, it is demonstrated that the conventional background in SERS ascribes to the photon emission of metallic nanostructures.

  14. Population transfer of a NaH molecule via stimulated Raman adiabatic passage

    Zai, Jing-Bo; Zhan, Wei-Shen; Wang, Shuo; Dang, Hai-Ping; Han, Xiao

    2016-09-01

    The population transfer of a NaH molecule from the ground state {{X}1}{Σ+} to the target state {{A}1}{Σ+} via stimulated Raman adiabatic passage (STIRAP) is investigated. The results show that the intensity, delay time and detuning have a significant effect on population transfer. A large population transfer is observed with increased pump and Stokes intensity, especially when the pump and Stokes intensity match. Population transfer also depends on the delay time between the pump laser pulse and the Stokes laser pulse. The detuning of the two pulses influences the population transfer. Efficient population transfer can be realized under the resonant or two-photon resonant condition.

  15. Species concentration measurements using coherent anti-Stokes Raman spectroscopy (CARS)

    The determination of combustion species concentrations using coherent anti-Stokes Raman spectroscopy, (CARS) often demands accurate modeling of the relative intensities of resonant (ro-vibrational) and nonresonant (electronic) contributions to the CARS spectrum. The ratio of these intensities is nearly always used to infer concentrations, whether indirectly through analyzing its effect on spectral profiles, or directly through comparing resonant signals to externally or internally generated non-resonant signals. Concentration information is derived from the fact that resonant intensities relate directly to the abundances of individual species, while nonresonance intensities are a function of the total gas composition. To analyze CARS data, theoretical susceptibility spectra are calculated, convolved with appropriate instrument and/or laser lineshapes, and varied for best fit to experimental spectra

  16. Tunable and amplified Raman gold nanoprobes for effective tracking (TARGET): in vivo sensing and imaging

    Gandra, Naveen; Hendargo, Hansford C.; Norton, Stephen J.; Fales, Andrew M.; Palmer, Gregory M.; Vo-Dinh, Tuan

    2016-04-01

    We describe the development of a highly tunable, physiologically stable, and ultra-bright Raman probe, named as TARGET (Tunable and Amplified Raman Gold Nanoprobes for Effective Tracking), for in vitro and in vivo surface-enhanced Raman scattering (SERS) applications. The TARGET structure consists of a gold core inside a larger gold shell with a tunable interstitial gap similar to a ``nanorattle'' structure. The combination of galvanic replacement and the seed mediated growth method was employed to load Raman reporter molecules and subsequently close the pores to prevent leaking and degradation of reporters under physiologically extreme conditions. Precise tuning of the core-shell gap width, core size, and shell thickness allows us to modulate the plasmonic effect and achieve a maximum electric-field (E-field) intensity. The interstitial gap of TARGET nanoprobes can be designed to exhibit a plasmon absorption band at 785 nm, which is in resonance with the dye absorption maximum and lies in the ``tissue optical window'', resulting in ultra-bright SERS signals for in vivo studies. The results of in vivo measurements of TARGETs in laboratory mice illustrated the usefulness of these nanoprobes for medical sensing and imaging.We describe the development of a highly tunable, physiologically stable, and ultra-bright Raman probe, named as TARGET (Tunable and Amplified Raman Gold Nanoprobes for Effective Tracking), for in vitro and in vivo surface-enhanced Raman scattering (SERS) applications. The TARGET structure consists of a gold core inside a larger gold shell with a tunable interstitial gap similar to a ``nanorattle'' structure. The combination of galvanic replacement and the seed mediated growth method was employed to load Raman reporter molecules and subsequently close the pores to prevent leaking and degradation of reporters under physiologically extreme conditions. Precise tuning of the core-shell gap width, core size, and shell thickness allows us to modulate the

  17. Raman-gain induced loss-compensation in whispering-gallery-microresonators and single-nanoparticle detection with whispering-gallery Raman-microlasers

    Ozdemir, Sahin Kaya; Yang, Xu; Peng, Bo; Yilmaz, Huzeyfe; He, Lina; Monifi, Faraz; Long, Gui Lu; Yang, Lan

    2014-01-01

    Recently optical whispering-gallery-mode resonators (WGMRs) have emerged as promising platforms to achieve label-free detection of nanoscale objects and to reach single molecule sensitivity. The ultimate detection performance of WGMRs are limited by energy dissipation in the material they are fabricated from. Up to date, to improve detection limit, either rare-earth ions are doped into the WGMR to compensate losses or plasmonic resonances are exploited for their superior field confinement. Here, we demonstrate, for the first time, enhanced detection of single-nanoparticle induced mode-splitting in a silica WGMR via Raman-gain assisted loss-compensation and WGM Raman lasing. Notably, we detected and counted individual dielectric nanoparticles down to a record low radius of 10 nm by monitoring a beatnote signal generated when split Raman lasing lines are heterodyne-mixed at a photodetector. This dopant-free scheme retains the inherited biocompatibility of silica, and could find widespread use for sensing in bio...

  18. Active resonance tuning of stretchable plasmonic structures

    Zhu, Xiaolong; Xiao, Sanshui; Mortensen, N. Asger

    2012-01-01

    Active resonance tuning is highly desired for the applications of plasmonic structures, such as optical switches and surface enhanced Raman substrates. In this paper, we demonstrate the active tunable plasmonic structures, which composed of monolayer arrays of metallic semishells with dielectric...... cores on stretchable elastic substrates. These composite structures support Bragg-type surface plasmon resonances whose frequencies are sensitive to the arrangement of the metallic semishells. Under uniaxial stretching, the lattice symmetry of these plasmonic structures can be reconfigured from...... hexagonal to monoclinic lattice, leading to not only large but also polarization-dependent shifts of the resonance frequency. The experimental results are supported by the numerical simulations. Our structures fabricated using simple and inexpensive self-assembly and lift-transfer techniques can open up...

  19. Raman spectroscopy of ZnS quantum dots

    Trajić, J., E-mail: jelena@ipb.ac.rs [Institute of Physics, University of Belgrade, 11080 Belgrade (Serbia); Kostić, R.; Romčević, N.; Romčević, M. [Institute of Physics, University of Belgrade, 11080 Belgrade (Serbia); Mitrić, M. [Institute Vinča, University of Belgrade, 11000 Belgrade (Serbia); Lazović, V. [Institute of Physics, University of Belgrade, 11080 Belgrade (Serbia); Balaž, P. [Institute of Geotechnics, Slovak Academy of Sciences, 043 53 Košice (Slovakia); Stojanović, D. [Institute of Physics, University of Belgrade, 11080 Belgrade (Serbia)

    2015-07-15

    Highlights: • ZnS nanoparticles were synthesized mechanochemically by high-energy milling. • Optical properties were investigated applying Raman spectroscopy. • Continuum medium model of optical phonon confinement in ZnS QD. • Second-order Raman modes in ZnS QDs. - Abstract: ZnS nanoparticles were synthesized mechanochemically by high-energy milling. In order to investigate influence off milling time to sample properties, samples were produced in three different milling times (5 min, 10 min and 20 min). The morphology of samples has been investigated by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). X-ray diffraction (XRD) investigation of synthesized nanocrystals identified cubic structure. From XRD, ZnS size of crystallites was estimated as 1.9 nm (after 5 min milling time), 2.3 nm (10 min) and 2.4 nm (20 min), implying that we are in strong confinement regime. The optical properties were studied by Raman spectroscopy, in spectral region 100–500 cm{sup −1}, excitation source was 514.5 nm (E{sub L} = 2.41 eV), which means that we are in off resonant regime. Dominant spectral structures, of comparable intensity, are registered in spectral region 130–180 cm{sup −1}, around 265 cm{sup −1} and around 345 cm{sup −1}. First two are assigned as second-order ZnS modes. A theoretical model of continuum medium was used to calculate frequencies of the confined optical phonons in ZnS. Satisfactory agreement with experimental results was found and mode at 345 cm{sup −1} is assigned as LO type phonon confined in ZnS nanocrystal.

  20. Classification of oral cancers using Raman spectroscopy of serum

    Sahu, Aditi; Talathi, Sneha; Sawant, Sharada; Krishna, C. Murali

    2014-03-01

    Oral cancers are the sixth most common malignancy worldwide, with low 5-year disease free survival rates, attributable to late detection due to lack of reliable screening modalities. Our in vivo Raman spectroscopy studies have demonstrated classification of normal and tumor as well as cancer field effects (CFE), the earliest events in oral cancers. In view of limitations such as requirement of on-site instrumentation and stringent experimental conditions of this approach, feasibility of classification of normal and cancer using serum was explored using 532 nm excitation. In this study, strong resonance features of β-carotenes, present differentially in normal and pathological conditions, were observed. In the present study, Raman spectra of sera of 36 buccal mucosa, 33 tongue cancers and 17 healthy subjects were recorded using Raman microprobe coupled with 40X objective using 785 nm excitation, a known source of excitation for biomedical applications. To eliminate heterogeneity, average of 3 spectra recorded from each sample was subjected to PC-LDA followed by leave-one-out-cross-validation. Findings indicate average classification efficiency of ~70% for normal and cancer. Buccal mucosa and tongue cancer serum could also be classified with an efficiency of ~68%. Of the two cancers, buccal mucosa cancer and normal could be classified with a higher efficiency. Findings of the study are quite comparable to that of our earlier study, which suggest that there exist significant differences, other than β- carotenes, between normal and cancerous samples which can be exploited for the classification. Prospectively, extensive validation studies will be undertaken to confirm the findings.

  1. Raman investigation of tannin foams

    Full text: Tannin-based organic foams are new foam materials which are environmentally friendly, resistant to re and inexpensive, and intended to be used for building insulation, and also as water absorber or shock absorber. These foams can be produced via an acid catalyzed polycondensation reaction between condensed flavonoids and furfuryl alcohol. Several studies deal with the mechanism involved in this process, but some ambiguities still persist. Raman spectroscopy is an analytical technique suitable for the non-destructive chemical investigation of polymers, allowing to determine the presence of functional groups within a polymer through the interaction of laser light with the vibrational modes of the molecules setting up the sample under investigation. By this spectroscopic technique we have characterized the tannin-based foams and compared their spectral signature with that of tannins, and of polymerized furfuryl alcohol. Similarities and differences to the spectral features of carbonaceous material are discussed. (author)

  2. Raman spectroscopy of 'Bisphenol A'

    Ullah, Ramzan; Zheng, Yuxiang

    2016-03-01

    Raman spectra (95 - 3000 cm-1) of 'Bisphenol A' are presented. Absorption peaks have been assigned by Density Functional Theory (DFT) with B3LYP 6 - 311 ++ G (3df, 3pd) and wB97XD 6 - 311 ++ G (3df, 3pd). B3LYP 6 - 311 ++ G (3df, 3pd) gives frequencies which are nearer to experimental frequencies than wB97XD 6 - 311 ++ G (3df, 3pd) which involves empirical dispersion. Scale factor for wB97XD 6 - 311 ++ G (3df, 3pd) is found out to be 0.95008 by least squares fit.

  3. Single-site surface-enhanced Raman scattering beyond spectroscopy

    Takase, Mai; Yasuda, Satoshi; Murakoshi, Kei

    2016-04-01

    Recent progress in the observation of surface-enhanced Raman scattering (SERS) is reviewed to examine the possibility of finding a novel route for the effective photoexcitation of materials. The importance of well-controlled SERS experiments on a single molecule at a single site is discussed based on the difference in the information obtained from ensemble SERS measurements using multiple active sites with an uncontrolled number of molecules. A single-molecule SERS observation performed at a mechanically controllable breaking junction with a simultaneous conductivity measurement provides clear evidence of the drastic changes both in the intensity and in the Raman mode selectivity of the electromagnetic field generated by localized surface plasmon resonance. Careful control of the field at a few-nanometer-wide gap of a metal nanodimer results in the modification of the selection rule of electronic excitation of an isolated single-walled carbon nanotube. The examples shown in this review suggest that a single-site SERS observation could be used as a novel tool to find, develop, and implement applications of plasmon-induced photoexcitation of materials.

  4. Wide-field Raman imaging for bone detection in tissue.

    Papour, Asael; Kwak, Jin Hee; Taylor, Zach; Wu, Benjamin; Stafsudd, Oscar; Grundfest, Warren

    2015-10-01

    Inappropriate bone growth in soft tissue can occur after trauma to a limb and can cause a disruption to the healing process. This is known as Heterotopic Ossification (HO) in which regions in the tissue start to mineralize and form microscopic bone-like structures. These structures continue to calcify and develop into large, non-functional bony masses that cause pain, limit limb movement, and expose the tissue to reoccurring infections; in the case of open wounds this can lead to amputation as a result of a failed wound. Both Magnetic Resonance Imaging (MRI) and X-ray imaging have poor sensitivity and specificity for the detection of HO, thus delaying therapy and leading to poor patient outcomes. We present a low-power, fast (1 frame per second) optical Raman imaging system with a large field of view (1 cm(2)) that can differentiate bone tissue from soft tissue without spectroscopy, this in contrast to conventional Raman microscopy systems. This capability may allow for the development of instrumentation which permits bedside diagnosis of HO. PMID:26504639

  5. Coded-aperture Raman imaging for standoff explosive detection

    McCain, Scott T.; Guenther, B. D.; Brady, David J.; Krishnamurthy, Kalyani; Willett, Rebecca

    2012-06-01

    This paper describes the design of a deep-UV Raman imaging spectrometer operating with an excitation wavelength of 228 nm. The designed system will provide the ability to detect explosives (both traditional military explosives and home-made explosives) from standoff distances of 1-10 meters with an interrogation area of 1 mm x 1 mm to 200 mm x 200 mm. This excitation wavelength provides resonant enhancement of many common explosives, no background fluorescence, and an enhanced cross-section due to the inverse wavelength scaling of Raman scattering. A coded-aperture spectrograph combined with compressive imaging algorithms will allow for wide-area interrogation with fast acquisition rates. Coded-aperture spectral imaging exploits the compressibility of hyperspectral data-cubes to greatly reduce the amount of acquired data needed to interrogate an area. The resultant systems are able to cover wider areas much faster than traditional push-broom and tunable filter systems. The full system design will be presented along with initial data from the instrument. Estimates for area scanning rates and chemical sensitivity will be presented. The system components include a solid-state deep-UV laser operating at 228 nm, a spectrograph consisting of well-corrected refractive imaging optics and a reflective grating, an intensified solar-blind CCD camera, and a high-efficiency collection optic.

  6. Using Raman spectroscopy to characterize biological materials.

    Butler, Holly J; Ashton, Lorna; Bird, Benjamin; Cinque, Gianfelice; Curtis, Kelly; Dorney, Jennifer; Esmonde-White, Karen; Fullwood, Nigel J; Gardner, Benjamin; Martin-Hirsch, Pierre L; Walsh, Michael J; McAinsh, Martin R; Stone, Nicholas; Martin, Francis L

    2016-04-01

    Raman spectroscopy can be used to measure the chemical composition of a sample, which can in turn be used to extract biological information. Many materials have characteristic Raman spectra, which means that Raman spectroscopy has proven to be an effective analytical approach in geology, semiconductor, materials and polymer science fields. The application of Raman spectroscopy and microscopy within biology is rapidly increasing because it can provide chemical and compositional information, but it does not typically suffer from interference from water molecules. Analysis does not conventionally require extensive sample preparation; biochemical and structural information can usually be obtained without labeling. In this protocol, we aim to standardize and bring together multiple experimental approaches from key leaders in the field for obtaining Raman spectra using a microspectrometer. As examples of the range of biological samples that can be analyzed, we provide instructions for acquiring Raman spectra, maps and images for fresh plant tissue, formalin-fixed and fresh frozen mammalian tissue, fixed cells and biofluids. We explore a robust approach for sample preparation, instrumentation, acquisition parameters and data processing. By using this approach, we expect that a typical Raman experiment can be performed by a nonspecialist user to generate high-quality data for biological materials analysis. PMID:26963630

  7. Raman chemical imaging of the rhizosphere bacterium Pantoea sp. YR343 and its co-culture with Arabidopsis thaliana.

    Polisetti, Sneha; Bible, Amber N; Morrell-Falvey, Jennifer L; Bohn, Paul W

    2016-04-01

    Chemical imaging of plant-bacteria co-cultures makes it possible to characterize bacterial populations and behaviors and their interactions with proximal organisms, under conditions closest to the environment in the rhizosphere. Here Raman micro-spectroscopy and confocal Raman imaging are used as minimally invasive probes to study the rhizosphere bacterial isolate, Pantoea sp. YR343, and its co-culture with model plant Arabidopsis thaliana by combining enhanced Raman spectroscopies with electron microscopy and principal component analysis (PCA). The presence of carotenoid pigments in the wild type Pantoea sp. YR343 was characterized using resonance Raman scattering, which was also used to confirm successful disruption of the crtB gene in an engineered carotenoid mutant strain. Other components of the Pantoea sp. YR343 cells were imaged in the presence of resonantly enhanced pigments using a combination of surface enhanced Raman imaging and PCA. Pantoea sp. YR343 cells decorated with Ag colloid synthesized ex situ gave spectra dominated by carotenoid scattering, whereas colloids synthesized in situ produced spectral signatures characteristic of flavins in the cell membrane. Scanning electron microscopy (SEM) of whole cells and transmission electron microscopy (TEM) images of thinly sliced cross-sections were used to assess structural integrity of the coated cells and to establish the origin of spectral signatures based on the position of Ag nanoparticles in the cells. Raman imaging was also used to characterize senescent green Arabidopsis thaliana plant roots inoculated with Pantoea sp. YR343, and PCA was used to distinguish spectral contributions from plant and bacterial cells, thereby establishing the potential of Raman imaging to visualize the distribution of rhizobacteria on plant roots. PMID:26948490

  8. Coherent anti-Stokes Raman scattering microscopy of single nanodiamonds

    Pope, Iestyn; Payne, Lukas; Zoriniants, George; Thomas, Evan; Williams, Oliver; Watson, Peter; Langbein, Wolfgang; Borri, Paola

    2014-11-01

    Nanoparticles have attracted enormous attention for biomedical applications as optical labels, drug-delivery vehicles and contrast agents in vivo. In the quest for superior photostability and biocompatibility, nanodiamonds are considered one of the best choices due to their unique structural, chemical, mechanical and optical properties. So far, mainly fluorescent nanodiamonds have been utilized for cell imaging. However, their use is limited by the efficiency and costs in reliably producing fluorescent defect centres with stable optical properties. Here, we show that single non-fluorescing nanodiamonds exhibit strong coherent anti-Stokes Raman scattering (CARS) at the sp3 vibrational resonance of diamond. Using correlative light and electron microscopy, the relationship between CARS signal strength and nanodiamond size is quantified. The calibrated CARS signal in turn enables the analysis of the number and size of nanodiamonds internalized in living cells in situ, which opens the exciting prospect of following complex cellular trafficking pathways quantitatively.

  9. Reduced Modeling of Electron Trapping Nonlinearity in Raman Scattering

    Strozzi, D. J.; Berger, R. L.; Rose, H. A.; Langdon, A. B.; Williams, E. A.

    2009-11-01

    The trapping of resonant electrons in Langmuir waves generated by stimulated Raman scattering (SRS) gives rise to several nonlinear effects, which can either increase or decrease the reflectivity. We have implemented a reduced model of these nonlinearities in the paraxial propagation code pF3D [R. L. Berger et al., Phys. Plasmas 5 (1998)], consisting of a Landau damping reduction and Langmuir-wave frequency downshift. Both effects depend on the local wave amplitude, and gradually turn on with amplitude. This model is compared with 1D seeded Vlasov simulations, that include a Krook relaxation operator to mimic, e.g., transverse sideloss out of a multi-D, finite laser speckle. SRS in these runs develops from a counter-propagating seed light wave. Applications to ICF experiments will also be presented.

  10. Light source for narrow and broadband coherent Raman scattering microspectroscopy.

    Brinkmann, Maximilian; Dobner, Sven; Fallnich, Carsten

    2015-12-01

    We present a light source that is well adapted to both narrow- and broadband coherent Raman scattering (CRS) methods. Based on a single oscillator, the light source delivers synchronized broadband pulses via supercontinuum generation and narrowband, frequency-tunable pulses via four-wave mixing in a photonic crystal fiber. Seeding the four-wave mixing with a spectrally filtered part of the supercontinuum yields high-pulse energies up to 8 nJ and the possibility of scanning a bandwidth of 2000  cm(-1) in 25 ms. All pulses are emitted with a repetition frequency of 1 MHz, which ensures efficient generation of CRS signals while avoiding significant damage of the samples. Consequently, the light source combines the performance of individual narrow- and broadband CRS light sources in one setup, thus enabling hyperspectral imaging and rapid single-resonance imaging in parallel. PMID:26625022

  11. Q-branch Raman scattering and modern kinetic thoery

    Monchick, L. [The Johns Hopkins Univ., Laurel, MD (United States)

    1993-12-01

    The program is an extension of previous APL work whose general aim was to calculate line shapes of nearly resonant isolated line transitions with solutions of a popular quantum kinetic equation-the Waldmann-Snider equation-using well known advanced solution techniques developed for the classical Boltzmann equation. The advanced techniques explored have been a BGK type approximation, which is termed the Generalized Hess Method (GHM), and conversion of the collision operator to a block diagonal matrix of symmetric collision kernels which then can be approximated by discrete ordinate methods. The latter method, which is termed the Collision Kernel method (CC), is capable of the highest accuracy and has been used quite successfully for Q-branch Raman scattering. The GHM method, not quite as accurate, is applicable over a wider range of pressures and has proven quite useful.

  12. Raman scattering from superhard rhenium diboride under high pressure

    Lattice vibrational properties of superhard rhenium diboride (ReB2) were examined up to 8 GPa in a diamond anvil cell using Raman spectroscopy techniques. Linear pressure coefficients and mode Grüneisen parameters are obtained. Good agreement is found between the experimental and theoretical calculated Grüneisen parameters. Examination of the calculated mode Grüneisen parameters reveals that both B-B and Re-B covalent bonds play a dominant role in supporting the applied load under pressure. A comparison of vibrations parallel and perpendicular to the c-axis indicates that bonds along the c-axis tend to take greater loads. Our results agree with observations of elastic lattice anisotropy obtained from both in situ X-ray diffraction measurements and ultrasonic resonance spectra

  13. Influence of the ordered structure of short-chain polymer molecule all-trans-β-carotene on Raman scattering cross section in liquid

    Qu Guan-Nan; OuYang Shun-Li; Wang Wei-Wei; Li Zuo-Wei; Sun Cheng-Lin; Men Zhi-Wei

    2011-01-01

    We measured the resonant Raman spectra of all-trans-β-carotene in solvents with different densities and concentrations at different temperatures. The results demonstrated that the Raman scattering cross section (RSCS) of short-chain polymer all-trans-β-carotene is extremely high in liquid. Resonance and strong coherent weakly damped CC bond vibrating properties play important roles under these conditions. Coherent weakly damped CC bond vibration strength is associated with molecular ordered structure. All-trans-β-carotene has highly ordered structure and strong coherent weakly damped CC bond vibrating properties, which lead to large RSCS in the solvent with large density and low concentration at low temperature.

  14. Neuroaesthetic Resonance

    Brooks, Anthony Lewis

    2013-01-01

    Neuroaesthetic Resonance emerged from a mature body of patient- centered gesture-control research investigating non-formal rehabilitation via ICT-enhanced-Art to question ‘Aesthetic Resonance’. Motivating participation, ludic engagement, and augmenting physical motion in non-formal (fun) treatment sessions are achieved via adaptive action-analyzed activities. These interactive virtual environments are designed to empower patients’ creative and/or playful expressions via digital feedback stimu...

  15. Possibility of VOx/SiO2 Complexes Speciation: Comparative Multi-wavelength Raman and DR UV-vis Study

    Bulánek, Roman; Čičmanec, Pavel; Setnička, Michal

    Raman spectroscopy is one of the very often used spectroscopic methods for characterization of vanadium surface species. However, Raman spectra of VOx-silica systems are more complex and interpretation is more difficult in comparison with other supports (like Al2O3, ZrO2, TiO2 or Nb2O5) because there is strong vibrational coupling between the vanadia species and the silica support. Therefore, assignment and interpretation of some vibrational bands is still subject of controversy. This fact results in incongruity of suggested molecular structure and population of individual vanadium surface complexes. In this contribution, we present systematic comparative study of diffuse reflectance UV-vis spectra and Raman spectra excited by 325 and 514.5 nm lasers obtained on set of dehydrated vanadium modifed hexagonal mesoporous silica (VOx-HMS) samples with vanadium loading from 2 up to 12 wt. %. We prove that changes in population of oligomeric and monomeric VOx species in individual samples are not manifested by significant changes in the character of Raman signals. On the other hand it is evident that with increasing of vanadium loadings the UV-vis spectra show systematic changes. Raman spectroscopy is useful characterization technique for detection presence of very small amount of V2O5 microcrystallites, especially if suitable wavelength of laser is used for remarkable resonant enhancement of Raman intensity of its bands (e.g. 514.5 nm).

  16. Analysis of lipsticks using Raman spectroscopy.

    Gardner, P; Bertino, M F; Weimer, R; Hazelrigg, E

    2013-10-10

    In this study, 80 lipsticks were obtained and evaluated using Raman spectroscopy at excitation wavelengths of 532 and 780 nm. Fluorescence severely limited analysis with the 532 nm line while the 780 nm line proved useful for all samples analyzed. It was possible to differentiate 95% of the lipsticks evaluated based on one or more Raman peaks. However, there were no peak trends observed that could be used to identify a manufacturer or categorize a sample. In situ analysis of lipstick smears was found to be possible even from several Raman active substrates, but was occasionally limited by background fluorescence and in extreme cases, photodegradation. PMID:24053867

  17. Differentiation of Lipsticks by Raman Spectroscopy

    Salahioglu, Fatma; Went, Michael J.

    2012-01-01

    Dispersive Raman spectra have been obtained using a Raman microscope and an excitation wavelength of 632.8 nm from 69 lipsticks of various colours and from a range of manufacturers without any pre-treatment of the samples. 10% of the samples were too fluorescent to give Raman spectra. 22% of the samples gave spectra which were unique to the brand and colour within the collected sample set. The remaining 68% of the samples gave spectra which could be classified into seven distinct groups. Dis...

  18. Raman spectroscopy as a tool for reagent free estimation

    Kumar, S

    2014-01-01

    We present results of Raman spectroscopic studies of urine to determine the suitability of near-infrared Raman spectroscopy for quantitative estimation of urinary urea. The Raman spectra were acquired from the urine samples with an inbuilt Raman spectroscopy setup that employs a 785-nm diode laser as the Raman excitation source. A multivariate algorithm based on partial least square (PLS) regression was developed to predict the concentration of urea depending on the measured sets of Raman spectra and the reference urea concentration. The computed results shows that Raman spectroscopy in amalgamation with PLS-based multivariate chemometric algorithm can detect urea in urine samples with an accuracy of >90 %.

  19. Hyperspectral Imaging with Stimulated Raman Scattering by Chirped Femtosecond Lasers

    Xie, Xiaoliang Sunney; Fu, Dan; Freudiger, Christian Wilhelm; Zhang, Xu; Holtom, Gary

    2013-01-01

    Raman microscopy is a quantitative, label-free, and noninvasive optical imaging technique for studying inhomogeneous systems. However, the feebleness of Raman scattering significantly limits the use of Raman microscopy to low time resolutions and primarily static samples. Recent developments in narrowband stimulated Raman scattering (SRS) microscopy have significantly increased the acquisition speed of Raman based label-free imaging by a few orders of magnitude, at the expense of reduced spec...

  20. Graphitic carbon nitride C6N9H3.HCl: Characterisation by UV and near-IR FT Raman spectroscopy

    The graphitic layered compound C6N9H3.HCl was prepared by reaction between melamine and cyanuric chloride under high pressure-high temperature conditions in a piston cylinder apparatus and characterised using SEM, powder X-ray diffraction, UV Raman and near-IR Fourier transform Raman spectroscopy with near-IR excitation. Theoretical calculations using density functional methods permitted evaluation of the mode of attachment of H atoms to nitrogen sites in the structure and a better understanding of the X-ray diffraction pattern. Broadening in the UV and near-IR FT Raman spectra indicate possible disordering of the void sites within the graphitic layers or it could be due to electron-phonon coupling effects. - Graphical abstract: The graphitic layered compound C6N9H3.HCl was prepared by reaction between melamine and cyanuric chloride under high pressure-high temperature conditions in a piston cylinder apparatus and characterised using SEM, powder X-ray diffraction, UV Raman and near-IR Fourier transform Raman spectroscopy using near-IR excitation. Theoretical calculations using density functional methods permitted evaluation of the mode of attachment of H atoms to nitrogen sites around the C12N12 voids within the layered structure and also led to better understanding of the X-ray diffraction pattern. Sharp peaks in the UV Raman spectra are due to C3N3 triazine ring units in the structure, that may be enhanced by resonance Raman effects. Broadening in the UV and near-IR FT Raman spectra indicate possible disordering within the graphitic layers or electron-phonon coupling effects.

  1. Random number generation from spontaneous Raman scattering

    Collins, M. J.; Clark, A. S.; Xiong, C.; Mägi, E.; Steel, M. J.; Eggleton, B. J.

    2015-10-01

    We investigate the generation of random numbers via the quantum process of spontaneous Raman scattering. Spontaneous Raman photons are produced by illuminating a highly nonlinear chalcogenide glass ( As 2 S 3 ) fiber with a CW laser at a power well below the stimulated Raman threshold. Single Raman photons are collected and separated into two discrete wavelength detuning bins of equal scattering probability. The sequence of photon detection clicks is converted into a random bit stream. Postprocessing is applied to remove detector bias, resulting in a final bit rate of ˜650 kb/s. The collected random bit-sequences pass the NIST statistical test suite for one hundred 1 Mb samples, with the significance level set to α = 0.01 . The fiber is stable, robust and the high nonlinearity (compared to silica) allows for a short fiber length and low pump power favourable for real world application.

  2. Raman spectroscopy at the tritium laboratory Karlsruhe

    Raman spectroscopy is employed successfully for analysis of hydrogen isotopologues at the Tritium Laboratory Karlsruhe (TLK). Raman spectroscopy is based on the inelastic scattering of photons off molecules. Energy is transferred to the molecules as rotational/vibrational excitation being characteristic for each type of molecule. Thus, qualitative analysis is possible from the Raman shifted light, while quantitative information can be obtained from the signal intensities. After years of research and development, the technique is now well-advanced providing fast (< 10 s), precise (< 0.1%) and true (< 3%) compositional analysis of gas mixtures of hydrogen isotopologues. In this paper, we summarize the recent achievements in the further development on this technique, and the various applications for which it is used at TLK. Raman spectroscopy has evolved as a versatile, highly accurate key method for quantitative analysis complementing the port-folio of analytic techniques at the TLK

  3. Energy dissipation by a longitudinal Raman process

    The concept of a longitudinal Raman process is introduced to encompass the indirect transmission of energy from slow electrons to nuclei through the reversible polarization of surrounding electrons. Experimental approaches are sought to assess this process quantitatively

  4. Identification of gemstone treatments with Raman spectroscopy

    Kiefert, Lore; Haenni, Henry A.; Chalain, Jean-Pierre

    2000-09-01

    The newest gemstone treatment concerns brownish diamonds of type IIa. These can be improved to near colorless by an enhancement process developed by General Electric, USA, using high temperature and pressure. A comparison of Raman spectroscopic features in the visible area (luminescence bands) of both treated and untreated colorless diamonds is given. Finally, examples of artificially colored peals and corals and their detection with Raman spectroscopy are shown.

  5. Control system of the Raman spectrograph

    Kostka, F. (František); Žďánský, K. (Karel); J. Zavadil; Starý, R. (Robert)

    2010-01-01

    Universal apparatus for measuring Raman spectrography (RS) on surface of solid state samples was designed and realized. It enables to obtain Raman spectrum from the measured semiconductor sample excited by powerful Ar-ion or HeNe lasers, alternatively. The PC controlled equipment consists of a composite optical setup, lasers, optical monochromator, very sensitive CCD camera, micromanipulators, and electric circuits serving to extract relevant signal from the noisy background

  6. Surface enhanced raman spectroscopy on chip

    Hübner, Jörg; Anhøj, Thomas Aarøe; Zauner, Dan;

    2007-01-01

    In this paper we report low resolution surface enhanced Raman spectra (SERS) conducted with a chip based spectrometer. The flat field spectrometer presented here is fabricated in SU-8 on silicon, showing a resolution of around 3 nm and a free spectral range of around 100 nm. The output facet...... fiber. The obtained spectra show that chip based spectrometer together with the SERS active surface can be used as Raman sensor....

  7. Ice thickness measurements by Raman scattering

    Pershin, Sergey M; Klinkov, Vladimir K; Yulmetov, Renat N; Bunkin, Alexey F

    2014-01-01

    A compact Raman LIDAR system with a spectrograph was used for express ice thickness measurements. The difference between the Raman spectra of ice and liquid water is employed to locate the ice-water interface while elastic scattering was used for air-ice surface detection. This approach yields an error of only 2 mm for an 80-mm-thick ice sample, indicating that it is promising express noncontact thickness measurements technique in field experiments.

  8. Raman assisted lightwave synthesized frequency sweeper

    Pedersen, Anders Tegtmeier; Rottwitt, Karsten

    2010-01-01

    We present a Lightwave Synthesized Frequency Sweeper comprising a Raman amplifier for loss compensation. The generated pulse train contains 123 pulses and has a flat signal level as well as a low noise level.......We present a Lightwave Synthesized Frequency Sweeper comprising a Raman amplifier for loss compensation. The generated pulse train contains 123 pulses and has a flat signal level as well as a low noise level....

  9. Candida parapsilosis Biofilm Identification by Raman Spectroscopy

    Ota Samek; Katarina Mlynariková; Silvie Bernatová; Jan Ježek; Vladislav Krzyžánek; Martin Šiler; Pavel Zemánek; Filip Růžička; Veronika Holá; Martina Mahelová

    2014-01-01

    Colonies of Candida parapsilosis on culture plates were probed directly in situ using Raman spectroscopy for rapid identification of specific strains separated by a given time intervals (up to months apart). To classify the Raman spectra, data analysis was performed using the approach of principal component analysis (PCA). The analysis of the data sets generated during the scans of individual colonies reveals that despite the inhomogeneity of the biological samples unambiguous associations to...

  10. Amplifier/compressor fiber Raman lasers.

    Islam, M N; Mollenauer, L F; Stolen, R H; Simpson, J R; Shang, H T

    1987-10-01

    We show that the chirp from cross-phase modulation (XPM) dominates the operation of fiber Raman lasers (FRL's). Thus a FRL in the anomalous group-velocity regime is best described as a XPM-chirped Raman amplifier followed by a linear fiber compressor. While the output of such a laser is generally a narrow pulse with a broad pedestal, we show both experimentally and by computer simulation that negligible background is achievable. PMID:19741882

  11. Nonlinear kinetic modeling of stimulated Raman scattering

    Benisti, Didier

    2011-10-01

    Despite its importance for many applications, such as or Raman amplification or inertial confinement fusion, deriving a nonlinear estimate of Raman reflectivity in a plasma has remained quite a challenge for decades. This is mainly due to the nonlinear modification of the electron distribution function induced by the plasma wave (EPW), which, in turn, modifies the propagation of this wave. In this paper is derived an envelope equation for the EPW valid in 3D and which accounts for the nonlinear change of its collisionless (Landau-like) damping rate, group velocity, coupling to the electromagnetic drive, frequency and wave number. Our theoretical predictions for each of these terms are carefully compared against results from Vlasov simulations of stimulated Raman scattering (SRS), as well as with other theories. Moreover, our envelope model shows to be as accurate as a Vlasov code in predicting Raman threshold in 1D. Making comparisons with experimental results nevertheless requires including transverse dimensions and letting Raman start from noise. To this end, we performed a completely new derivation of the electrostatic fluctuations in a plasma, which accounts nonlinear effects. Moreover, based on our Multi-D simulations of Raman scattering with our envelope code BRAMA, we discuss the effect on SRS of wave front bowing, transverse detrapping and of a completely new defocussing effect due to the local change in the direction of the EPW group velocity induced by the nonlinear decrease of Landau damping.

  12. Visualizing cell state transition using Raman spectroscopy.

    Taro Ichimura

    Full Text Available System level understanding of the cell requires detailed description of the cell state, which is often characterized by the expression levels of proteins. However, understanding the cell state requires comprehensive information of the cell, which is usually obtained from a large number of cells and their disruption. In this study, we used Raman spectroscopy, which can report changes in the cell state without introducing any label, as a non-invasive method with single cell capability. Significant differences in Raman spectra were observed at the levels of both the cytosol and nucleus in different cell-lines from mouse, indicating that Raman spectra reflect differences in the cell state. Difference in cell state was observed before and after the induction of differentiation in neuroblastoma and adipocytes, showing that Raman spectra can detect subtle changes in the cell state. Cell state transitions during embryonic stem cell (ESC differentiation were visualized when Raman spectroscopy was coupled with principal component analysis (PCA, which showed gradual transition in the cell states during differentiation. Detailed analysis showed that the diversity between cells are large in undifferentiated ESC and in mesenchymal stem cells compared with terminally differentiated cells, implying that the cell state in stem cells stochastically fluctuates during the self-renewal process. The present study strongly indicates that Raman spectral morphology, in combination with PCA, can be used to establish cells' fingerprints, which can be useful for distinguishing and identifying different cellular states.

  13. Optical nanoantennas for multiband surface-enhanced infrared and raman spectroscopy

    D'Andrea, Cristiano

    2013-04-23

    In this article we show that linear nanoantennas can be used as shared substrates for surface-enhanced Raman and infrared spectroscopy (SERS and SEIRS, respectively). This is done by engineering the plasmonic properties of the nanoantennas, so to make them resonant in both the visible (transversal resonance) and the infrared (longitudinal resonance), and by rotating the excitation field polarization to selectively take advantage of each resonance and achieve SERS and SEIRS on the same nanoantennas. As a proof of concept, we have fabricated gold nanoantennas by electron beam lithography on calcium difluoride (1-2 μm long, 60 nm wide, 60 nm high) that exhibit a transverse plasmonic resonance in the visible (640 nm) and a particularly strong longitudinal dipolar resonance in the infrared (tunable in the 1280-3100 cm -1 energy range as a function of the length). SERS and SEIRS detection of methylene blue molecules adsorbed on the nanoantenna\\'s surface is accomplished, with signal enhancement factors of 5 × 102 for SERS (electromagnetic enhancement) and up to 105 for SEIRS. Notably, we find that the field enhancement provided by the transverse resonance is sufficient to achieve SERS from single nanoantennas. Furthermore, we show that by properly tuning the nanoantenna length the signals of a multitude of vibrational modes can be enhanced with SEIRS. This simple concept of plasmonic nanosensor is highly suitable for integration on lab-on-a-chip schemes for label-free chemical and biomolecular identification with optimized performances. © 2013 American Chemical Society.

  14. Polarization modulated background-free hyperspectral stimulated Raman scattering microscopy (Conference Presentation)

    Houle, Marie-Andrée.; Andreana, Marco; Ridsdale, Andrew; Moffatt, Doug; Lausten, Rune; Légaré, François; Stolow, Albert

    2016-03-01

    Stimulated Raman Scattering (SRS) microscopy is a nonlinear microscopy technique based on Raman vibrational resonances determined by the frequency difference between Pump and Stokes laser pulses. Modulation of one laser beam transfers the modulation to the other, as either a gain in Stokes (SRG) or a loss in Pump power (SRL). SRS microscopy does not exhibit the four-wave mixing nonresonant background characteristic of CARS microscopy. However, other background signals due to two-photon absorption, thermal lensing or cross-phase modulation (XPM) do reduce the detection sensitivity and can distort the hyperspectral scans. Phase sensitive lock-in detection can reduce contributions from two-photon absorption, which is out-of-phase for the SRG case. However, the background signal due to XPM, which can be in-phase with SRS, can reduce the detection sensitivity. We present a novel polarization modulation (PM) scheme in SRS microscopy which greatly reduces the nonresonant XPM background, demonstrated here for the SRL case. Since many Raman vibrational transitions are parallel polarized, the SRS signal is maximum (minimum) when the polarizations of the pump and the Stokes beams are parallel (perpendicular). However, in both parallel and perpendicular Pump-Stokes geometries, XPM is non-zero in many media. Therefore, PM can remove the XPM background without significantly reducing the SRS signal. Our results show that the PM-SRS successfully removes the nonresonant signal due to XPM. High imaging contrast is observed, concomitant with high sensitivity at very low analyte concentrations and undistorted Raman spectra.

  15. Advances in Low-Frequency 3-color Broadband Coherent Raman Spectroscopy of Condensed Phase Samples

    Ujj, Laszlo

    2016-05-01

    Low-frequency dispersive spontaneous Raman spectroscopy is a very useful method to measure phonon frequencies in crystals or characterize collective vibrational motions of macromolecules. The coherent version of the method has not been fully explored yet. It is shown here that the 3-color Broadband Coherent Raman scattering can be a very powerful extension to not only gas phase but condensed phase low frequency (5-500 cm-1) vibrational measurements with large frequency separation between the narrowband and broadband radiation generating the signal. The spectral measurements presented here used volumetric Brag filters for the first time to record coherent Raman spectra. Specific spectral analysis using model independent methods to derive the vibrational information is also presented. The technic can be extended to measure electronic resonance enhanced spectra by tuning only the frequency of the narrowband laser close to the electronic transition frequencies. This makes the method suitable for coherent Raman microscopy. The polarization properties of the signal is also explained and experimentally verified. Financial support from the College of Sciences and Engineering of UWF is acknowledged.

  16. Fourier transform Raman spectroscopy of polyacrylamide gels (PAGs) for radiation dosimetry

    Polyacrylamide gels (Pages) are used for magnetic resonance imaging radiation dosimetry. Fourier transform (FT) Raman spectroscopy studies were undertaken to investigate cross-linking changes during the copolymerization of polyacrylamide gels in the spectral range of 200-3500 cm-1. Vibrational bands of 1285 cm-1 and 1256 cm-1 were assigned to acrylamide and bis-acrylamide single CH2 δCH2 binding modes. Bands were found to decrease in amplitude with increasing absorbed radiation dose as a result of copolymerization. Principal component regression was performed on FT-Raman spectra of PAG samples irradiated to 50 Gy. Two components were found to be sufficient to account for 98.7% of the variance in the data. Cross validation was used to establish the absorbed radiation dose of an unknown PAG sample from the FT-Raman spectra. The calculated correlation coefficient between measured and predictive samples was 0.997 with a standard error of estimate of 0.976 and a standard error of prediction of 1.140. Results demonstrate the potential of FT-Raman spectroscopy for ionizing radiation dosimetry using polyacrylamide gels. (author)

  17. Raman scattering measurements in flames using a tunable KrF excimer laser

    Wehrmeyer, Joseph A.; Cheng, Tsarng-Sheng; Pitz, Robert W.

    1992-01-01

    A narrow-band tunable KrF excimer laser is used as a spontaneous vibrational Raman scattering source to demonstrate that single-pulse concentration and temperature measurements, with only minimal fluorescence interference, are possible for all major species (O2, N2, H2O, and H2) at all stoichiometries (fuel-lean to fuel rich) of H2-air flames. Photon-statistics-limited precisions in these instantaneous and spatially resolved single-pulse measurements are typically 5 percent, which are based on the relative standard deviations of single-pulse probability distributions. In addition to the single-pulse N2 Stokes/anti-Stokes ratio temperature measurement technique, a time-averaged temperature measurement technique is presented that matches the N2 Stokes Raman spectrum to theoretical spectra by using a single intermediate state frequency to account for near-resonance enhancement. Raman flame spectra in CH4-air flames are presented that have good signal-to-noise characteristics and show promise for single-pulse UV Raman measurements in hydrocarbon flames.

  18. Tunable and amplified Raman gold nanoprobes for effective tracking (TARGET): in vivo sensing and imaging.

    Gandra, Naveen; Hendargo, Hansford C; Norton, Stephen J; Fales, Andrew M; Palmer, Gregory M; Vo-Dinh, Tuan

    2016-04-28

    We describe the development of a highly tunable, physiologically stable, and ultra-bright Raman probe, named as TARGET (Tunable and Amplified Raman Gold Nanoprobes for Effective Tracking), for in vitro and in vivo surface-enhanced Raman scattering (SERS) applications. The TARGET structure consists of a gold core inside a larger gold shell with a tunable interstitial gap similar to a "nanorattle" structure. The combination of galvanic replacement and the seed mediated growth method was employed to load Raman reporter molecules and subsequently close the pores to prevent leaking and degradation of reporters under physiologically extreme conditions. Precise tuning of the core-shell gap width, core size, and shell thickness allows us to modulate the plasmonic effect and achieve a maximum electric-field (E-field) intensity. The interstitial gap of TARGET nanoprobes can be designed to exhibit a plasmon absorption band at 785 nm, which is in resonance with the dye absorption maximum and lies in the "tissue optical window", resulting in ultra-bright SERS signals for in vivo studies. The results of in vivo measurements of TARGETs in laboratory mice illustrated the usefulness of these nanoprobes for medical sensing and imaging. PMID:27064259

  19. The disorder-induced Raman scattering in Au/MoS2 heterostructures

    K. Gołasa

    2015-07-01

    Full Text Available The Raman scattering has been studied in heterostructures composed of a thin MoS2 flake and a 1-1.5 nm layer of thermally evaporated gold (Au. There have been Au nanoislands detected in the heterostructure. It has been found that their surface density and the average size depend on the MoS2 thickness. The Raman scattering spectrum in the heterostructure with a few monolayer MoS2 only weakly depends on the excitation (resonant vs. non-resonant mode. The overall Raman spectrum corresponds to the total density of phonon states, which is characteristic for disordered systems. The disorder in the MoS2 layer is related to the mechanical strain induced in the MoS2 layer by the Au nanoislands. The strain results in the localization of phonon modes, which leads to the relaxation of the momentum conservation rule in the scattering process. The relaxation allows phonons from the whole MoS2 Brillouin zone to interact with electronic excitations. Our results show that the Au nanoislands resulted from thermal evaporation of a thin metal layer introduce substantial disorder into the crystalline structure of the thin MoS2 layers.

  20. Improving resolution in quantum subnanometre-gap tip-enhanced Raman nanoimaging

    Zhang, Yingchao; Voronine, Dmitri V.; Qiu, Shangran; Sinyukov, Alexander M.; Hamilton, Mary; Liege, Zachary; Sokolov, Alexei V.; Zhang, Zhenrong; Scully, Marlan O.

    2016-05-01

    Two-dimensional (2D) materials beyond graphene such as transition metal dichalcogenides (TMDs) have unique mechanical, optical and electronic properties with promising applications in flexible devices, catalysis and sensing. Optical imaging of TMDs using photoluminescence and Raman spectroscopy can reveal the effects of structure, strain, doping, edge states, and surface functionalization from materials to bioscience. However, Raman signals are inherently weak and so far have been limited in spatial resolution in TMDs to a few hundred nanometres which is much larger than the intrinsic scale of these effects. Here we overcome the diffraction limit by using resonant tip-enhanced Raman scattering (TERS) of few-layer MoS2, and obtain nanoscale optical images with ~20 nm spatial resolution. This becomes possible due to electric field enhancement in an optimized subnanometre-gap resonant tip-substrate configuration. We investigate the limits of signal enhancement by varying the tip-sample gap with sub-Angstrom precision and observe a quantum quenching behavior, as well as a Schottky-Ohmic transition, for subnanometre gaps, which enable surface mapping based on this new contrast mechanism. This quantum regime of plasmonic gap-mode enhancement with a few nanometre thick MoS2 junction may be used for designing new quantum optoelectronic devices and sensors with a wide range of applications.

  1. Improving resolution in quantum subnanometre-gap tip-enhanced Raman nanoimaging.

    Zhang, Yingchao; Voronine, Dmitri V; Qiu, Shangran; Sinyukov, Alexander M; Hamilton, Mary; Liege, Zachary; Sokolov, Alexei V; Zhang, Zhenrong; Scully, Marlan O

    2016-01-01

    Two-dimensional (2D) materials beyond graphene such as transition metal dichalcogenides (TMDs) have unique mechanical, optical and electronic properties with promising applications in flexible devices, catalysis and sensing. Optical imaging of TMDs using photoluminescence and Raman spectroscopy can reveal the effects of structure, strain, doping, edge states, and surface functionalization from materials to bioscience. However, Raman signals are inherently weak and so far have been limited in spatial resolution in TMDs to a few hundred nanometres which is much larger than the intrinsic scale of these effects. Here we overcome the diffraction limit by using resonant tip-enhanced Raman scattering (TERS) of few-layer MoS2, and obtain nanoscale optical images with ~20 nm spatial resolution. This becomes possible due to electric field enhancement in an optimized subnanometre-gap resonant tip-substrate configuration. We investigate the limits of signal enhancement by varying the tip-sample gap with sub-Angstrom precision and observe a quantum quenching behavior, as well as a Schottky-Ohmic transition, for subnanometre gaps, which enable surface mapping based on this new contrast mechanism. This quantum regime of plasmonic gap-mode enhancement with a few nanometre thick MoS2 junction may be used for designing new quantum optoelectronic devices and sensors with a wide range of applications. PMID:27220882

  2. Raman spectroscopic investigation of the confined optical phonon modes in the aligned CdSe nanorod arrays

    Nobile, Concetta; Carbone, Luigi; Kudera, Stefan; Manna, Liberato; Cingolani, Roberto; Krahne, Roman; Fonoberov, Vladimir A.; Balandin, Alexander A.; Chilla, Gerwin; Kipp, Tobias; Heitmann, Detlef

    2007-03-01

    Nanocrystal rods have emerged as promising nanostructured material for both fundamental studies of nanoscale effects and for optical and electronic device applications. We investigated the optical phonon excitations in laterally aligned CdSe nanocrystal rod arrays using resonant Raman scattering. Electric-field mediated alignment between interdigitated electrodes has been used to prepare the samples. We report Raman experiments that probe the optical lattice vibrations in ordered arrays of CdSe nanorods with respect to the nanorod orientation. The packing of nanorods into dense arrays leads to the suppression of the surface optical phonon modes. In the longitudinal-optical phonon peak we observe a fine structure that depends on the relative orientation of the nanorods with respect to the incident light polarization. Detailed comparison of the experimental data with the first-principle calculations for corresponding nanostructures, which reveal the symmetry of the phonon potentials for the Raman active modes, provides a qualitative explanation of the experimentally observed phonon modes.

  3. Enhancement of Raman Scattering of 1,4-Benzenedithiol by CdS Nanoparticles Assembled on a Silver Surface

    ZHOU Qun; ZHAO Hong; LI Xiao-wei; ZHENG Jun-wei

    2004-01-01

    CdS nanoparticles were assembled on the smooth surface of a piece of silver by using 1,4-benzenedithiol as coupling molecules. The SEM and resonance Raman spectroscopic characterizations demonstrate that the nanosized structure of CdS was still preserved upon assembly, and a two-dimensional structure of CdS nanoparticles was formed on the substrate surface. The FT-Raman spectra indicate that 1,4-benzenedithiol was coupled between CdS nanoparticles and the silver surface with a tilted orientation. The Raman scattering of 1,4-benzenedithiol was substantially enhanced by the assembled CdS nanoparticles, probably due to the alteration of the polarizability of 1,4-benzenedithiol and the electromagnetic interaction between the dipoles of the CdS particle with its image in the metal substrate.

  4. Laser Raman Spectroscopy with Different Excitation Sources and Extension to Surface Enhanced Raman Spectroscopy

    Md. Wahadoszamen

    2015-01-01

    Full Text Available A dispersive Raman spectrometer was used with three different excitation sources (Argon-ion, He-Ne, and Diode lasers operating at 514.5 nm, 633 nm, and 782 nm, resp.. The system was employed to a variety of Raman active compounds. Many of the compounds exhibit very strong fluorescence while being excited with a laser emitting at UV-VIS region, hereby imposing severe limitation to the detection efficiency of the particular Raman system. The Raman system with variable excitation laser sources provided us with a desired flexibility toward the suppression of unwanted fluorescence signal. With this Raman system, we could detect and specify the different vibrational modes of various hazardous organic compounds and some typical dyes (both fluorescent and nonfluorescent. We then compared those results with the ones reported in literature and found the deviation within the range of ±2 cm−1, which indicates reasonable accuracy and usability of the Raman system. Then, the surface enhancement technique of Raman spectrum was employed to the present system. To this end, we used chemically prepared colloidal suspension of silver nanoparticles as substrate and Rhodamine 6G as probe. We could observe significant enhancement of Raman signal from Rhodamine 6G using the colloidal solution of silver nanoparticles the average magnitude of which is estimated to be 103.

  5. Multimodality Raman and photoacoustic imaging of surface-enhanced-Raman-scattering-targeted tumor cells

    Shi, Wei; Paproski, Robert J.; Shao, Peng; Forbrich, Alexander; Lewis, John D.; Zemp, Roger J.

    2016-02-01

    A multimodality Raman and photoacoustic imaging system is presented. This system has ultralow background and can detect tumor cells labeled with modified surface-enhanced-Raman-scattering (SERS) nanoparticles in vivo. Photoacoustic imaging provides microvascular context and can potentially be used to guide magnetic trapping of circulating tumor cells for SERS detection in animal models.

  6. Two-step pulse observation for Raman-Ramsey coherent population trapping atomic clocks

    Yano, Yuichiro; Kajita, Masatoshi

    2014-01-01

    We propose a two-step pulse observation method to enhance frequency stability for coherent population trapping (CPT) atomic clocks. The proposed method is a Raman-Ramsey scheme with low light intensity at resonance observation, and provides a Ramsey-CPT resonance with both reduced frequency sensitivity to the light intensity and a high signal-to-noise ratio by reducing the repumping into a steady dark state. The resonance characteristics were calculated based on density matrix analysis of a $\\Lambda$-type three level system that was modeled on the $^{133}$Cs-D$_1$ line, and the characteristics were also measured using a vertical-cavity surface-emitting laser and a Cs vapor cell.

  7. Raman parametric excitation effect upon the third harmonic generation by a metallic nanoparticle lattice

    This work is a theoretical study on third harmonic generation in the nonlinear propagation of an intense laser pulse through a periodic three-dimensional lattice of nanoparticles. Using a perturbative method, the nonlinear equations that describe the laser–nanoparticle interaction in the weakly relativistic regime are derived. Additionally, the nonlinear dispersion relation and the amplitude of the third harmonic are obtained. Finally, the effects of the nanoparticle radius and separation length, the distribution of the nanoparticle electron density, and the laser frequency upon the third harmonic efficiency are investigated. In addition to the expected resonance that occurs when the third harmonic resonates with the plasmon wave, another resonance appears when the nonlinear interaction of the fundamental mode with the third harmonic excites a longitudinal collective plasmon wave via the parametric Raman mechanism

  8. Raman amplification in plasma: thermal effects and damping

    Farmer, J. P.; Ersfeld, B.; Raj, G.; Jaroszynski, D. A.

    2009-05-01

    The role of thermal effects on Raman amplification are investigated. The direct effects of damping on the process are found to be limited, leading only to a decrease from the peak output intensity predicted by cold plasma models. However, the shift in plasma resonance due to the Bohm-Gross shift can have a much larger influence, changing the required detuning between pump and probe and introducing an effective chirp through heating of the plasma by the pump pulse. This "thermal chirp" can both reduce the efficiency of the interaction and alter the evolution of the amplified probe, avoiding the increase in length observed in the linear regime without significant pump depletion. The influence of this chirp can be reduced by using a smaller ratio of laser frequency to plasma frequency, which simultaneously increases the growth rate of the probe and decreases the shift in plasma resonance. As such, thermal effects only serve to suppress the amplification of noise at low growth rates. The use of a chirped pump pulse can be used to suppress noise for higher growth rates, and has a smaller impact on the peak output intensity for seeded amplification. For the parameter ranges considered, Landau damping was found to be negligible, as Landau damping rates are typically small, and the low collisionality of the plasma causes the process to saturate quickly.

  9. Simultaneous Spectral Temporal Adaptive Raman Spectrometer - SSTARS

    Blacksberg, Jordana

    2010-01-01

    Raman spectroscopy is a prime candidate for the next generation of planetary instruments, as it addresses the primary goal of mineralogical analysis, which is structure and composition. However, large fluorescence return from many mineral samples under visible light excitation can render Raman spectra unattainable. Using the described approach, Raman and fluorescence, which occur on different time scales, can be simultaneously obtained from mineral samples using a compact instrument in a planetary environment. This new approach is taken based on the use of time-resolved spectroscopy for removing the fluorescence background from Raman spectra in the laboratory. In the SSTARS instrument, a visible excitation source (a green, pulsed laser) is used to generate Raman and fluorescence signals in a mineral sample. A spectral notch filter eliminates the directly reflected beam. A grating then disperses the signal spectrally, and a streak camera provides temporal resolution. The output of the streak camera is imaged on the CCD (charge-coupled device), and the data are read out electronically. By adjusting the sweep speed of the streak camera, anywhere from picoseconds to milliseconds, it is possible to resolve Raman spectra from numerous fluorescence spectra in the same sample. The key features of SSTARS include a compact streak tube capable of picosecond time resolution for collection of simultaneous spectral and temporal information, adaptive streak tube electronics that can rapidly change from one sweep rate to another over ranges of picoseconds to milliseconds, enabling collection of both Raman and fluorescence signatures versus time and wavelength, and Synchroscan integration that allows for a compact, low-power laser without compromising ultimate sensitivity.

  10. Resonant Nucleation

    Gleiser, M; Gleiser, Marcelo; Howell, Rafael

    2004-01-01

    We investigate the role played by fast quenching on the decay of metastable (or false vacuum) states. Instead of the exponentially-slow decay rate per unit volume, $\\Gamma_{\\rm HN} \\sim \\exp[-E_b/k_BT]$ ($E_b$ is the free energy of the critical bubble), predicted by Homogeneous Nucleation theory, we show that under fast enough quenching the decay rate is, in fact, a power law $\\Gamma_{\\rm RN} \\sim [E_b/k_BT]^{-B}$, where $B$ is weakly sensitive to the temperature. We argue that the fast quench generates large-amplitude fluctuations about the metastable state which promote its rapid decay via parametric resonance. Possible decay mechanisms and their dependence on $E_b$ are proposed and illustrated in a (2+1)-dimensional scalar field model with an asymmetric double-well potential.

  11. Laser printing of resonant plasmonic nanovoids.

    Kuchmizhak, A; Vitrik, O; Kulchin, Yu; Storozhenko, D; Mayor, A; Mirochnik, A; Makarov, S; Milichko, V; Kudryashov, S; Zhakhovsky, V; Inogamov, N

    2016-06-16

    Hollow reduced-symmetry resonant plasmonic nanostructures possess pronounced tunable optical resonances in the UV-vis-IR range, being a promising platform for advanced nanophotonic devices. However, the present fabrication approaches require several consecutive technological steps to produce such nanostructures, making their large-scale fabrication rather time-consuming and expensive. Here, we report on direct single-step fabrication of large-scale arrays of hollow parabolic- and cone-shaped nanovoids in silver and gold thin films, using single-pulse femtosecond nanoablation at high repetition rates. The lateral and vertical size of such nanovoids was found to be laser energy-tunable. Resonant light scattering from individual nanovoids was observed in the visible spectral range, using dark-field confocal microspectroscopy, with the size-dependent resonant peak positions. These colored geometric resonances in far-field scattering were related to excitation and interference of transverse surface plasmon modes in nanovoid shells. Plasmon-mediated electromagnetic field enhancement near the nanovoids was evaluated via finite-difference time-domain calculations for their model shapes simulated by three-dimensional molecular dynamics, and experimentally verified by means of photoluminescence microscopy and Raman spectroscopy. PMID:27273005

  12. Applied neutron resonance theory

    Utilisation of resonance theory in basic and applications-oriented neutron cross section work is reviewed. The technically important resonance formalisms, principal concepts and methods as well as representative computer programs for resonance parameter extraction from measured data, evaluation of resonance data, calculation of Doppler-broadened cross sections and estimation of level-statistical quantities from resonance parameters are described. (orig.)

  13. Immunoassay utilizing biochemistry reaction product via surface-enhanced Raman scattering in near field

    ZHAO Haiying; NI Yi; JIANG Wei; LUO Peiqing; HUANG Meizheng; YIN Guangzhong; DOU Xiaoming

    2005-01-01

    We propose here a kind of applications of surface-enhanced Raman scattering (SERS) to immunology. It is a new enzyme immunoassay based on SERS. In the proposed system, antibody immobilized on a solid substrate reacts with antigen, which binds with another antibody labeled with peroxidase. If this immunocomplex is subjected to reaction with o-phenylenediamine and hydrogenperoxide, azoaniline is generated. This azo compound is adsorbed on a silver colloid and only the azo compound gives a strong surface-enhanced resonance Raman (SERRS) spectrum. A linear relationship was observed between the peak intensity of the N=N stretching band and the concentration of antigen, revealing that one can determine the concentration of antigen by the SERRS measurement of the reaction product. The detection limit of this SERS enzyme immunoassay method was found to be about 10-15 mol/L.

  14. A filter based analyzer for studies of X-ray Raman scattering

    Seidler, G T

    2001-01-01

    Non-resonant X-ray Raman scattering (XRS) with hard X-rays holds the potential for measuring local structure and local electronic properties around low-Z atoms in environments where traditional soft X-ray techniques are inapplicable. However, the small cross-section for XRS requires that experiments must simultaneously achieve high detection efficiency, large collection solid angles, and good energy resolution. We report here that a simple X-ray analyzer consisting of an absorber and a point-focusing spatial filter can be used to study some X-ray Raman near-edge features. This apparatus has greater than 10% detection efficiency, has an energy resolution of 8 eV, and can be readily extended to collection angles of more than 1 sr. We present preliminary measurements of the XRS from the nitrogen 1 s shell in pyrolitic boron nitride.

  15. Raman Barcode for Counterfeit Drug Product Detection.

    Lawson, Latevi S; Rodriguez, Jason D

    2016-05-01

    Potential infiltration of counterfeit drug products-containing the wrong or no active pharmaceutical ingredient (API)-into the bona fide drug supply poses a significant threat to consumers worldwide. Raman spectroscopy offers a rapid, nondestructive avenue to screen a high throughput of samples. Traditional qualitative Raman identification is typically done with spectral correlation methods that compare the spectrum of a reference sample to an unknown. This is often effective for pure materials but is quite challenging when dealing with drug products that contain different formulations of active and inactive ingredients. Typically, reliable identification of drug products using common spectral correlation algorithms can only be made if the specific product under study is present in the library of reference spectra, thereby limiting the scope of products that can be screened. In this paper, we introduce the concept of the Raman barcode for identification of drug products by comparing the known peaks in the API reference spectrum to the peaks present in the finished drug product under study. This method requires the transformation of the Raman spectra of both API and finished drug products into a barcode representation by assigning zero intensity to every spectral frequency except the frequencies that correspond to Raman peaks. By comparing the percentage of nonzero overlap between the expected API barcode and finished drug product barcode, the identity of API present can be confirmed. In this study, 18 approved finished drug products and nine simulated counterfeits were successfully identified with 100% accuracy utilizing this method. PMID:27043140

  16. Raman-based microarray readout: a review.

    Haisch, Christoph

    2016-07-01

    For a quarter of a century, microarrays have been part of the routine analytical toolbox. Label-based fluorescence detection is still the commonest optical readout strategy. Since the 1990s, a continuously increasing number of label-based as well as label-free experiments on Raman-based microarray readout concepts have been reported. This review summarizes the possible concepts and methods and their advantages and challenges. A common label-based strategy is based on the binding of selective receptors as well as Raman reporter molecules to plasmonic nanoparticles in a sandwich immunoassay, which results in surface-enhanced Raman scattering signals of the reporter molecule. Alternatively, capture of the analytes can be performed by receptors on a microarray surface. Addition of plasmonic nanoparticles again leads to a surface-enhanced Raman scattering signal, not of a label but directly of the analyte. This approach is mostly proposed for bacteria and cell detection. However, although many promising readout strategies have been discussed in numerous publications, rarely have any of them made the step from proof of concept to a practical application, let alone routine use. Graphical Abstract Possible realization of a SERS (Surface-Enhanced Raman Scattering) system for microarray readout. PMID:26973235

  17. Confocal Raman imaging for cancer cell classification

    Mathieu, Evelien; Van Dorpe, Pol; Stakenborg, Tim; Liu, Chengxun; Lagae, Liesbet

    2014-05-01

    We propose confocal Raman imaging as a label-free single cell characterization method that can be used as an alternative for conventional cell identification techniques that typically require labels, long incubation times and complex sample preparation. In this study it is investigated whether cancer and blood cells can be distinguished based on their Raman spectra. 2D Raman scans are recorded of 114 single cells, i.e. 60 breast (MCF-7), 5 cervix (HeLa) and 39 prostate (LNCaP) cancer cells and 10 monocytes (from healthy donors). For each cell an average spectrum is calculated and principal component analysis is performed on all average cell spectra. The main features of these principal components indicate that the information for cell identification based on Raman spectra mainly comes from the fatty acid composition in the cell. Based on the second and third principal component, blood cells could be distinguished from cancer cells; and prostate cancer cells could be distinguished from breast and cervix cancer cells. However, it was not possible to distinguish breast and cervix cancer cells. The results obtained in this study, demonstrate the potential of confocal Raman imaging for cell type classification and identification purposes.

  18. Raman microspectroscopic study of oral buccal mucosa

    Behl, Isha; Mamgain, Hitesh; Deshmukh, Atul; Kukreja, Lekha; Hole, Arti R.; Krishna, C. Murali

    2014-03-01

    Oral cancer is the most common cancer among Indian males, with 5-year- survival-rates of less than 50%. Efficacy of Raman spectroscopic methods in non-invasive and objective diagnosis of oral cancers and confounding factors has already been demonstrated. The present Raman microspectroscopic study was undertaken for in-depth and site-specific analysis of normal and tumor tissues. 10 normal and 10 tumors unstained sections from 20 tissues were accrued. Raman data of 160 x 60 μm and 140 x 140 μm in normal and tumor sections, respectively, were acquired using WITec alpha 300R equipped with 532 nm laser, 50X objective and 600 gr/mm grating. Spectral data were corrected for CCDresponse, background. First-derivitized and vector-normalized data were then subjected to K-mean cluster analysis to generate Raman maps and correlated with their respective histopathology. In normal sections, stratification among epithelial layers i.e. basal, intermediate, superficial was observed. Tumor, stromal and inflammatory regions were identified in case of tumor section. Extracted spectra of the pathologically annotated regions were subjected to Principal component analysis. Findings suggest that all three layers of normal epithelium can be differentiated against tumor cells. In epithelium, basal and superficial layers can be separated while intermediate layer show misclassifications. In tumors, discrimination of inflammatory regions from tumor cells and tumor-stroma regions were observed. Finding of the study indicate Raman mapping can lead to molecular level insights of normal and pathological states.

  19. Raman spectroscopy of Alzheimer's diseased tissue

    Sudworth, Caroline D.; Krasner, Neville

    2004-07-01

    Alzheimer's disease is one of the most common forms of dementia, and causes steady memory loss and mental regression. It is also accompanied by severe atrophy of the brain. However, the pathological biomarkers of the disease can only be confirmed and examined upon the death of the patient. A commercial (Renishaw PLC, UK) Raman system with an 830 nm NIR diode laser was used to analyse brain samples, which were flash frozen at post-mortem. Ethical approval was sought for these samples. The Alzheimer's diseased samples contained a number of biomarkers, including neuritic plaques and tangles. The Raman spectra were examined by order to differentiate between normal and Alzheimer's diseased brain tissues. Preliminary results indicate that Alzheimer's diseased tissues can be differentiated from control tissues using Raman spectroscopy. The Raman spectra differ in terms of peak intensity, and the presence of a stronger amide I band in the 1667 cm-1 region which occurs more prominently in the Alzheimer's diseased tissue. These preliminary results indicate that the beta-amyloid protein originating from neuritic plaques can be identified with Raman spectroscopy.

  20. Vibrational dynamics (IR, Raman, NRVS) and a DFT study of a new antitumor tetranuclearstannoxane cluster, Sn(iv)-oxo-{di-o-vanillin} dimethyl dichloride.

    Arjmand, F; Sharma, S; Usman, M; Leu, B M; Hu, M Y; Toupet, L; Gosztola, D; Tabassum, S

    2016-07-21

    The vibrational dynamics of a newly synthesized tetrastannoxane was characterized with a combination of experimental (Raman, IR and tin-based nuclear resonance vibrational spectroscopy) and computational (DFT/B3LYP) methods, with an emphasis on the vibrations of the tin sites. The cytotoxic activity revealed a significant regression selectively against the human pancreatic cell lines. PMID:27328161

  1. Submicron Raman and photoluminescence topography of InAs/Al(Ga)As quantum dots structures

    Kolomys, O.F., E-mail: olkolomys@gmail.com [V. Lashkaryov Institute of Semiconductor Physics National Academy of Sciences of Ukraine, 45 Nauky pr., 03028 Kyiv (Ukraine); Strelchuk, V.V. [V. Lashkaryov Institute of Semiconductor Physics National Academy of Sciences of Ukraine, 45 Nauky pr., 03028 Kyiv (Ukraine); Shamirzaev, T.S. [A.V. Rzhanov Institute of Semiconductor Physics, Siberian Branch of the Russian Academy of Sciences, RU-630090 Novosibirsk (Russian Federation); Romanyuk, A.S. [V. Lashkaryov Institute of Semiconductor Physics National Academy of Sciences of Ukraine, 45 Nauky pr., 03028 Kyiv (Ukraine); Tronc, P. [Centre National de la Recherche Scientifique, Ecole Superieure de Physique et de Chimie Industrielles de la Villede Paris, 10 rue Vauquelin, 75005 Paris (France)

    2012-11-01

    Highlights: Black-Right-Pointing-Pointer Exciton recombination in an ensemble of indirect/direct band-gap (In,Al)As/AlAs QDs with type-I band alignment is studied. Black-Right-Pointing-Pointer Resonant Raman scattering was applied for evaluation of composition at various depths InAlAs/AlAs QDs sandwich structures. Black-Right-Pointing-Pointer Depth distribution of composition in In(Ga,Al)As alloy layers explained by strain-driven enhanced interdiffusion. - Abstract: Two-period structures with and without vertical coupling between indirect and direct bandgap InAs quantum dots (QDs) both with type I band alignment, grown by molecular-beam epitaxy, were investigated by confocal Raman and photoluminescence (PL) microspectroscopy. The observed blue shift of PL band of the indirect (direct) bandgap QD by 20 (80) meV with decrease of thickness of Ga(Al)As intermediate layer between two InAs QD layers from 30 to 8 nm is considered as caused by increase of elastic strains (decrease of QDs sizes) in QD layers and by coupling between QDs electronic states. Scanning confocal resonant Raman microspectroscopy was applied for non-destructive evaluation of composition at various depths along the thickness of vertical coupling of the upper InAs/AlGaAs and lower InAs/AlAs QDs layers of the sandwich structures. Based on the analysis of determined from the in-depth Raman spectra optical phonons frequencies, the depth distribution of composition in InAlAs and GaAlAs alloy layers formed as a result of strain-driven enhanced interdiffusion was determined.

  2. Submicron Raman and photoluminescence topography of InAs/Al(Ga)As quantum dots structures

    Highlights: ► Exciton recombination in an ensemble of indirect/direct band-gap (In,Al)As/AlAs QDs with type-I band alignment is studied. ► Resonant Raman scattering was applied for evaluation of composition at various depths InAlAs/AlAs QDs sandwich structures. ► Depth distribution of composition in In(Ga,Al)As alloy layers explained by strain-driven enhanced interdiffusion. - Abstract: Two-period structures with and without vertical coupling between indirect and direct bandgap InAs quantum dots (QDs) both with type I band alignment, grown by molecular-beam epitaxy, were investigated by confocal Raman and photoluminescence (PL) microspectroscopy. The observed blue shift of PL band of the indirect (direct) bandgap QD by 20 (80) meV with decrease of thickness of Ga(Al)As intermediate layer between two InAs QD layers from 30 to 8 nm is considered as caused by increase of elastic strains (decrease of QDs sizes) in QD layers and by coupling between QDs electronic states. Scanning confocal resonant Raman microspectroscopy was applied for non-destructive evaluation of composition at various depths along the thickness of vertical coupling of the upper InAs/AlGaAs and lower InAs/AlAs QDs layers of the sandwich structures. Based on the analysis of determined from the in-depth Raman spectra optical phonons frequencies, the depth distribution of composition in InAlAs and GaAlAs alloy layers formed as a result of strain-driven enhanced interdiffusion was determined.

  3. MRI (Magnetic Resonance Imaging)

    ... Procedures Medical Imaging MRI (Magnetic Resonance Imaging) MRI (Magnetic Resonance Imaging) Share Tweet Linkedin Pin it More sharing options ... 8 MB) Also available in Other Language versions . Magnetic Resonance Imaging (MRI) is a medical imaging procedure for making ...

  4. Human cardiac troponin I sensor based on silver nanoparticle doped microsphere resonator

    Human cardiac troponin I (cTnI) is a specific biomarker for diagnosis of acute myocardial infarction (AMI). In this paper, a composite sensing system of an optical microsphere resonator and silver nanoparticles based on surface enhanced Raman scattering (SERS) and stimulated Raman scattering (SRS) techniques towards a point of care diagnostic system for AMI using the cTnI biomarker in HEPES buffered solution (HBS) is proposed. Pump and Raman signals enter the optical fiber coupling into the microsphere, and then SRS occurs in the microsphere. The presence of silver nanoparticles on the microsphere surface provides a tremendous enhancement of the resulting Raman signal through an electromagnetic enhancement of both the laser excitation and Stokes-shifted light of the order of 1010. This enhancement occurs in metals as surface plasmon resonance (SPR), which increases the Raman gain through the SERS effect. Our simulation results show that this sensor presents a linear response for cTnI detection. The calculated enhanced Raman signal can be employed to detect the cTnI molecules around the microsphere. (fast track communication)

  5. Sub-micrometer-scale mapping of magnetite crystals and sulfur globules in magnetotactic bacteria using confocal Raman micro-spectrometry.

    Eder, Stephan H K; Gigler, Alexander M; Hanzlik, Marianne; Winklhofer, Michael

    2014-01-01

    The ferrimagnetic mineral magnetite Fe3O4 is biomineralized by magnetotactic microorganisms and a diverse range of animals. Here we demonstrate that confocal Raman microscopy can be used to visualize chains of magnetite crystals in magnetotactic bacteria, even though magnetite is a poor Raman scatterer and in bacteria occurs in typical grain sizes of only 35-120 nm, well below the diffraction-limited optical resolution. When using long integration times together with low laser power (greigite (cubic Fe3S4; Raman lines of 253 and 351 cm(-1)) is often found in the Deltaproteobacteria class, it is not present in our samples. In intracellular sulfur globules of Candidatus Magnetobacterium bavaricum (Nitrospirae), we identified the sole presence of cyclo-octasulfur (S8: 151, 219, 467 cm(-1)), using green (532 nm), red (638 nm) and near-infrared excitation (785 nm). The Raman-spectra of phosphorous-rich intracellular accumulations point to orthophosphate in magnetic vibrios and to polyphosphate in magnetic cocci. Under green excitation, the cell envelopes are dominated by the resonant Raman lines of the heme cofactor of the b or c-type cytochrome, which can be used as a strong marker for label-free live-cell imaging of bacterial cytoplasmic membranes, as well as an indicator for the redox state. PMID:25233081

  6. Study of boron carbide evolution under neutron irradiation by Raman spectroscopy

    Boron carbide, B12C3, is an absorbing material used to control the reactivity of nuclear reactors by taking advantage of nuclear reactions (e.g. 10B(n,α)7Li), where neutrons are absorbed. During such reactions, radiation damages originating both from these nuclear reactions and from elastic collisions between neutrons and atoms lead to a partial destruction of this material, which gives the main limitation of its lifetime in nuclear reactors. In order to understand the evolution of B12C3 in nuclear plants, the effect of neutron irradiation in B12C3 has been investigated by Raman and nuclear magnetic resonance (NMR) spectroscopies. Comparisons of B12C3 samples irradiated by 1 MeV electrons, 180 keV helium ions and neutrons are used to study the microstructure evolution of this material by Raman scattering. The analysis of Raman spectra of different B12C3 samples irradiated by neutrons clearly shows that during the cascade displacements, the 485 and 527 cm-1 modes disappear. These characteristic features of Raman spectra of the neutron irradiated samples are interpreted by a microscopic model. This model assumes that the CBC linear chain is destroyed whereas icosahedra are self-healed. 10B atoms destroyed during the neutron irradiation are replaced in icosahedra by other boron and carbon atoms coming from the linear CBC chain. The 11B NMR analysis performed on unirradiated and irradiated B4C samples shows the vanishing of a strong quadrupolar interaction associated to the CBC chain during the high neutron irradiation. The 11B NMR spectroscopy confirms the previous Raman spectroscopy and the proposed microscopic model of B12C3 evolution under neutron irradiation

  7. Gold nanorods combine photoacoustic and Raman imaging for detection and treatment of ovarian cancer

    Jokerst, Jesse V.; Cole, Adam J.; Bohndiek, Sarah E.; Gambhir, Sanjiv S.

    2014-03-01

    Gold nanorods (GNRs) were synthesized with surfactant templating and coated with IR792 to produce surface-enhanced Raman signal (SERS). Subcutaneous and orthotopic tumor models were created in nude mice using the OV2008 cell line, and a Nexus128 scanner from Endra LifeSciences was used to collect the photoacoustic data. We used GNRs with resonance at 756 nm, and the Raman signal was 10-fold larger than 60 nm gold core/silica shell nanoparticles. This signal was stable for over 24 hours in 50% serum. The batch-to-batch reproducibility was 15.5% and 3.6% in the SERS and photoacoustic modalities for n=4 batches. Animals were injected with 200 μL of 2.5, 5.4, and 16.8 nM GNRs. Relative to baseline photoacoustic signal, these concentrations increased tumor signal 1.3-, 1.6-, and 2.5-fold, respectively. The maximum signal increase occurred within 2 hours of injection persisted for at least 24 hours and was significant at panimals. Assaying for gold in the tumors validated signal—we found a strong correlation (R2>0.90) between tumor gold concentration and photoacoustic signal. By 24 hours, free GNRs had been sequestered to the liver and spleen with 2%ID/g immobilized in the tumor. The same GNRs produced SERS signal, and Raman maps were created with least squares analysis. We used the Raman signal to identify tumor margins and also to monitor resection and ensure complete removal of tumor tissue. Thus, the GNRs allow pre-surgical photoacoustic visualization for tumor staging and intra-operative Raman imaging to guide resection. Future work will study GNRs targeted to cell surface proteins to increase tumor accumulation.

  8. Drug Stability Analysis by Raman Spectroscopy

    Chetan Shende

    2014-12-01

    Full Text Available Pharmaceutical drugs are available to astronauts to help them overcome the deleterious effects of weightlessness, sickness and injuries. Unfortunately, recent studies have shown that some of the drugs currently used may degrade more rapidly in space, losing their potency before their expiration dates. To complicate matters, the degradation products of some drugs can be toxic. Here, we present a preliminary investigation of the ability of Raman spectroscopy to quantify mixtures of four drugs; acetaminophen, azithromycin, epinephrine, and lidocaine, with their primary degradation products. The Raman spectra for the mixtures were replicated by adding the pure spectra of the drug and its degradant to determine the relative percent contributions using classical least squares. This multivariate approach allowed determining concentrations in ~10 min with a limit of detection of ~4% of the degradant. These results suggest that a Raman analyzer could be used to assess drug potency, nondestructively, at the time of use to ensure crewmember safety.

  9. Drug stability analysis by Raman spectroscopy.

    Shende, Chetan; Smith, Wayne; Brouillette, Carl; Farquharson, Stuart

    2014-01-01

    Pharmaceutical drugs are available to astronauts to help them overcome the deleterious effects of weightlessness, sickness and injuries. Unfortunately, recent studies have shown that some of the drugs currently used may degrade more rapidly in space, losing their potency before their expiration dates. To complicate matters, the degradation products of some drugs can be toxic. Here, we present a preliminary investigation of the ability of Raman spectroscopy to quantify mixtures of four drugs; acetaminophen, azithromycin, epinephrine, and lidocaine, with their primary degradation products. The Raman spectra for the mixtures were replicated by adding the pure spectra of the drug and its degradant to determine the relative percent contributions using classical least squares. This multivariate approach allowed determining concentrations in ~10 min with a limit of detection of ~4% of the degradant. These results suggest that a Raman analyzer could be used to assess drug potency, nondestructively, at the time of use to ensure crewmember safety. PMID:25533308

  10. Differentiation of lipsticks by Raman spectroscopy.

    Salahioglu, Fatma; Went, Michael J

    2012-11-30

    Dispersive Raman spectra have been obtained using a Raman microscope and an excitation wavelength of 632.8 nm from 69 lipsticks of various colours and from a range of manufacturers without any pre-treatment of the samples. 10% of the samples were too fluorescent to give Raman spectra. 22% of the samples gave spectra which were unique to the brand and colour within the collected sample set. The remaining 68% of the samples gave spectra which could be classified into seven distinct groups. Discrimination of red lipsticks by this technique was the most difficult. The spectra of deposited lipstick samples remained unchanged over a period of a least a year. PMID:22959771

  11. Resonances, resonance functions and spectral deformations

    The present paper is aimed at an analysis of resonances and resonance states from a mathematical point of view. Resonances are characterized as singular points of the analytically continued Lippman-Schwinger equation, as complex eigenvalues of the Hamiltonian with a purely outgoing, exponentially growing eigenfunction, and as poles of the S-matrix. (orig./HSI)

  12. Magnetic resonance angiography

    MRA; Angiography - magnetic resonance ... Kwong RY. Cardiovascular Magnetic Resonance Imaging. In: Bonow RO, Mann DL, Zipes DP, Libby P, eds. Braunwald's Heart Disease: A Textbook of Cardiovascular Medicine . ...

  13. Raman spectroscopy of C-irradiated graphite

    Highly oriented pyrolytic graphite samples were irradiated with C+ ions at 35 keV in a direction normal to the basal plane and subsequently annealed up to 1,373 K. Substantial surface topography changes were observed at fluences of 5 x 1018 ions/m2 and higher using scanning electron and atomic force microscopies. Intricate networks of surface cracks and ridges developed after high dose implantation. A systematic study of the irradiation effects was conducted using Raman spectroscopy. Microstructural changes in irradiated regions were first detected at a dose of 1 x 1017 ions/n2 through the appearance of the Raman D-line at ∼ 1,360 cm-1. The intensity of this line increases while that of the Raman G-line at 1,580 cm-1 decreases as the irradiation dose is increased or the irradiation temperature is decreased. After irradiation at 280K to a fluence of 5 x 1019 ions/m2 or higher the first order spectrum exhibits one single line at a wavelength intermediate between the D and G-lines. Damage recovery upon thermal annealing depends not only on the initial damage state but also on the annealing temperature sequence. Samples irradiated to a damage level where two distinct Raman peaks are no longer resolvable exhibited upon direct annealing at a high temperature two distinct Raman lines. By contrast, pre-annealing these highly irradiated specimens at lower temperatures produced less pronounced changes in the Raman spectra. Pre-annealing appears to stabilize damage structures that are more resistant to high-temperature annealing than those induced by irradiation

  14. Effects of corner radius on periodic nanoantenna for surface-enhanced Raman spectroscopy

    Chao, Bo-Kai; Lin, Shih-Che; Nien, Li-Wei; Li, Jia-Han; Hsueh, Chun-Hway

    2015-12-01

    Corner radius is a concept to approximate the fabrication limitation due to the effective beam broadening at the corner in using electron-beam lithography. The purpose of the present study is to investigate the effects of corner radius on the electromagnetic field enhancement and resonance wavelength for three periodic polygon dimers of bowtie, twin square, and twin pentagon. The enhancement factor of surface-enhanced Raman spectroscopy due to the localized surface plasmon resonances in fabricated gold bowtie nanostructures was investigated using both Raman spectroscopy and finite-difference time-domain simulations. The simulated enhancement factor versus corner radius relation was in agreement with measurements and it could be fitted by a power-law relation. In addition, the resonance wavelength showed blue shift with the increasing corner radius because of the distribution of concentrated charges in a larger area. For different polygons, the corner radius instead of the tip angle is the dominant factor of the electromagnetic field enhancement because the surface charges tend to localize at the corner. Greater enhancements can be obtained by having both the smaller gap and sharper corner although the corner radius effect on intensity enhancement is less than the gap size effect.

  15. FT-IR and UV Raman spectroscopic studies on thermal modification of Scots pine wood and its extractable compounds

    Nuopponen, Mari

    2005-01-01

    The aim of this study was to examine, in some detail, the thermally induced changes in Scots pine (Pinus sylvestris) wood with Fourier transform infrared (FT-IR) and UV resonance Raman (UVRR) spectroscopies. These techniques were also utilised to identify lipophilic and hydrophilic extracts from heat-treated and native wood samples. Furthermore, the molecular structures of the extractable compounds characteristic for Scots pine wood were comprehensively studied with UVRR spectroscopy. Spe...

  16. Ultra low-threshold monolithic micro-Raman laser

    Spillane, S. M.; Armani, D. K.; Vahala, K. J.

    2003-01-01

    We demonstrate a Raman laser integrated onto a silicon microchip, using an ultra-high-Q toroidal microcavity. Low pump power thresholds (210 microwatts) and Raman output powers of 1.2 milliWatts were obtained at 1650 nm.

  17. Coherent Raman studies of optical nonlinearities in conjugated molecules and polymers

    Nonlinear optics are increasingly being exploited in optoelectronic and photonic applications. Third-order nonlinear optical processes are particularly interesting, opening the possibility of all-optical switching due the intensity-dependent refractive index. The main materials considered for these applications have been molecular conjugated materials where the π-electron delocalization is believed to give rise to a high response. In order to maximise the efficiency of third-order nonlinear optical devices using these materials an improved understanding of the microscopic origin of the nonlinearity is necessary. A knowledge of the structure-property relationship would allow synthesis to be used to tune the properties of the molecular materials. This thesis contains a study of the third-order nonlinear optical properties of several conjugated molecules and polymers. The molecular contribution has been isolated by studying dilute solutions. However the macroscopic nature of third-order measurements make concentration studies necessary in order to isolate the response due to the solute. The magnitude of a nonlinear signal is determined by the electronic and two-photon allowed resonances of the medium, as well as the intrinsic response. To compare quantitatively several chemical systems, it is necessary to quantify and separate out the effect of these contributions. The third-order technique that has been used here is frequency domain coherent Raman spectroscopy, specifically Coherent Anti-Stokes Raman Spectroscopy (CARS). The Raman resonant signal is sensitive to the electronic resonances within the medium, manifested by a change in the intensity and lineshape of the coherent Raman signal. The results presented in this thesis probe the intrinsic response of the conjugated materials by separating the resonant and intrinsic terms from the coherent Raman lineshapes. The initial material was the conjugated 11 double bond molecule trans-β-carotene studied using CARS at

  18. Implementation of Deep Ultraviolet Raman Spectroscopy

    Liu, Chuan; Berg, Rolf W.

    2011-01-01

    Denne afhandling, "Implementation of Deep Ultraviolet Raman spectroscopy”, består i hovedsagen af to dele. Deep Ultraviolet – også kaldt DUV – står for bølgelængdeområdet 200 til 300 nm. Første del, kapitlerne 1 til 4, handler om den instrumentelle teknologi i DUV Raman-systemet. Anden del, kapitlerne 5 og 6 fokuserer på nogle få anvendelser af DUV Ramanspektroskopien. Kapitel 1 giver en kort introduktion til Ramanspektroskopi i almindelighed og DUVs relation hertil. DUV Ramanspektrometrien h...

  19. Raman Fingerprints of Atomically Precise Graphene Nanoribbons

    Verzhbitskiy, Ivan A.; Corato, Marzio De; Ruini, Alice; Molinari, Elisa; Narita, Akimitsu; Hu, Yunbin; Schwab, Matthias G.; Bruna, Matteo; Yoon, Duhee; Milana, Silvia; Feng, Xinliang; Müllen, Klaus; Ferrari, Andrea C.; Casiraghi, Cinzia; Prezzi, Deborah

    2016-06-01

    Bottom-up approaches allow the production of ultra-narrow and atomically precise graphene nanoribbons (GNRs), with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab-initio simulations, we show that GNR width, edge geometry and functional groups all influence their Raman spectra. The low-energy spectral region below 1000 cm-1 is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs, and differentiates them from other sp2 carbon nanostructures.

  20. Raman Amplifier Based on Amorphous Silicon Nanoparticles

    M.A. Ferrara; Rendina, I.; S. N. Basu; Dal Negro, L.; Sirleto, L.

    2012-01-01

    The observation of stimulated Raman scattering in amorphous silicon nanoparticles embedded in Si-rich nitride/silicon superlattice structures (SRN/Si-SLs) is reported. Using a 1427 nm continuous-wavelength pump laser, an amplification of Stokes signal up to 0.9 dB/cm at 1540.6 nm and a significant reduction in threshold power of about 40% with respect to silicon are experimentally demonstrated. Our results indicate that amorphous silicon nanoparticles are a great promise for Si-based Raman la...

  1. Raman Fingerprints of Atomically Precise Graphene Nanoribbons

    2016-01-01

    Bottom-up approaches allow the production of ultranarrow and atomically precise graphene nanoribbons (GNRs) with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab initio simulations, we show that GNR width, edge geometry, and functional groups all influence their Raman spectra. The low-energy spectral region below 1000 cm–1 is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs and differentiates them from other sp2 carbon nanostructures. PMID:26907096

  2. Raman investigations of rare earth orthovanadates

    Santos, C. C.; Silva, E. N.; Ayala, A. P.; Guedes, I.; Pizani, P. S.; Loong, C.-K.; Boatner, L. A.

    2007-03-01

    Polarized Raman spectroscopy has been used to obtain the room-temperature phonon spectra of the series of rare earth orthovanadate single crystals: SmVO4, HoVO4, YbVO4, and LuVO4. The observed Raman frequencies follow the overall mode distribution expected for REVO4 compounds with the tetragonal zircon structure. The variation of the mode frequency with atomic number across the lanthanide orthovanadate series was investigated, and the trend exhibited by the internal modes was explained by considering the force constants of VO4 tetrahedron.

  3. Raman Investigations of Rare-Earth Orthovanadates

    Santos, C. C. [Universidade Federal do Ceara, Ceara, Brazil; Silva, E. N. [Universidade Federal do Ceara, Ceara, Brazil; Ayala, A. P. [Universidade Federal do Ceara, Ceara, Brazil; Guedes, I. [Universidade Federal do Ceara, Ceara, Brazil; Pizani, P. S. [Universidade Federal de Sao Carlos, Caixa Postal, Brazil; Loong, C. K. [Argonne National Laboratory (ANL); Boatner, Lynn A [ORNL

    2007-01-01

    Polarized Raman spectroscopy has been used to obtain the room-temperature phonon spectra of the series of rare earth orthovanadate single crystals: SmVO4, HoVO4, YbVO4 and LuVO4. The observed Raman frequencies follow the overall mode distribution expected for RVO4 compounds with the tetragonal zircon structure. The variation of the mode frequency with atomic number across the lanthanide orthovanadate series was investigated, and the trend exhibited by the internal modes was explained by considering the force constants of VO4 tetrahedron.

  4. Raman study of CuO single crystals

    Goldstein, H.F.; Kim, D.; Yu, P.Y.; Bourne, L.C. (Department of Physics, University of California, Berkeley, California 94720 (USA)); Chaminade, J.; Nganga, L. (Laboratoire de Chimie du Solide du Centre National de la Recherche Scientifique, 33405 Talence CEDEX, France (FR))

    1990-04-01

    Raman scattering in single-crystalline CuO samples has been studied. From the polarization dependence, the symmetries of the three Raman-active optical phonons have been identified. The {ital A}{sub {ital g}} Raman mode with frequency of 290 cm{sup {minus}1} was found to be strongly polarized along one of the crystal axes. This suggests that there are cancellations between different components of its Raman tensor.

  5. Quantitative Chemical Imaging with Multiplex Stimulated Raman Scattering Microscopy

    Fu, Dan; Lu, Fake; Zhang, Xu; Freudiger, Christian Wilhelm; Pernik, Douglas R.; Holtom, Gary; Xie, Xiaoliang Sunney

    2012-01-01

    Stimulated Raman scattering (SRS) microscopy is a newly developed label-free chemical imaging technique that overcomes the speed limitation of confocal Raman microscopy while avoiding the nonresonant background problem of coherent anti-Stokes Raman scattering (CARS) microscopy. Previous demonstrations have been limited to single Raman band measurements. We present a novel modulation multiplexing approach that allows real-time detection of multiple species using the fast Fourier transform. ...

  6. Suppression of two-photon resonantly enhanced nonlinear processes in extended media

    On the basis of combined experimental and theoretical studies of nonlinear processes associated with two-photon excitations near 3d and 4d states in Na, we show how resonantly enhanced stimulated hyper-Raman emission, parametric four-wave mixing processes and total resonant two-photon absorption can become severely suppressed through the actions of internally generated fields on the total atomic response in extended media. 7 refs., 3 figs

  7. The Impact of Array Detectors on Raman Spectroscopy

    Denson, Stephen C.; Pommier, Carolyn J. S.; Denton, M. Bonner

    2007-01-01

    The impact of array detectors in the field of Raman spectroscopy and all low-light-level spectroscopic techniques is examined. The high sensitivity of array detectors has allowed Raman spectroscopy to be used to detect compounds at part per million concentrations and to perform Raman analyses at advantageous wavelengths.

  8. Scaling the Raman gain coefficient: Applications to Germanosilicate fibers

    Rottwitt, Karsten; Bromage, J.; Stentz, A.J.;

    2003-01-01

    This paper presents a comprehensive analysis of the temperature dependence of a Raman amplifier and the scaling of the Raman gain coefficient with wavelength, modal overlap, and material composition. The temperature dependence is derived by applying a quantum theoretical description, whereas the...... scaling of the Raman gain coefficient is derived using a classical electromagnetic model. We also present experimental verification of our theoretical findings....

  9. Raman spectroscopy as a tool for investigating lipid protein interactions

    Petersen, Frederic Nicolas Rønne; Helix Nielsen, Claus

    2009-01-01

    Raman spectroscopy is a very well-established technique for noninvasive probing of chemical compounds. The fad that Raman scattering is an inherently weak effect has prompted many new developments in sample signal enhancement and techniques (such as surface-enhancement Raman spectroscopy [SERS]) ...

  10. Raman scattering enhanced by plasmonic clusters and its application to single-molecule imaging

    The optical response of the linear Au8 cluster is investigated by the linear response theory based on the density functional theory. It is revealed that the observed many peaks in the visible region originate from the interaction of the ideal plasmonic excitation along the molecular axis with the background d-electron excitations, i.e., the Landau damping. In spite of the existence of the damping, the Raman scattering is shown to be enhanced remarkably by the incident light resonant to the visible excitations. The novel imaging experiment with the atomic resolution is proposed by utilizing a plasmonic cluster as the probing tip

  11. Optimizing coherent anti-Stokes Raman scattering by genetic algorithm controlled pulse shaping

    Yang, Wenlong; Sokolov, Alexei

    2010-10-01

    The hybrid coherent anti-Stokes Raman scattering (CARS) has been successful applied to fast chemical sensitive detections. As the development of femto-second pulse shaping techniques, it is of great interest to find the optimum pulse shapes for CARS. The optimum pulse shapes should minimize the non-resonant four wave mixing (NRFWM) background and maximize the CARS signal. A genetic algorithm (GA) is developed to make a heuristic searching for optimized pulse shapes, which give the best signal the background ratio. The GA is shown to be able to rediscover the hybrid CARS scheme and find optimized pulse shapes for customized applications by itself.

  12. Raman Spectra of Interchanging β lactamase Inhibitor Intermediates on the Millisecond Time Scale

    Torkabadi, Hossein Heidari; Che, Tao; Shou, Jingjing; Shanmugam, Sivaprakash; Crowder, Michael W.; Robert A Bonomo; Pusztai-Carey, Marianne; Carey, Paul R.

    2013-01-01

    Rapid mix - rapid freeze is a powerful method to study the mechanisms of enzyme-substrate reactions in solution. Here we report a protocol that combines this method with normal (non-resonance) Raman microscopy to enable us to define molecular details of intermediates at early time points. With this combined method, SHV-1, a class A β-lactamase, and tazobactam, a commercially available β-lactamase inhibitor, were rapidly mixed on the millisecond time-scale, then were flash-frozen by injecting ...

  13. Inverse bremsstrahlung stabilization of noise in the generation of ultrashort intense pulses by backward Raman amplification

    Inverse bremsstrahlung absorption of the pump laser beam in a backward Raman amplifier over the round-trip light transit time through the subcritical density plasma can more than double the electron temperature of the plasma and produce time-varying axial temperature gradients. The resulting increased Landau damping of the plasma wave and detuning of the resonance can act to stabilize the pump against unwanted amplification of Langmuir noise without disrupting nonlinear amplification of the femtosecond seed pulse. Because the heating rate increases with the charge state Z, only low-Z plasmas (hydrogen, helium, or helium-hydrogen mixtures) will maintain a low enough temperature for efficient operation

  14. The analysis of Raman scattering in a free-electron laser with a rectangular hybrid wiggler

    Kordbacheh, A., E-mail: akordbacheh@iust.ac.ir; Shahsavand, M. [Department of Physics, Iran University of Science and Technology, 1684613114 Tehran (Iran, Islamic Republic of)

    2015-10-15

    A one dimensional theory of the stimulated Raman backscattering process in a free electron laser with rectangular hybrid wiggler (RHW) is analyzed. The dispersion relation in the rest frame of the electron beam and also a formula for the lab-frame spatial growth rate are derived. A numerical computation of the growth rate for RHW is conducted and a comparison with that for coaxial hybrid wiggler is made away from the resonance. The growth rate is found larger for the rectangular wiggler than for the coaxial wiggler. A much narrower magnetoresonance associated with the third spatial harmonic is also obtained compared to the first one.

  15. The analysis of Raman scattering in a free-electron laser with a rectangular hybrid wiggler

    A one dimensional theory of the stimulated Raman backscattering process in a free electron laser with rectangular hybrid wiggler (RHW) is analyzed. The dispersion relation in the rest frame of the electron beam and also a formula for the lab-frame spatial growth rate are derived. A numerical computation of the growth rate for RHW is conducted and a comparison with that for coaxial hybrid wiggler is made away from the resonance. The growth rate is found larger for the rectangular wiggler than for the coaxial wiggler. A much narrower magnetoresonance associated with the third spatial harmonic is also obtained compared to the first one

  16. Cavity-Enhanced Raman Spectroscopy of Natural Gas with Optical Feedback cw-Diode Lasers

    Hippler, M

    2015-01-01

    We report on improvements made on our previously introduced technique of cavity-enhanced Raman spectroscopy (CERS) with optical feedback cw-diode lasers in the gas phase, including a new mode-matching procedure which keeps the laser in resonance with the optical cavity without inducing long-term frequency shifts of the laser, and using a new CCD camera with improved noise performance. With 10 mW of 636.2 nm diode laser excitation and 30 s integration time, cavity enhancement achieves noise-eq...

  17. Stimulated Raman scattering in hydrogen pumped with a tunable, high power, narrow linewidth alexandrite laser

    The conversion efficiencies and the linewidth of the Stokes components which result from stimulated Raman scattering in hydrogen gas pumped with a high power alexandrite laser have been studied. Measurements of the Stokes components under varying conditions reveal that there is no effect on the conversion efficiency by the narrowing of the pump linewidth and that the linewidth of the first Stokes component is broader than the expected linewidth of the injection seeded pump. Modelling of the conversion from the pump to the Stokes components shows a strong dependence of this conversion on a specific, resonant four wave mixing process. (author)

  18. THz-Raman: accessing molecular structure with Raman spectroscopy for enhanced chemical identification, analysis, and monitoring

    Heyler, Randy A.; Carriere, James T. A.; Havermeyer, Frank

    2013-05-01

    Structural analysis via spectroscopic measurement of rotational and vibrational modes is of increasing interest for many applications, since these spectra can reveal unique and important structural and behavioral information about a wide range of materials. However these modes correspond to very low frequency (~5cm-1 - 200cm-1, or 150 GHz-6 THz) emissions, which have been traditionally difficult and/or expensive to access through conventional Raman and Terahertz spectroscopy techniques. We report on a new, inexpensive, and highly efficient approach to gathering ultra-low-frequency Stokes and anti-Stokes Raman spectra (referred to as "THz-Raman") on a broad range of materials, opening potential new applications and analytical tools for chemical and trace detection, identification, and forensics analysis. Results are presented on explosives, pharmaceuticals, and common elements that show strong THz-Raman spectra, leading to clear discrimination of polymorphs, and improved sensitivity and reliability for chemical identification.

  19. Surface and waveguide collection of Raman emission in waveguide-enhanced Raman spectroscopy.

    Wang, Zilong; Zervas, Michalis N; Bartlett, Philip N; Wilkinson, James S

    2016-09-01

    We demonstrate Raman spectroscopy on a high index thin film tantalum pentoxide waveguide and compare collection of Raman emission from the waveguide end with that from the waveguide surface. Toluene was used as a convenient model analyte, and a 40-fold greater signal was collected from the waveguide end. Simulations of angular and spatial Raman emission distributions showed good agreement with experiments, with the enhancement resulting from efficient collection of power from dipoles near the surface into the high-index waveguide film and substrate, combined with long interaction length. The waveguide employed was optimized at the excitation wavelength but not at emission wavelengths, and full optimization is expected to lead to enhancements comparable to surface-enhanced Raman spectroscopy in robust low-cost metal-free and nanostructure-free chips. PMID:27607994

  20. Time-encoded Raman scattering (TICO-Raman) with Fourier domain mode locked (FDML) lasers

    Karpf, Sebastian; Eibl, Matthias; Wieser, Wolfgang; Klein, Thomas; Huber, Robert

    2015-07-01

    We present a new concept for performing stimulated Raman spectroscopy and microscopy by employing rapidly wavelength swept Fourier Domain Mode locked (FDML) lasers [1]. FDML lasers are known for fastest imaging in swept-source optical coherence tomography [2, 3]. We employ this continuous and repetitive wavelength sweep to generate broadband, high resolution stimulated Raman spectra with a new, time-encoded (TICO) concept [4]. This allows for encoding and detecting the stimulated Raman gain on the FDML laser intensity directly in time. Therefore we use actively modulated pump lasers, which are electronically synchronized to the FDML laser, in combination with a fast analog-to-digital converter (ADC) at 1.8 GSamples/s. We present hyperspectral Raman images with color-coded, molecular contrast.