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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

    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

  8. 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.

  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; 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

  20. 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.

  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. 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

  4. 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

  5. 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...

  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. 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

  7. 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.

  8. 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...

  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. 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.

  4. 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.

  5. 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.

  6. 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)

  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

    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.

  13. 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

  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. 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

  19. 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.

  20. 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

  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. 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.

  9. 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.

  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. 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.

  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. 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

  2. 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

  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. 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

  5. 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.

  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. 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.

  15. 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

  16. 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.

  17. 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.

  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. 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.

  10. 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.

  11. 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.

  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. 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

  8. 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

  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. 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

  19. 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

  20. 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.

  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. 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

  3. 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

  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. 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.

  6. 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

  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. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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

  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

    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

    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.

  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.