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Sample records for enhanced resonance raman

  1. Ultraviolet Resonant Raman Enhancements in the Detection of Explosives

    SciTech Connect

    Short Jr., Billy Joe

    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.

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

    PubMed

    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

  3. Experimental evaluation of the twofold electromagnetic enhancement theory of surface-enhanced resonance Raman scattering

    SciTech Connect

    Yoshida, Ken-ichi; Itoh, Tamitake; Biju, Vasudevanpillai; Ishikawa, Mitsuru; Ozaki, Yukihiro

    2009-02-15

    We examined an electromagnetic (EM) theory of surface-enhanced resonance Raman scattering (SERRS) using single Ag nanoaggregates. The SERRS-EM theory is characterized by twofold EM enhancement induced by the coupling of plasmon resonance with both excitation and emission of Raman scattering plus fluorescence. The total emission cross-section spectra of enhanced Raman scattering and enhanced fluorescence were calculated using the following parameters: the spectrum of enhancement factor induced by plasmon resonance, resonance Raman scattering overlapped with fluorescence, and excitation wavelengths. The calculations well agreed with experimental total emission cross-section spectra, thus providing strong indications that the SERRS-EM theory is quantitatively correct.

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    Guddala, Sriram; Narayana Rao, D.; Ramakrishna, S. Anantha

    2016-06-01

    A tri-layer metamaterial perfect absorber of light, consisting of (Al/ZnS/Al) films with the top aluminum layer patterned as an array of circular disk nanoantennas, is investigated for resonantly enhancing Raman scattering from C60 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 C60 on metamaterials with off-resonant absorption bands peaking 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 numerical simulations.

  6. Electronic Resonance Enhancement in Raman and CARS Spectroscopy: Surface Enhanced Scattering of Highly Fluorescent Molecules

    NASA Astrophysics Data System (ADS)

    Lawhead, Carlos; Ujj, Laszlo

    2015-03-01

    Surface enhanced Raman spectroscopy (SERS) is an extremely useful tool in increasing sensitivity of Raman spectroscopy; this technique significantly increases the signal from vibrational resonances which can overcome background fluoresces. Silver nanoparticles coated substrates and the silver nanoparticles in solution were used on a variety of fluorescent molecules in order to overcome sample complexities and measure the vibrational spectra. The possible enhancement of SERS using a coherent Raman (CARS) method was investigated, but enhancement factors due to Surface Enhanced CARS have yet to be verified. The instrument used was developed in the University of West Florida Physics Department utilized the second harmonic of a Nd:YAG laser to provide the excitation wavelength at 532 nm and is capable of both transmission and reflection Raman measurements. Special thanks to the UWF Office of Undergraduate Research.

  7. Surface-enhanced resonance hyper-Raman scattering and surface-enhanced resonance Raman scattering of dyes adsorbed on silver electrode and silver colloid: a comparison study

    NASA Astrophysics Data System (ADS)

    Li, Wu-Hu; Li, Xiao-Yuan; Yu, Nai-Teng

    1999-10-01

    Surface-enhanced resonance hyper-Raman scattering (SERHRS) and surface-enhanced resonance Raman scattering (SERRS) of three dyes, rhodamine 6G, crystal violet and basic fuchsin, are studied comparatively on electrochemically roughened silver electrode and silver colloid, respectively. All three dyes show a better SERHRS efficiency on the silver colloid than on the silver electrode, a phenomenon just opposite to what we have recently observed for pyridine and pyrazine [Chem. Phys. Lett. 305 (1999) 303]. These results suggest that the efficiency of SEHRS depends not only on the active surfaces employed (colloidal metals versus roughened electrodes) but also on the types of the adsorbed molecules.

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Comparative study of resonance Raman and surface-enhanced resonance Raman chlorophyll a spectra using soret and red excitation

    SciTech Connect

    Thomas, L.L.; Kim, Jaeho; Cotton, T.M. )

    1990-12-05

    Surface-enhanced resonance Raman scattering (SERRS) spectra are reported for chlorophyll a adsorbed on a silver electrode at 298 and 77 K with 406.7-, 457.9-, 514.5-, and 647.1-nm excitation. Submerging the electrode in degassed water at 298 K was found to improve the spectral quality by minimizing sample heating and photooxidation. Spectral intensities and peak resolutions were greater at all excitation wavelengths at liquid nitrogen temperature. Most significantly, roughened silver at the low temperature quenched the fluorescence accompanying red excitation and minimized sample photooxidation, resulting in richly detailed SERRS spectra of chlorophyll a. The close correspondence between chlorophyll a resonance Raman (RR) and SERRS spectra suggests that an electromagnetic mechanism is the major source of the surface enhancement, rather than a chemical mechanism (e.g. a charge-transfer complex between chlorophyll a and the metal). The spectral similarities, together with the presence of the MgN{sub 4} vibration band in the SERRS spectra, also provide evidence that structural alterations (e.g. cleavage of ring V or loss of Mg) do not occur in chlorophyll a after adsorption at the electrode surface. A distinctive SERRS spectrum was obtained for each excitation wavelength. Selective excitation within the various electronic transitions can thus be utilized to verify assignments of the vibrational modes of chlorophyll a and to monitor its interactions and photochemical behavior in biomimetic systems.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Double resonance surface enhanced Raman scattering substrates: an intuitive coupled oscillator model.

    PubMed

    Chu, Yizhuo; Wang, Dongxing; Zhu, Wenqi; Crozier, Kenneth B

    2011-08-01

    The strong coupling between localized surface plasmons and surface plasmon polaritons in a double resonance surface enhanced Raman scattering (SERS) substrate is described by a classical coupled oscillator model. The effects of the particle density, the particle size and the SiO2 spacer thickness on the coupling strength are experimentally investigated. We demonstrate that by tuning the geometrical parameters of the double resonance substrate, we can readily control the resonance frequencies and tailor the SERS enhancement spectrum. PMID:21934853

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

    PubMed

    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

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

    PubMed

    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

  15. Surface-Enhanced Raman Scattering Using Silica Whispering-Gallery Mode Resonators

    NASA Technical Reports Server (NTRS)

    Anderson, Mark S.

    2013-01-01

    The motivation of this work was to have robust spectroscopic sensors for sensitive detection and chemical analysis of organic and molecular compounds. The solution is to use silica sphere optical resonators to provide surface-enhanced spectroscopic signal. Whispering-gallery mode (WGM) resonators made from silica microspheres were used for surface-enhanced Raman scattering (SERS) without coupling to a plasmonic mechanism. Large Raman signal enhancement is observed by exclusively using 5.08-micron silica spheres with 785-nm laser excitation. The advantage of this non-plasmonic approach is that the active substrate is chemically inert silica, thermally stable, and relatively simple to fabricate. The Raman signal enhancement is broadly applicable to a wide range of molecular functional groups including aliphatic hydrocarbons, siloxanes, and esters. Applications include trace organic analysis, particularly for in situ planetary instruments that require robust sensors with consistent response.

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

    SciTech Connect

    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.

  17. Resonance Raman enhancement optimization in the visible range by selecting different excitation wavelengths

    NASA Astrophysics Data System (ADS)

    Wang, Zhong; Li, Yuee

    2015-09-01

    Resonance enhancement of Raman spectroscopy (RS) has been used to significantly improve the sensitivity and selectivity of detection for specific components in complicated environments. Resonance RS gives more insight into the biochemical structure and reactivity. In this field, selecting a proper excitation wavelength to achieve optimal resonance enhancement is vital for the study of an individual chemical/biological ingredient with a particular absorption characteristic. Raman spectra of three azo derivatives with absorption spectra in the visible range are studied under the same experimental conditions at 488, 532, and 633 nm excitations. Universal laws in the visible range have been concluded by analyzing resonance Raman (RR) spectra of samples. The long wavelength edge of the absorption spectrum is a better choice for intense enhancement and the integrity of a Raman signal. The obtained results are valuable for applying RR for the selective detection of biochemical constituents whose electronic transitions take place at energies corresponding to the visible spectra, which is much friendlier to biologial samples compared to ultraviolet.

  18. Maximizing the electromagnetic and chemical resonances of surface-enhanced Raman scattering for nucleic acids.

    PubMed

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

    2014-08-26

    Although surface-enhanced Raman spectroscopy (SERS) has previously been performed with nucleic acids, the measured intensities for each nucleic acid have varied significantly depending on the SERS substrate and excitation wavelength. We have demonstrated that the charge-transfer (CT) mechanism, also known as the chemical enhancement of SERS, is responsible for the discrepancies previously reported in literature. The electronic states of cytosine and guanine attached to silver atoms are computationally calculated and experimentally measured to be in the visible range, which leads to a resonance Raman effect at the corresponding maximum wavelengths. The resulting SERS measurements are in good agreement with the simulated values, in which cytosine-silver shows stronger enhancement at 532 nm and guanine-silver shows stronger enhancement at 785 nm. An atomic layer of aluminum oxide is deposited on substrates to prevent charge-transfer, and corresponding measurements show weaker Raman signals caused by the suppression of the chemical resonance. These findings suggest the optimal SERS signal can be achieved by tuning the excitation wavelength to match both the electromagnetic and chemical resonances, paving the way for future single molecule detection of nucleic acids other than adenine. PMID:25065837

  19. Quantitative evaluation of blinking in surface enhanced resonance Raman scattering and fluorescence by electromagnetic mechanism

    NASA Astrophysics Data System (ADS)

    Itoh, Tamitake; Iga, Mitsuhiro; Tamaru, Hiroharu; Yoshida, Ken-ichi; Biju, Vasudevanpillai; Ishikawa, Mitsuru

    2012-01-01

    We analyze blinking in surface enhanced resonance Raman scattering (SERRS) and surface enhanced fluorescence (SEF) of rhodamine 6G molecules as intensity and spectral instability by electromagnetic (EM) mechanism. We find that irradiation of intense NIR laser pulses induces blinking in SERRS and SEF. Thanks to the finding, we systematically analyze SERRS and SEF from stable to unstable using single Ag nanoparticle (NP) dimers. The analysis reveals two physical insights into blinking as follows. (1) The intensity instability is inversely proportional to the enhancement factors of decay rate of molecules. The estimation using the proportionality suggests that separation of the molecules from Ag NP surfaces is several angstroms. (2) The spectral instability is induced by blueshifts in EM enhancement factors, which have spectral shapes similar to the plasmon resonance. This analysis provides us with a quantitative picture for intensity and spectral instability in SERRS and SEF within the framework of EM mechanism.

  20. Resonant Raman scattering in nanoscale pentacene films

    NASA Astrophysics Data System (ADS)

    He, Rui; Dujovne, Irene; Chen, Liwei; Miao, Qian; Hirjibehedin, Cyrus F.; Pinczuk, Aron; Nuckolls, Colin; Kloc, Christian; Ron, Arza

    2004-02-01

    Resonant Raman scattering intensities from nanoscale films of pentacene display large resonant enhancements that enable observation of vibrational modes in monolayer cluster films. The resonant enhancements occur when the outgoing photon energy overlaps the free exciton optical transitions observed in luminescence. The results point to the significant potential of resonant Raman methods in the characterization of nanoscale structures of organic molecular semiconductors.

  1. Surface-enhanced resonance Raman spectroscopy of iron-dopamine complexes

    NASA Astrophysics Data System (ADS)

    Kowalchyk, Will K.; Davis, Kevin L.; Morris, Michael D.

    1995-01-01

    Surface-enhanced resonance Raman spectroscopy (SERRS) at silver colloids is used to detect the catecholamines, 3-hydroxytyramine (dopamine) and 3,4-dihydroxyphenylacetic acid (DOPAC), in a modified Ringer's solution. Catecholamines form very strong complexes with iron(III) in solution ( Kf > 10 40) and exhibit a broad ligand-to-metal charge-transfer (LMCT) absorption in the visible (˜ 500 nm). Resonance enhancement is achieved by excitation at 532 nm from a frequency doubled Nd:YAG laser with high quality spectra attainable in 1 s. Maximum SERRS signal is observed when basic buffer is added to a dopamine sample containing 50 × 10 -6 M ferric ion. Dopamine concentrations in the nanomolar (resting level) range are obtained using this technique.

  2. Magnetic field enriched surface enhanced resonance Raman spectroscopy for early malaria diagnosis

    NASA Astrophysics Data System (ADS)

    Yuen, Clement; Liu, Quan

    2012-01-01

    Hemozoin is a by-product of malaria infection in erythrocytes, which has been explored as a biomarker for early malaria diagnosis. We report magnetic field-enriched surface-enhanced resonance Raman spectroscopy (SERRS) of β--hematin crystals, which are the equivalent of hemozoin biocrystals in spectroscopic features, by using magnetic nanoparticles with iron oxide core and silver shell (Fe3O4@Ag). The external magnetic field enriches β--hematin crystals and enhances the binding between β--hematin crystals and magnetic nanoparticles, which provides further improvement in SERRS signals. The magnetic field-enriched SERRS signal of β--hematin crystals shows approximately five orders of magnitude enhancement in the resonance Raman signal, in comparison to about three orders of magnitude improvement in the SERRS signal without the influence of magnetic field. The improvement has led to a β--hematin detection limit at a concentration of 5 nM (roughly equivalent to 30 parasites/μl at the early stages of malaria infection), which demonstrates the potential of magnetic field-enriched SERRS technique in early malaria diagnosis.

  3. Combined dielectric and plasmon resonance for giant enhancement of Raman scattering

    NASA Astrophysics Data System (ADS)

    Kukushkin, V. I.; Grishina, Ya. V.; Egorov, S. V.; Solov'ev, V. V.; Kukushkin, I. V.

    2016-04-01

    Combined dielectric/metal resonators for colossal enhancement of inelastic light scattering are developed and their properties are investigated. It is shown that a record enhancement factor of 2 × 108 can be obtained using these structures. The dielectric resonators are fabricated on Si/SiO2 substrates where periodic arrays of square 10- to 200-nm-high dielectric pillars are produced via electron-beam lithography and plasma etching. The lateral size a of the pillars varies between 50 and 1500 nm, and their period in the array is 2 a. To make a combined dielectric/metal resonator, a nanostructured layer of silver is deposited onto the fabricated periodic dielectric structure by thermal evaporation. It is established that, for a fixed height of the dielectric pillars, the Raman scattering enhancement factor experiences pronounced oscillations as a function of the period (and size) of the pillars. It is shown that these oscillations are determined by the modes of the dielectric resonator and governed by the relation between the excitation laser wavelength and the planar size of the dielectric pillars.

  4. Surface-enhanced resonance Raman scattering of hemoproteins and those in complicated biological systems.

    PubMed

    Kitahama, Yasutaka; Ozaki, Yukihiro

    2016-08-15

    In this review article, we discuss surface-enhanced resonance Raman scattering (SERRS) studies of hemeproteins such as myoglobin, hemoglobin, and cytochrome on various metal substrates; for example, colloidal silver nanoparticles coated with and without self-assembled monolayers (SAM), a roughened silver electrode protected with and without SAM, a sharp silver tip, and colloidal gold nanoparticles coated with and without SAM. Moreover, we classify the studies in terms of an excitation wavelength; namely, excitation at the B- (Soret) band, Q- (α and β) band, and in the near infrared (NIR) range. In the SERRS studies with B band excitation, it has been shown that the hemeprotein on a silver surface takes a non-native form through detachment from the heme pocket in the protein. With Q band excitation, on the other hand, the change in SERRS has been explained by the orientation of the hemeprotein on the surface. Even by excitation in the NIR range, the peak positions are consistent with the assignment of the major vibrational modes of heme despite there being no resonance Raman effect. Thus, the SERRS of hemeproteins is influenced by a resonance Raman effect, LSPR, and interactions with the metal surface such as structural changes, orientation, and selective adsorption. Moreover, we discuss how SERRS has been applied to complicated biological systems such as living cells containing hemeprotein. For mitochondria, a change of the oxidation-state was observed by the electron transport chain in the cell and at different positions. As an example of a biomedical application of SERRS, the sensitive detection of malaria is presented. PMID:27381192

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Single molecule surface enhanced resonance Raman scattering (SERRS) of the enhanced green fluorescent protein (EGFP)

    NASA Astrophysics Data System (ADS)

    Hofkens, Johan; De Schryver, Frans C.; Cotlet, Mircea; Habuchi, Satoshi

    2004-06-01

    One of the most intriguing findings in single molecule spectroscopy (SMS) is the observation of Raman spectra of individual molecules, despite the small cross section of the transitions involved. The observation of the spectra can be explained by the surface enhanced Raman scattering (SERRS) effect. At the single-molecule level, the SERRS-spectra recorded as a function of time reveal inhomogeneous behaviour such as on/off blinking, spectral diffusion, intensity fluctuations of vibrational line, and even splitting of some lines within the spectrum of one molecule. Single-molecule SERRS (SM-SERRS) spectroscopy opens up exciting opportunities in the field of biophysics and biomedical spectroscopy. The first example of single protein SERRS was performed on hemoglobin. However, the possibility of extracting the heme group by silver sols can not be excluded. Here we report on SM-SERRS spectra of enhanced green fluorescent protein (EGFP) in which the chromophore is kept in the protein. The time series of SM-SERRS spectra suggest the conversion of the EGFP chromophore between the deprotonated and the protonated form. Autocorrelation analysis of SM-SERRS trajectory reveals the presence of fast dynamics taking place in the protein. Our findings show the potential of the technique to study structural dynamics of protein molecules.

  7. Auger resonant Raman spectroscopy

    SciTech Connect

    Azuma, Y.; LeBrun, T.; MacDonald, M.; Southworth, S.H.

    1995-08-01

    As noted above, traditional spectroscopy of the electronic structure of the inner shells of atoms, molecules, and solids is limited by the lifetime broadening of the core-excited states. This limitation can also be avoided with the non-radiative analog of X-ray Raman scattering - resonant Auger Raman spectroscopy. We have used this technique to study the K-shell excitation spectrum of argon as the photon energy is continuously scanned across threshold.

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

    ERIC Educational Resources Information Center

    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…

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

    PubMed

    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

  10. Hollow Au/Ag nanostars displaying broad plasmonic resonance and high surface-enhanced Raman sensitivity

    NASA Astrophysics Data System (ADS)

    Garcia-Leis, Adianez; Torreggiani, Armida; Garcia-Ramos, Jose Vicente; Sanchez-Cortes, Santiago

    2015-08-01

    Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars. The size, shape, and composition of Ag as well as their optical properties were studied by extinction spectroscopy, hyperspectral dark field microscopy, transmission and scanning electron microscopy (TEM and SEM), and energy dispersive X-ray spectroscopy (EDX). Finally, the surface-enhanced Raman scattering (SERS) activity of these HNS was investigated by using thioflavin T, a biomarker of the β-amyloid fibril formation, responsible for Alzheimer's disease. Lucigenin, a molecule displaying different SERS activities on Au and Ag, was also used to explore the presence of these metals on the NP surface. Thus, a relationship between the morphology, plasmon resonance and SERS activity of these new NPs was made.Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars

  11. Surface-enhanced resonance Raman scattering spectroscopy of photosystem II pigment-protein complexes

    SciTech Connect

    Picorel, R. Estacion Experimental Aula Dei, Zaragoza ); Chumanov, G.; Cotton, T.M. ); Montoya, G. ); Toon, S.; Seibert, M. )

    1994-06-09

    Three different photosystem II (PSII) pigment-protein complexes (D1-D2-Cyt b[sub 559]-CP47, D1-D2-Cyt b[sub 559], and CP47) isolated from spinach were studied by surface-enhanced resonance Raman scattering (SERRS) spectroscopy. Surface-enhanced Raman scattering (SERS) is a distance sensitive (on a 5-10-[angstrom] scale) spectroscopic tool that can be used to examine structural properties of large biological molecules. It is demonstrated here that SERS can also be used to determine organizational relationships between different pigment-protein complexes. Strong SERRS spectra from the above PSII complexes before and after treatment with sodium dithionite were obtained on roughened Ag electrodes and in citrate-reduced Ag colloids. The D1-D2-Cyt b[sub 559] complex adsorbs with the Cyt b[sub 559] heme close to the surface in the colloid, whereas the complex adsorbs differently on the Ag electrode due to the differing surface properties of the two types of substrates. An analysis of the SERRS spectra led to the following conclusions: CP47 binds next to Cyt b[sub 559] in the D1-D2-Cyt b[sub 559]-CP47 complex and covers the heme, the Cyt b[sub 559] heme is located closer to one side of the complex (the stromal side in the intact thylakoid membrane), and both Chl and [beta]-carotene molecules are located closer to the opposite side of the complex. 37 refs., 7 figs.

  12. Resonant Raman scattering in antiferromagnets

    NASA Astrophysics Data System (ADS)

    Morr, Dirk K.; Chubukov, Andrey V.

    1997-10-01

    Two-magnon Raman scattering provides important information about electronic correlations in the insulating parent compounds of high-Tc materials. Recent experiments have shown a strong dependence of the Raman signal in B1g geometry on the frequency of the incoming photon. We present an analytical and numerical study of the Raman intensity in the resonant regime. It has been previously argued by Chubukov and Frenkel that the most relevant contribution to the Raman vertex at resonance is given by the triple resonance diagram. We derive an expression for the Raman intensity in which we simultaneously include the enhancement due to the triple resonance and a final-state interaction. We compute the two-magnon peak height (TMPH) as a function of incident frequency and find two maxima at ω(1)res~2Δ+3J and ω(2)res~2Δ+8J. We argue that the high-frequency maximum is cut only by a quasiparticle damping, while the low-frequency maximum has a finite amplitude even in the absence of damping. We also obtain an evolution of the Raman profile from an asymmetric form around ω(1)res to a symmetric form around ω(2)res. We further show that the TMPH depends on the fermionic quasiparticle damping, the next-nearest-neighbor hopping term t', and the corrections to the interaction vertex between light and the fermionic current. We discuss our results in the context of recent experiments by Blumberg et al. on Sr2CuO2Cl2 and YBa2Cu3O6.1 and Rübhausen et al. on PrBa2Cu3O7 and show that the triple resonance theory yields a qualitative and to some extent also quantitative understanding of the experimental data.

  13. A triple-resonance Raman chip for simultaneous enhancement of Stokes and anti-Stokes lines utilizing both localized and non-localized plasmonic resonance

    NASA Astrophysics Data System (ADS)

    Lin, Jiao; Zhang, Yuan; Lee, El-Hang; He, Sailing

    2015-10-01

    In this paper we report a triple-resonance surface-enhanced Raman scattering (SERS) chip that is able to provide simultaneous field enhancement for both the Stokes and anti-Stokes lines. The structure consists of an array of periodic gold bowties placed on the surface of a uniform gold film. It can support two localized surface plasmonic resonances (LSPRs): an electric dipole binding resonance (EDBR) and a magnetic dipole resonance (MDR). A third field enhancement peak is obtained by utilizing the strong interaction between the non-localized surface plasmonic resonance (non-localized SPR) and the LSPR, which greatly raises the field enhancement for the non-localized SPR. In addition, a gold strip-line resonator is incorporated to further enhance the local field intensity. Consequently, the field enhancement of the three peaks are all increased. Compared with the same structure without strip, the periodic bowtie-strip compound structure on gold film can gain as much as ∼22.8 times and ∼3.6 times larger Raman intensity enhancement simultaneously for both the Stokes and anti-Stokes lines.

  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

    NASA Astrophysics Data System (ADS)

    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. Localized surface plasmon resonance immunoassay and verification using surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Yonzon, Chanda R.; Zhang, Xiaoyu; Van Duyne, Richard P.

    2003-11-01

    This work exploits the localized surface plasmon resonance (LSPR) spectroscopy of noble metal nanoparticles to achieve sensitive and selective detection of biological analytes. Noble metal nanoparticles exhibit an LSPR that is strongly dependent on their size, shape, material, and the local dielectric environment. The LSPR is also responsible for the intense signals observed in surface-enhanced Raman scattering (SERS). Ag nanoparticles fabricated using the nanosphere lithography (NSL) technique exploits this LSPR sensitivity as a signal transduction method in biosensing applications. The current work implements LSPR biosensing for the anti dinitrophenyl (antiDNP) immunoassay system. Upon forming the 2,4 dinitrobenzoic acid/antiDNP complex, this system shows a large LSPR shift of 44 nm when exposed to antiDNP concentration of 1.5 x 10-6 M. In addition, due to the unique molecular characteristics of the functional groups on the biosensor, it can also be characterized using SERS. First, the nanoparticles are functionalized with a mixed self-assembled monolayer (SAM) comprised of 2:1 octanethiol and 11-amino undecanethiol. The SAM is exposed to 2,4-dinitrobenzoic acid with the 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC) coupling reagent. Finally, the 2,4-dinitrophenyl terminated SAM is exposed to various concentration of antiDNP. LSPR shifts indicate the occurrence of a binding event. SER spectra confirm binding of 2,4 dinitrobenzoic acid with amine-terminated SAM. This LSPR/SERS biosensing method can be generalized to a myriad of biologically relevant systems.

  16. Exploring the Potential of Stable Isotope (Resonance) Raman Microspectroscopy and Surface-Enhanced Raman Scattering for the Analysis of Microorganisms at Single Cell Level.

    PubMed

    Kubryk, Patrick; Kölschbach, Janina S; Marozava, Sviatlana; Lueders, Tillmann; Meckenstock, Rainer U; Niessner, Reinhard; Ivleva, Natalia P

    2015-07-01

    Raman microspectroscopy is a prime tool to characterize the molecular and isotopic composition of microbial cells. However, low sensitivity and long acquisition times limit a broad applicability of the method in environmental analysis. In this study, we explore the potential, the applicability, and the limitations of stable isotope Raman microspectroscopy (SIRM), resonance SIRM, and SIRM in combination with surface-enhanced Raman scattering (SERS) for the characterization of single bacterial cells. The latter two techniques have the potential to significantly increase sensitivity and decrease measurement times in SIRM, but to date, there are no (SERS-SIRM) or only a limited number (resonance SIRM) of studies in environmental microbiology. The analyzed microorganisms were grown with substrates fully labeled with the stable isotopes (13)C or (2)H and compounds with natural abundance of atomic isotopes ((12)C 98.89% or (1)H 99.9844%, designated as (12)C or (1)H, respectively). Raman bands of bacterial cell compounds in stable isotope-labeled microorganisms exhibited a characteristic red-shift in the spectra. In particular, the sharp phenylalanine band was found to be an applicable marker band for SIRM analysis of the Deltaproteobacterium strain N47 growing anaerobically on (13)C-naphthalene. The study of G. metallireducens grown with (13)C- and (2)H-acetate showed that the information on the chromophore cytochrome c obtained by resonance SIRM at 532 nm excitation wavelength can be successfully complemented by whole-organism fingerprints of bacteria cells achieved by regular SIRM after photobleaching. Furthermore, we present here for the first time the reproducible SERS analysis of microbial cells labeled with stable isotopes. Escherichia coli strain DSM 1116 cultivated with (12)C- or (13)C-glucose was used as a model organism. Silver nanoparticles synthesized in situ were applied as SERS media. We observed a reproducible red-shift of an adenine-related marker band

  17. Silver Nanoparticle-Enhanced Resonance Raman Sensor of Chromium(III) in Seawater Samples

    PubMed Central

    Ly, Nguyễn Hoàng; Joo, Sang-Woo

    2015-01-01

    Tris(hydroxymethyl)aminomethane ethylenediaminetetraacetic acid (Tris-EDTA), upon binding Cr(III) in aqueous solutions at pH 8.0 on silver nanoparticles (AgNPs), was found to provide a sensitive and selective Raman marker band at ~563 cm−1, which can be ascribed to the metal-N band. UV-Vis absorption spectra also supported the aggregation and structural change of EDTA upon binding Cr(III). Only for Cr(III) concentrations above 500 nM, the band at ~563 cm−1 become strongly intensified in the surface-enhanced Raman scattering spectra. This band, due to the metal-EDTA complex, was not observed in the case of 50 μM of K+, Cd2+, Mg2+, Ca2+, Mn2+, Co2+, Na+, Cu2+, NH4+, Hg2+, Ni2+, Fe3+, Pb2+, Fe2+, and Zn2+ ions. Seawater samples containing K, Mg, Ca, and Na ion concentrations higher than 8 mM also showed the characteristic Raman band at ~563 cm−1 above 500 nM, validating our method. Our approach may be useful in detecting real water samples by means of AgNPs and Raman spectroscopy. PMID:25938200

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

    PubMed

    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

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

    SciTech Connect

    Fang Yingcui; Li Xiaxi; Blinn, Kevin; Mahmoud, Mahmoud A.; Liu Meilin

    2012-09-15

    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.

  20. Generating monomeric 5-coordinated microperoxidase-11 using carboxylic acid functionalized silver nanoparticles: A surface-enhanced resonance Raman scattering analysis.

    PubMed

    Kalaivani, Govindasamy; Sivanesan, Arumugam; Kannan, Ayyadurai; Sevvel, Ranganathan

    2016-10-01

    Microperoxidase-11 (MP-11), a heme undecapeptide obtained by proteolytic digestion of cytochrome c, resembles peroxidase enzyme when its heme center is 5-coordinated with a vacant sixth coordination site. However, MP-11 always tends to aggregate in both solution and on surface and eventually forms the 6-coordinated heme. Thus, the present study investigates the immobilization strategy of MP-11 on nanoparticle surface in order to generate monomeric 5-coordinated MP-11 and make them as an efficient biocatalyst. The powerful surface-enhanced resonance Raman scattering (SERRS) technique is being employed to attain the detailed structural information of the catalytic site i.e., the heme center. The localized surface plasmon resonance (LSPR) tuned and 6-mercaptohexanoic acid (MHA) functionalized silver nanoparticles (Ag@MHA NPs) are used as Raman signal amplifier. The outcome of the SERRS study unambiguously portrays the existence of monomeric 5-coordinated MP-11 on Ag@MHA NPs surface. Here, Ag@MHA NPs plays a dual role of providing a platform to create monomeric 5-coordinated MP-11 and to load large number of MP-11 due to its high surface to volume ratio. Further, the electrostatic interaction between Ag@MHA NPs and MP-11 leads to instantaneous SERRS signal enhancement with a Raman enhancement factor (EFSERS) of 2.36×10(6). Langmuir adsorption isotherm has been employed for the adsorption of MP-11 on Ag@MHA NPs surface, which provides the real surface coverage (ΓS(*)) and equilibrium constant (K) value of 1.54nm and 5×10(11)M(-1). Furthermore, the peroxidase activity of MP-11 has been demonstrated through electrocatalytic oxygen reduction reaction. PMID:27434160

  1. Guided-mode-resonance-coupled plasmonic-active SiO2 nanotubes for surface enhanced Raman spectroscopy

    PubMed Central

    Xu, Xiaobin; Hasan, Dihan; Wang, Lei; Chakravarty, Swapnajit; Chen, Ray T.; Fan, D. L.; Wang, Alan X.

    2012-01-01

    We demonstrate a surface enhanced Raman scattering (SERS) substrate by integrating plasmonic-active SiO2 nanotubes into Si3N4 gratings. First, the dielectric grating that is working under guided mode resonance (GMR) provides enhanced electric field for localized surface plasmon polaritons on the surface of metallic nanoparticles. Second, we use SiO2 nanotubes with densely assembled silver nanoparticles to provide a large amount of “hot spots” without significantly damping the GMR mode of the grating. Experimental measurement on Rhodamine-6G shows a constant enhancement factor of 8 ∼ 10 in addition to the existing SERS effect across the entire surface of the SiO2 nanotubes. PMID:22685345

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

    PubMed Central

    Chong, Xinyuan; Fan, Donglei; Chakravarty, Swapnajit; Wang, Zheng; Chen, Ray T.; Wang, Alan X.

    2016-01-01

    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. PMID:26958546

  3. Theoretical studies of Resonance Enhance Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor

    NASA Technical Reports Server (NTRS)

    Lawandy, N. M.

    1986-01-01

    It is well known that the presence of a real atomic level which is nearly resonant with the pump field can greatly enhance the Raman emission cross section. In order to accurately calculate the Raman gain in systems where resonance enhancement plays a dominant role, expressions for the pump and signal susceptibilities must be derived. These expressions should be valid for arbitrary field strengths in order to allow for pump and signal saturation. In addition, the theory should allow for arbitrary longitudinal and transverse relaxation rates. This latter point is extremely vital for three level atomic systems such as the alkali earth metals since they do not have population reservoirs and can have widely varying spontaneous lifetimes on the three pertinent transitions. Moreover, the dephasing rates are strong functions of electron states and are therefore also different for the three coupled pairs of levels. These considerations are not as important when molecular systems are concerned since the large reservoir of rotational states serve to produce essentially equal longitudinal recovery rates for the population of the three levels. The three level system with three arbitrary longitudinal and transverse relaxation rates was solved. There is no need for setting either pair of rates equal and the expressions are valid for arbitrarily strong fields.

  4. Theoretical studies of resonance enhance stimulated raman scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor. Semiannual report

    SciTech Connect

    Lawandy, N.M.

    1986-01-01

    It is well known that the presence of a real atomic level which is nearly resonant with the pump field can greatly enhance the Raman emission cross section. In order to accurately calculate the Raman gain in systems where resonance enhancement plays a dominant role, expressions for the pump and signal susceptibilities must be derived. These expressions should be valid for arbitrary field strengths in order to allow for pump and signal saturation. In addition, the theory should allow for arbitrary longitudinal and transverse relaxation rates. This latter point is extremely vital for three level atomic systems such as the alkali earth metals since they do not have population reservoirs and can have widely varying spontaneous lifetimes on the three pertinent transitions. Moreover, the dephasing rates are strong functions of electron states and are therefore also different for the three coupled pairs of levels. These considerations are not as important when molecular systems are concerned since the large reservoir of rotational states serve to produce essentially equal longitudinal recovery rates for the population of the three levels. The three level system with three arbitrary longitudinal and transverse relaxation rates was solved. There is no need for setting either pair of rates equal and the expressions are valid for arbitrarily strong fields.

  5. Fiber enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    Fiber enhanced Raman sensing is presented for versatile and extremely sensitive analysis of pharmaceutical drugs and biogenic gases. Elaborated micro-structured optical fibers guide the light with very low losses within their hollow core and provide at the same time a miniaturized sample container for the analytes. Thus, fiber enhanced Raman spectroscopy (FERS) allows for chemically selective detection of minimal sample amounts with high sensitivity. Two examples are presented in this contribution: (i) the detection of picomolar concentrations of pharmaceutical drugs; and (ii) the analysis of biogenic gases within a complex mixture of gases with analytical sensitivities in the ppm range.

  6. Rapid analysis of malachite green and leucomalachite green in fish muscles with surface-enhanced resonance Raman scattering.

    PubMed

    Zhang, Yuanyuan; Yu, Wansong; Pei, Lu; Lai, Keqiang; Rasco, Barbara A; Huang, Yiqun

    2015-02-15

    Surface-enhanced resonance Raman scattering (SERRS) coupled with gold nanospheres was applied for rapid analysis of the hazardous substances malachite green (MG) and leucomalachite green (LMG) in fish muscle tissues. The lowest concentration of MG that could be detected was 0.5ngmL(-1) with high linear correlation (R(2)=0.970-0.998) between MG concentration and intensities of characteristic Raman peaks. A simplified sample preparation method taking less than 1h for recovering MG and LMG in fish fillets was developed for SERRS analysis, and 4-8 samples could be handled in parallel. MG and LMG could be detected in extracts of tilapia fish fillets at as low as 2ngg(-1) with SERRS and a simple principle component analysis method. For six other fish species, the lowest detectable concentration of MG ranged from 1ngg(-1) to 10ngg(-1). This study provides a new sensitive approach for the detection of trace amounts of the prohibited drugs MG and LMG in muscle food, which has the potential for rapidly screening a large number of samples. PMID:25236201

  7. Third-order nonlinearities in molecular hydrogen - Two-photon resonance enhanced third-harmonic generation and Raman scattering

    NASA Technical Reports Server (NTRS)

    Pan, C.-L.; She, C.-Y.; Fairbank, W. M., Jr.; Billman, K. W.

    1977-01-01

    Effects of quantum mechanical interferences on third-order susceptibilities in molecules are studied. First principle calculations for molecular hydrogen are presented and shown to agree with results derived from experimental stimulated Raman gain and spontaneous Raman cross-section data. 10 percent third-harmonic conversion efficiency in H2 at 1 atm without phase matching should require a 150 MW per sq cm at 4.81 microns. As little as 5.9-MW power is sufficient when the beam is properly focused. Resonance Raman scattering (RRS) is proposed for experimentally investigating the interference effects, which tend to reduce the strength of third-order nonlinear susceptibilities.

  8. Characterization and identification of contraband using UV resonant Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Lacey, Richard J.; Hayward, Ian P.; Sands, H. S.; Batchelder, David N.

    1997-02-01

    A range of explosives and narcotics have been examined using Raman spectroscopy with 244 nm excitation. This wavelength of excitation eliminates the fluorescence problems associated with excitation at visible wavelengths. Comparison with spectra obtained using visible excitation reveals that resonance Raman scattering is occurring. This results in simplified spectra, and enhanced Raman scattering efficiencies.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Multiple relaxation and inhomogeneous broadening in resonance enhanced Raman scattering - Application to tunable infrared generation

    NASA Technical Reports Server (NTRS)

    Ryan, J. C.; Lawandy, N. M.

    1989-01-01

    The solutions for the imaginary susceptibility of the Raman field transition with arbitrary relaxation rates and field strengths are examined for differing sets of relaxation rates with emphasis on alkali metal vapors which have spontaneous emission dominated relaxation. The model is further expanded to include Doppler broadening and used to predict the peak gain as a function of detuning for a frequency doubled alexandrite laser-pumped cesium vapor gain cell.

  11. Raman-resonance-enhanced composite nonlinearity of air-guided modes in hollow photonic-crystal fibers.

    PubMed

    Fedotov, Il'ya V; Fedotov, Andrei B; Zheltikov, Aleksei M

    2006-09-01

    Coherent anti-Stokes Raman scattering (CARS) is used to measure relations between the resonant (Raman) and nonresonant (Kerr-type) optical nonlinearities of air-guided modes in a hollow-core photonic-crystal fiber (PCF). We demonstrate that, due to its interference nature, CARS provides a convenient tool for measuring the contribution of the fiber cladding to the total nonlinearity sensed by air-guided modes in hollow PCFs. On a Raman resonance with molecular vibrations in the gas that fills the fiber core, a two-color laser field is shown to induce optical nonlinearities that are several orders of magnitude higher than the nonresonant Kerr-type nonlinearities typical of air-guided PCF modes. PMID:16902633

  12. Strong dependence of surface plasmon resonance and surface enhanced Raman scattering on the composition of Au-Fe nanoalloys.

    PubMed

    Amendola, Vincenzo; Scaramuzza, Stefano; Agnoli, Stefano; Polizzi, Stefano; Meneghetti, Moreno

    2014-01-01

    Nanoalloys of noble metals with transition metals are crucial components for the integration of plasmonics with magnetic and catalytic properties, as well as for the production of low-cost photonic devices. However, due to synthetic challenges in the realization of nanoscale solid solutions of noble metals and transition metals, very little is known about the composition dependence of plasmonic response in nanoalloys. Here we demonstrate for the first time that the elemental composition of Au-Fe nanoalloys obtained by laser ablation in liquid solution can be tuned by varying the liquid environment. Due to surface passivation and reaction with thiolated ligands, the nanoalloys obtained by our synthetic protocol are structurally and colloidally stable. Hence, we studied the dependence of the surface plasmon resonance (SPR) on the iron fraction and, for the first time, we observed surface enhanced Raman scattering (SERS) in Au-Fe nanoalloys. SPR and SERS performances are strongly affected by the iron content and are investigated using analytical and numerical models. By demonstrating the strong modification of plasmonic properties on the composition, our results provide important insights into the exploitation of Au-Fe nanoalloys in photonics, nanomedicine, magneto-plasmonic and plasmon-enhanced catalysis. Moreover, our findings show that several other plasmonic materials exist beyond gold and silver nanostructures. PMID:24309909

  13. Detection of DNA Sequences Refractory to PCR Amplification Using a Biophysical SERRS Assay (Surface Enhanced Resonant Raman Spectroscopy)

    PubMed Central

    Feuillie, Cécile; Merheb, Maxime M.; Gillet, Benjamin; Montagnac, Gilles; Daniel, Isabelle; Hänni, Catherine

    2014-01-01

    The analysis of ancient or processed DNA samples is often a great challenge, because traditional Polymerase Chain Reaction – based amplification is impeded by DNA damage. Blocking lesions such as abasic sites are known to block the bypass of DNA polymerases, thus stopping primer elongation. In the present work, we applied the SERRS-hybridization assay, a fully non-enzymatic method, to the detection of DNA refractory to PCR amplification. This method combines specific hybridization with detection by Surface Enhanced Resonant Raman Scattering (SERRS). It allows the detection of a series of double-stranded DNA molecules containing a varying number of abasic sites on both strands, when PCR failed to detect the most degraded sequences. Our SERRS approach can quickly detect DNA molecules without any need for DNA repair. This assay could be applied as a pre-requisite analysis prior to enzymatic reparation or amplification. A whole new set of samples, both forensic and archaeological, could then deliver information that was not yet available due to a high degree of DNA damage. PMID:25502338

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

    PubMed Central

    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

  15. Strong dependence of surface plasmon resonance and surface enhanced Raman scattering on the composition of Au-Fe nanoalloys

    NASA Astrophysics Data System (ADS)

    Amendola, Vincenzo; Scaramuzza, Stefano; Agnoli, Stefano; Polizzi, Stefano; Meneghetti, Moreno

    2014-01-01

    Nanoalloys of noble metals with transition metals are crucial components for the integration of plasmonics with magnetic and catalytic properties, as well as for the production of low-cost photonic devices. However, due to synthetic challenges in the realization of nanoscale solid solutions of noble metals and transition metals, very little is known about the composition dependence of plasmonic response in nanoalloys. Here we demonstrate for the first time that the elemental composition of Au-Fe nanoalloys obtained by laser ablation in liquid solution can be tuned by varying the liquid environment. Due to surface passivation and reaction with thiolated ligands, the nanoalloys obtained by our synthetic protocol are structurally and colloidally stable. Hence, we studied the dependence of the surface plasmon resonance (SPR) on the iron fraction and, for the first time, we observed surface enhanced Raman scattering (SERS) in Au-Fe nanoalloys. SPR and SERS performances are strongly affected by the iron content and are investigated using analytical and numerical models. By demonstrating the strong modification of plasmonic properties on the composition, our results provide important insights into the exploitation of Au-Fe nanoalloys in photonics, nanomedicine, magneto-plasmonic and plasmon-enhanced catalysis. Moreover, our findings show that several other plasmonic materials exist beyond gold and silver nanostructures.Nanoalloys of noble metals with transition metals are crucial components for the integration of plasmonics with magnetic and catalytic properties, as well as for the production of low-cost photonic devices. However, due to synthetic challenges in the realization of nanoscale solid solutions of noble metals and transition metals, very little is known about the composition dependence of plasmonic response in nanoalloys. Here we demonstrate for the first time that the elemental composition of Au-Fe nanoalloys obtained by laser ablation in liquid solution can

  16. A Poly Adenine-Mediated Assembly Strategy for Designing Surface-Enhanced Resonance Raman Scattering Substrates in Controllable Manners.

    PubMed

    Zhu, Ying; Jiang, Xiangxu; Wang, Houyu; Wang, Siyi; Wang, Hui; Sun, Bin; Su, Yuanyuan; He, Yao

    2015-07-01

    In this article, we introduce a Poly adenine (Poly A)-assisted fabrication method for rationally designing surface-enhanced resonance Raman scattering (SERRS) substrates in controllable and reliable manners, enabling construction of core-satellite SERRS assemblies in both aqueous and solid phase (e.g., symmetric core (Au)-satellite (Au) nanoassemblies (Au-Au NPs), and asymmetric Ag-Au NPs-decorated silicon wafers (Ag-Au NPs@Si)). Of particular significance, assembly density is able to be controlled by varying the length of the Poly A block (e.g., 10, 30, and 50 consecutive adenines at the 5' end of DNA sequence, Poly A10/A30/A50), producing the asymmetric core-satellite nanoassemblies with adjustable surface density of Au NPs assembly on core NPs surface. Based on quantitative interrogation of the relationship between SERRS performance and assemble density, the Ag-Au NPs@Si featuring the strongest SERRS enhancement factor (EF ≈ 10(7)) and excellent reproducibility can be achieved under optimal conditions. We further employ the resultant Ag-Au NPs@Si as a high-performance SERRS sensing platform for the selective and sensitive detection of mercury ions (Hg(2+)) in a real system, with a low detection limit of 100 fM, which is ∼5 orders of magnitude lower than the United States Environmental Protection Agency (USEPA)-defined limit (10 nM) in drinkable water. These results suggest the Poly A-mediated assembly method as new and powerful tools for designing high-performance SERRS substrates with controllable structures, facilitating improvement of sensitivity, reliability, and reproducibility of SERRS signals. PMID:26028356

  17. Resonance IR: a coherent multidimensional analogue of resonance Raman.

    PubMed

    Boyle, Erin S; Neff-Mallon, Nathan A; Handali, Jonathan D; Wright, John C

    2014-05-01

    This work demonstrates the use of triply resonant sum frequency (TRSF) spectroscopy as a "resonance IR" analogue to resonance Raman spectroscopy. TRSF is a four-wave-mixing process where three lasers with independent frequencies interact coherently with a sample to generate an output at their triple summation frequency. The first two lasers are in the infrared and result in two vibrational excitations, while the third laser is visible and induces a two-quantum anti-Stokes resonance Raman transition. The signal intensity grows when the laser frequencies are all in resonance with coupled vibrational and electronic states. The method therefore provides electronic enhancement of IR-active vibrational modes. These modes may be buried beneath solvent in the IR spectrum and also be Raman-inactive and therefore inaccessible by other techniques. The method is presented on the centrosymmetric complex copper phthalocyanine tetrasulfonate. In this study, the two vibrational frequencies were scanned across ring-breathing modes, while the visible frequency was left in resonance with the copper phthalocyanine tetrasulfonate Q band, resulting in a two-dimensional infrared plot that also reveals coupling between vibrational states. TRSF has the potential to be a very useful probe of structurally similar biological motifs such as hemes, as well as synthetic transition-metal complexes. PMID:24707979

  18. Electronic resonances in broadband stimulated Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Batignani, G.; Pontecorvo, E.; Giovannetti, G.; Ferrante, C.; Fumero, G.; Scopigno, T.

    2016-01-01

    Spontaneous Raman spectroscopy is a formidable tool to probe molecular vibrations. Under electronic resonance conditions, the cross section can be selectively enhanced enabling structural sensitivity to specific chromophores and reaction centers. The addition of an ultrashort, broadband femtosecond pulse to the excitation field allows for coherent stimulation of diverse molecular vibrations. Within such a scheme, vibrational spectra are engraved onto a highly directional field, and can be heterodyne detected overwhelming fluorescence and other incoherent signals. At variance with spontaneous resonance Raman, however, interpreting the spectral information is not straightforward, due to the manifold of field interactions concurring to the third order nonlinear response. Taking as an example vibrational spectra of heme proteins excited in the Soret band, we introduce a general approach to extract the stimulated Raman excitation profiles from complex spectral lineshapes. Specifically, by a quantum treatment of the matter through density matrix description of the third order nonlinear polarization, we identify the contributions which generate the Raman bands, by taking into account for the cross section of each process.

  19. Electronic resonances in broadband stimulated Raman spectroscopy

    PubMed Central

    Batignani, G.; Pontecorvo, E.; Giovannetti, G.; Ferrante, C.; Fumero, G.; Scopigno, T.

    2016-01-01

    Spontaneous Raman spectroscopy is a formidable tool to probe molecular vibrations. Under electronic resonance conditions, the cross section can be selectively enhanced enabling structural sensitivity to specific chromophores and reaction centers. The addition of an ultrashort, broadband femtosecond pulse to the excitation field allows for coherent stimulation of diverse molecular vibrations. Within such a scheme, vibrational spectra are engraved onto a highly directional field, and can be heterodyne detected overwhelming fluorescence and other incoherent signals. At variance with spontaneous resonance Raman, however, interpreting the spectral information is not straightforward, due to the manifold of field interactions concurring to the third order nonlinear response. Taking as an example vibrational spectra of heme proteins excited in the Soret band, we introduce a general approach to extract the stimulated Raman excitation profiles from complex spectral lineshapes. Specifically, by a quantum treatment of the matter through density matrix description of the third order nonlinear polarization, we identify the contributions which generate the Raman bands, by taking into account for the cross section of each process. PMID:26728791

  20. Resonant Raman Scattering in Antiferromagnets

    NASA Astrophysics Data System (ADS)

    Chubukov, Andrey V.; Morr, Dirk K.

    1996-03-01

    Two-magnon Raman scattering provides important information about electronic correlations in the insulating parent compounds of high-Tc materials. Recent experiments have shown a strong dependence of the Raman signal in B_1g geometry on the frequency of the incoming photon. We present a detailed numerical study of the diagram which was previously identified(A.V. Chubukov and D.M. Frenkel, Phys. Rev. B 52), 9760 (1995) as the most relevant in the resonant regime. We found two maxima of the two-magnon peak hight at transferred frequencies of ω ≈ 3J and ω ≈ 8J. These results agree with recent experiments by Blumberg(G. Blumberg et al.), preprint et al. on Sr_2CuO_2Cl_2. Furthermore, we study how the two-magnon profile depends on a quasiparticle damping and a hopping between next-nearest neighbors. We also study resonance scattering in other scattering geometries, in particular, A_1g scattering.

  1. Single molecular detection of a perylene dye dispersed in a Langmuir-Blodgett fatty acid monolayer using surface-enhanced resonance Raman scattering

    NASA Astrophysics Data System (ADS)

    Constantino, C. J. L.; Lemma, T.; Antunes, P. A.; Aroca, R.

    2002-02-01

    The Langmuir-Blodgett (LB) monolayer technique was used to fabricate single molecule LB monolayer containing bis(phenethylimido)perylene (PhPTCD), a red dye dispersed in arachidic acid (AA) with an average doping of 1 molecule per μm 2. The monolayer was transferred onto Ag island films to obtain spatially resolved surface-enhanced resonance Raman scattering (SERRS) spectra. The mixed LB monolayers were fabricated with a concentration, on average, of 1, 6, 19 and 118 PhPTCD molecules per μm 2 in AA. The AA provides a two-dimensional host matrix whose background signal does not interfere with the detection of the probe molecule's SERRS signal. The properties of the single molecule detection were investigated using micro-Raman with a 514.5-nm laser line. The Ag island surfaces coated with the LB monolayer were mapped with spatial steps of 3 μm and global chemical imaging of the most intense SERRS band in the spectrum was also recorded. The SERRS and surface-enhanced fluorescence (SEF) of the neat and single molecule LB monolayer were recorded in a temperature range from liquid nitrogen to +200°C. Neat PhPTCD LB monolayer spectra served as reference for the identification of characteristic signatures of the single molecule behavior. The spatial resolution of Raman-microscopy experiments, the multiplicative effect of resonance Raman and SERRS, and the high sensitivity of the new dispersive Raman instruments, allow SERRS to be part of the family of single molecular spectroscopies.

  2. Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor

    NASA Technical Reports Server (NTRS)

    Lawandy, N. M.

    1986-01-01

    This work focused on understanding the effects of arbitrary transverse and longitudinal relaxation rates on the susceptibilities of coherently driven three-level systems. The approximation of a single relaxation rate often made in previous work is strongly invalidated by the variation in the spontaneous emission lifetime between various atomic level pairs in systems such as cesium. It is of great importance to the problem of nonlinear infrared generation to determine the dependence of both real and imaginary susceptibility on relaxation rates. The imaginary susceptibility on the pump transition determines the absorption of pump photons and the imaginary susceptibility on the laser transition determines the spectral dependence of the gain. This is of particular importance for pure Raman emission (i.e., absorption at linecenter of the gain transition) as it determines the tunability characteristics we are aiming to predict. The real susceptibility is important when cavities are used at the signal field as this will determine the loaded resonance of the Raman oscillator. Researchers show that in some cases which result from having different relaxation rates mode splitting may result, allowing more than one frequency to have the same Raman wavelength, possibly resulting in a temporal instability.

  3. Theoretical studies of resonance enhanced stimulated raman scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor. Progress report

    SciTech Connect

    Lawandy, N.M.

    1986-10-01

    This work focused on understanding the effects of arbitrary transverse and longitudinal relaxation rates on the susceptibilities of coherently driven three-level systems. The approximation of a single relaxation rate often made in previous work is strongly invalidated by the variation in the spontaneous emission lifetime between various atomic level pairs in systems such as cesium. It is of great importance to the problem of nonlinear infrared generation to determine the dependence of both real and imaginary susceptibility on relaxation rates. The imaginary susceptibility on the pump transition determines the absorption of pump photons and the imaginary susceptibility on the laser transition determines the spectral dependence of the gain. This is of particular importance for pure Raman emission (i.e., absorption at linecenter of the gain transition) as it determines the tunability characteristics we are aiming to predict. The real susceptibility is important when cavities are used at the signal field as this will determine the loaded resonance of the Raman oscillator. Researchers show that in some cases which result from having different relaxation rates mode splitting may result, allowing more than one frequency to have the same Raman wavelength, possibly resulting in a temporal instability.

  4. Surface-Enhanced Raman Scattering and Biophysics

    NASA Astrophysics Data System (ADS)

    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.

  5. UV Resonant Raman Spectrometer with Multi-Line Laser Excitation

    NASA Technical Reports Server (NTRS)

    Lambert, James L.; Kohel, James M.; Kirby, James P.; Morookian, John Michael; Pelletier, Michael J.

    2013-01-01

    A Raman spectrometer employs two or more UV (ultraviolet) laser wavel engths to generate UV resonant Raman (UVRR) spectra in organic sampl es. Resonant Raman scattering results when the laser excitation is n ear an electronic transition of a molecule, and the enhancement of R aman signals can be several orders of magnitude. In addition, the Ra man cross-section is inversely proportional to the fourth power of t he wavelength, so the UV Raman emission is increased by another fact or of 16, or greater, over visible Raman emissions. The Raman-scatter ed light is collected using a high-resolution broadband spectrograph . Further suppression of the Rayleigh-scattered laser light is provi ded by custom UV notch filters.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Near-resonance enhanced O2 detection for dual-broadband pure rotational coherent anti-Stokes Raman scattering with an ultraviolet-visible setup at 266 nm

    SciTech Connect

    Schenk, Martin; Seeger, Thomas; Leipertz, Alfred

    2005-07-01

    Broadband and dual-broadband coherent anti-Stokes Raman scattering (CARS) are widely established tools for nonintrusive gas diagnostics. Up to now the investigations have been mainly performed for electronic nonresonant conditions of the gas species of interest. We report on the enhancement of the O2-N2 detection limit of dual-broadband pure rotational CARS by shifting the wavelength of the narrowband pump laser from the commonly used 532-266 nm. This enhancement is caused when the Schumann-Runge absorption band is approached near 176 nm. The principal concept of this experiment, i.e., covering the Raman resonance with a single- or dual-broadband combination of lasers in the visible range and moving only the narrowband probe laser near or directly into electronic resonant conditions in the UV range, should also be applicable to broadband CARS experiments to directly exploit electronic resonance effects for the purpose of single-shot concentration measurements of minority species. To quantify the enhancement in O2 sensitivity, comparative measurements at both a 266 and a 532 nm narrowband pump laser wavelength are presented, employing a 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyram (DCM) dye laser as a broadband laser source at 635 nm. An increase of approximately 13% in the ratio of the rotational CARS cross sections of O2 and N2 was obtained. The broad spectral width of the CARS excitation profile was approximately equal for both setups. Further enhancement should be achievable by shifting the narrowband pump laser closer toward 176 nm, for example, with a frequency-doubled optical parametric oscillator or an excimer laser. The principal concept of this experiment should also be applicable to broadband CARS experiments to directly exploit electronic resonance effects of the narrowband pump laser with electronic transitions of minority species for the purpose of single-shot concentration measurements of those species.

  8. Application of resonance Raman LIDAR for chemical species identification

    SciTech Connect

    Chen, C.L.; Heglund, D.L.; Ray, M.D.; Harder, D.; Dobert, R.; Leung, K.P.; Wu, M.; Sedlacek, A.

    1997-07-01

    BNL has been developing a remote sensing technique for the detection of atmospheric pollutants based on the phenomenon of resonance Raman LIDAR that has also incorporated a number of new techniques/technologies designed to extend it`s performance envelope. When the excitation frequency approaches an allowed electronic transition of the molecule, an enormous enhancement of the inelastic scattering cross-section can occur, often up to 2 to 4 orders-of-magnitude, and is referred to as resonance Raman (RR), since the excitation frequency is in resonance with an allowed electronic transition. Exploitation of this enhancement along with new techniques such as pattern recognition algorithms to take advantage of the spectral fingerprint and a new laser frequency modulation technique designed to suppress broadband fluorescence, referred to as Frequency modulated Excitation Raman Spectroscopy (FreMERS) and recent developments in liquid edge filter technology, for suppression of the elastic channel, all help increase the overall performance of Raman LIDAR.

  9. Remote sensing of the atmosphere by resonance Raman LIDAR

    SciTech Connect

    Sedlacek, A.J.; Harder, D.; Leung, K.P.; Zuhoski, P.B. Jr.; Burr, D.; Chen, C.L.

    1994-12-01

    When in resonance, Raman scattering exhibits strong enhancement ranging from four to six orders of magnitude. This physical phenomenon has been applied to remote sensing of the Earth`s atmosphere. With a 16 inch Cassegrain telescope and spectrometer/ CCD-detector system, 70-150 ppm-m of SO{sub 2} in the atmosphere has been detected at a distance of 0.5 kilometer. This system can be used to detect/monitor chemical effluence in the atmosphere by their unique Raman fingerprints. Experimental result together with detailed resonance Raman and atmospheric laser propagation effects will be discussed.

  10. Probing Nanoscale Pentacene Films by Resonant Raman Scattering

    NASA Astrophysics Data System (ADS)

    He, Rui; Dujovne, Irene; Chen, Liwei; Miao, Qian; Hirjibehedin, Cyrus F.; Pinczuk, Aron; Nuckolls, Colin; Kloc, Christian; Blanchet, Graciela B.

    2005-06-01

    Resonant enhancements of Raman scattering intensities offer the sensitivity required to study nanoscale pentacene films that reach into monolayer thickness. In the results reported here structural characterization of ultra-thin layers and of their fundamental optical properties are investigated by resonant Raman scattering from intra-molecular and inter-molecular vibrations. In this work Raman methods emerge as ideal tools for the study of physics and characterization of ultra-thin nanoscale films of molecular organic materials fabricated on diverse substrates of current and future devices.

  11. Sensitive algorithm for multiple-excitation-wavelength resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Yellampalle, Balakishore; Wu, Hai-Shan; McCormick, William; Sluch, Mikhail; Martin, Robert; Ice, Robert; Lemoff, Brian E.

    2014-05-01

    Raman spectroscopy is a widely used spectroscopic technique with a number of applications. During the past few years, we explored the use of simultaneous multiple-excitation-wavelengths (MEW) in resonance Raman spectroscopy. This approach takes advantage of Raman band intensity variations across the Resonance Raman spectra obtained from two or more excitation wavelengths. Amplitude variations occur between corresponding Raman bands in Resonance Raman spectra due to complex interplay of resonant enhancement, self-absorption and laser penetration depth. We have developed a very sensitive algorithm to estimate concentration of an analyte from spectra obtained using the MEW technique. The algorithm uses correlations and least-square minimization approach to calculate an estimate for the concentration. For two or more excitation wavelengths, measured spectra were stacked in a two dimensional matrix. In a simple realization of the algorithm, we approximated peaks in the ideal library spectra as triangles. In this work, we present the performance of the algorithm with measurements obtained from a dual-excitation-wavelength Resonance Raman sensor. The novel sensor, developed at WVHTCF, detects explosives from a standoff distance. The algorithm was able to detect explosives with very high sensitivity even at signal-to-noise ratios as low as ~1.6. Receiver operating characteristics calculated using the algorithm showed a clear benefit in using the dual-excitation-wavelength technique over single-excitation-wavelength techniques. Variants of the algorithm that add more weight to amplitude variation information showed improved specificity to closely resembling spectra.

  12. Water in the hydration shell of halide ions has significantly reduced Fermi resonance and moderately enhanced Raman cross section in the OH stretch regions.

    PubMed

    Ahmed, Mohammed; Singh, Ajay K; Mondal, Jahur A; Sarkar, Sisir K

    2013-08-22

    Water in the presence of electrolytes plays an important role in biological and industrial processes. The properties of water, such as the intermolecular coupling, Fermi resonance (FR), hydrogen-bonding, and Raman cross section were investigated by measuring the Raman spectra in the OD and OH stretch regions in presence of alkali halides (NaX; X = F, Cl, Br, I). It is observed that the changes in spectral characteristics by the addition of NaX in D2O are similar to those obtained by the addition of H2O in D2O. The spectral width decreases significantly by the addition of NaX in D2O (H2O) than that in the isotopically diluted water. Quantitative estimation, on the basis of integrated Raman intensity, revealed that the relative Raman cross section, σ(H)/σ(b) (σ(H) and σ(b) are the average Raman cross section of water in the first hydration shell of X(-) and in bulk, respectively), in D2O and H2O is higher than those in the respective isotopically diluted water. These results suggest that water in the hydration shell has reduced FR and intermolecular coupling compared to those in bulk. In the isotopically diluted water, the relative Raman cross section increases with increase in size of the halide ions (σ(H)/σ(b) = 0.6, 1.1, 1.5, and 1.9 for F(-), Cl(-), Br(-), and I(-), respectively), which is assignable to the enhancement of Raman cross section by charge transfer from halide ions to the hydrating water. Nevertheless, the experimentally determined σ(H)/σ(b) is lower than the calculated values obtained on the basis of the energy of the charge transfer state of water. The weak enhancement of σ(H)/σ(b) signifies that the charge transfer transition in the hydration shell of halide ions causes little change in the OD (OH) bond lengths of hydrating water. PMID:23895453

  13. Studies on adsorption of mono- and multi-chromophoric hemicyanine dyes on silver nanoparticles by surface-enhanced resonance raman and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Biswas, Nandita; Thomas, Susy; Kapoor, Sudhir; Mishra, Amaresh; Wategaonkar, Sanjay; Mukherjee, Tulsi

    2008-11-01

    Structural and vibrational properties of mono- and multichromophoric hemicyanine (HC) dyes in solution and adsorbed on silver-coated films have been investigated using optical absorption and resonance Raman scattering techniques, with interpretations aided by theoretical calculations. This is the first report on the Raman spectroscopic studies of multichromophoric HC derivatives. The structure of the monomer, N-propyl-4-(p-N,N-dimethylamino styryl)pyridinium bromide (HC3), and its charged and neutral silver complexes (HC3-Ag) in the ground electronic (S0) state were optimized using density functional calculations with the B3LYP method using the 6-31G* and LANL2DZ basis sets. The ground state structure of N-hexyl-4-(p-N,N-dimethylamino styryl)pyridinium bromide (HC6) and multichromophoric HC dyes were computed using the HF /6-31G* method. The negligible shift or broadening observed in the electronic absorption and resonance Raman spectra in solution with increasing size of the HC chromophore suggests that the excitations are localized within individual monomer units in bis and tetra chromophores. However, in the tris chromophore, considerable redshift and broadening were observed, indicating a significant electronic interaction between the nonbonded electrons of the N atom and the aromatic π-system that is supported by the calculated excitation energies using the time-dependent density functional theory method. The effect of HC dye concentration on the electronic absorption spectra of the silver-coated film showed significant broadening, which was attributed to the formation of H- and J-aggregates in addition to the formation of a metal-molecule complex. A considerable redshift along various vibrations observed in the surface-enhanced resonance Raman scattering (SERRS) spectra of the HC derivatives indicates that adsorption on the silver surface leads to a considerable interaction of the electron rich moiety of HC derivatives with the silver surface. The

  14. Fluctuating single sp2 carbon clusters at single hotspots of silver nanoparticle dimers investigated by surface-enhanced resonance Raman scattering

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    We evaluate spectral changes in surface enhanced resonance Raman scattering (SERRS) of near-single dye molecules in hotspots of single Ag nanoparticle (NP) dimers. During the laser excitation, surface enhance florescence (SEF) of dye disappeared and the number of SERRS lines decreased until finally ca. two lines remained around 1600 and 1350 cm-1, those are evidence of G and D lines of single sp2 carbon clusters. Analysis of the G and D line intensity ratios reveals the temporal fluctuation in the crystallite size of the clusters within several angstroms; whereas, broadening and splitting in the lines enable us for identifying directly the dynamics of various defects in the clusters. This analysis reveals that the detailed fluctuations of single sp2 carbon clusters, which would be impossible to gain with other microscopic methods.

  15. Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelength in cesium vapor

    NASA Technical Reports Server (NTRS)

    Lawandy, Nabil M.

    1987-01-01

    The third phase of research will focus on the propagation and energy extraction of the pump and SERS beams in a variety of configurations including oscillator structures. In order to address these questions a numerical code capable of allowing for saturation and full transverse beam evolution is required. The method proposed is based on a discretized propagation energy extraction model which uses a Kirchoff integral propagator coupled to the three level Raman model already developed. The model will have the resolution required by diffraction limits and will use the previous density matrix results in the adiabatic following limit. Owing to its large computational requirements, such a code must be implemented on a vector array processor. One code on the Cyber is being tested by using previously understood two-level laser models as guidelines for interpreting the results. Two tests were implemented: the evolution of modes in a passive resonator and the evolution of a stable state of the adiabatically eliminated laser equations. These results show mode shapes and diffraction losses for the first case and relaxation oscillations for the second one. Finally, in order to clarify the computing methodology used to exploit the speed of the Cyber's computational speed, the time it takes to perform both of the computations previously mentioned to run on the Cyber and VAX 730 must be measured. Also included is a short description of the current laser model (CAVITY.FOR) and a flow chart of the test computations.

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

    NASA Astrophysics Data System (ADS)

    Rösch, P.; Popp, J.; Kiefer, W.

    1999-05-01

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

  17. Intensity enhancement and selective detection of proximate solvent molecules by molecular near-field effect in resonance hyper-Raman scattering

    NASA Astrophysics Data System (ADS)

    Shimada, Rintaro; Kano, Hideaki; Hamaguchi, Hiro-o.

    2008-07-01

    A new molecular phenomenon associated with resonance hyper-Raman (HR) scattering in solution has been discovered. Resonance HR spectra of all-trans-β-carotene and all-trans-lycopene in various solvents exhibited several extra bands that were not assignable to the solute but were unequivocally assigned to the solvents. Neat solvents did not show detectable HR signals under the same experimental conditions. Similar experiments with all-trans-retinal did not exhibit such enhancement either. All-trans-β-carotene and all-trans-lycopene have thus been shown to induce enhanced HR scattering of solvent molecules through a novel molecular effect that is not associated with all-trans-retinal. We call this new effect the "molecular near-field effect." In order to explain this newly found effect, an extended vibronic theory of resonance HR scattering is developed where the vibronic interaction including the proximate solvent molecule (intermolecular vibronic coupling) is explicitly introduced in the solute hyperpolarizability tensor. The potential of "molecular near-field HR spectroscopy," which selectively detects molecules existing in the close vicinity of a HR probe in complex chemical or biological systems, is discussed.

  18. Exploitation of resonance Raman spectroscopy as a remote chemical sensor

    SciTech Connect

    Sedlacek, A.J.; Chen, C.L.

    1995-08-01

    We have discussed recent experimental results using a resonance-Raman-based LIDAR system as a remote chemical sensor. This spectroscopy has the fundamental advantage that it is based on optical fingerprints that are insensitive to environmental perturbations. By taking advantage of resonance enhancement, which 6 orders-of-magnitude, can be as large as 4 to an increased sensing range for a given chemical concentration or lower detection limit for a given stand-off distance can be realized. The success discussed above can in part be traced back to the use of new state-of-the-art technologies which, only recently, have allowed the phenomenon of resonance-enhanced Raman spectroscopy to be fully exploited as a remote chemical sensor platform. Since many chemicals have electronic transitions in the UV/IS, it is expected that many will have pronounced resonance enhancements.

  19. Enhancing the efficiency of silicon Raman converters

    NASA Astrophysics Data System (ADS)

    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.

  20. Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency-doubled Alexandrite laser wavelength in cesium vapor

    NASA Technical Reports Server (NTRS)

    Lawandy, Nabil M.

    1987-01-01

    The solutions for the imaginary susceptibility of the Raman field transition with arbitrary relaxation rates and field strengths are examined for three different sets of relaxation rates. These rates correspond to: (1) Far Infrared (FIR) Raman lasers in the diabatic collision regime without consideration of coupled population decay in a closed system, (2) Raman FIR lasers in the diabatic collision regime with coupled population conserving decay, and (3) IR Raman gain in cesium vapor. The model is further expanded to include Doppler broadening and used to predict the peak gain as a function of detuning for a frequency doubled Alexandrite laser-pumped cesium vapor gain cell.

  1. Dual-excitation wavelength resonance Raman explosives detector

    NASA Astrophysics Data System (ADS)

    Yellampalle, Balakishore; Sluch, Mikhail; Wu, Hai-Shan; Martin, Robert; McCormick, William; Ice, Robert; 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: 1) resonant enhancement of Raman cross-section, 2) λ-4-cross-section enhancement, and 3) fluorescence and solar background free signatures. For trace detection, these signal enhancements more than offset the small penetration depth due to DUV absorption. A key challenge for stand-off sensors is to distinguish explosives, with high confidence, from a myriad of unknown background materials that may have interfering spectral peaks. To address this, we are developing a stand-off explosive sensor using DUVRRS with two simultaneous DUV excitation wavelengths. Due to complex interplay of resonant enhancement, self-absorption and laser penetration depth, significant amplitude variation is observed between corresponding Raman bands with different excitation wavelengths. These variations with excitation wavelength provide an orthogonal signature that complements the traditional Raman signature to improve specificity relative to single-excitation-wavelength techniques. As part of this effort, we are developing two novel CW DUV lasers, which have potential to be compact, and a compact dual-band high throughput DUV spectrometer, capable of simultaneous detection of Raman spectra in two spectral windows. We have also developed a highly sensitive algorithm for the detection of explosives under low signal-to-noise situations.

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

    PubMed

    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

  3. Proliferation detection using a remote resonance Raman chemical sensor

    SciTech Connect

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

    1993-08-01

    The authors discussed the potential of the resonance Raman chemical sensor as a remote sensor that can be used for gases, liquids or solids. This spectroscopy has the fundamental advantage that it is based on optical fingerprints that are insensitive to environmental perturbations or excitation frequency. By taking advantage of resonance enhancement, the inelastic scattering cross-section can increase anywhere from 4 to 6 orders of magnitude which translates into increased sensing range or lower detection limits. It was also shown that differential cross-sections as small as 10{sup {minus}27} cm{sup 2}/sr do not preclude the use of this technique as being an important component in one`s remote-sensing arsenal. The results obtained in the early 1970s on various pollutants and the more recent work on atmospheric water cast a favorable light on the prospects for the successful development of a resonance Raman remote sensor. Currently, of the 20 CW agent-related {open_quotes}signature{close_quotes} chemicals that the authors have investigated, 18 show enhancements ranging from 3 to 6 orders of magnitude. The absolute magnitudes of the measured resonance enhanced Raman cross-sections for these 18 chemicals suggest that detection and identification of trace quantities of the {open_quotes}signature{close_quotes} chemicals, through a remote resonance Raman chemical sensor, could be achieved.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Surface-Enhanced Raman Spectroscopy.

    ERIC Educational Resources Information Center

    Garrell, Robin L.

    1989-01-01

    Reviews the basis for the technique and its experimental requirements. Describes a few examples of the analytical problems to which surface-enhanced Raman spectroscopy (SERS) has been and can be applied. Provides a perspective on the current limitations and frontiers in developing SERS as an analytical technique. (MVL)

  6. Resonant Raman spectroscopy of twisted multilayer graphene.

    PubMed

    Wu, Jiang-Bin; Zhang, Xin; Ijäs, Mari; Han, Wen-Peng; Qiao, Xiao-Fen; Li, Xiao-Li; Jiang, De-Sheng; Ferrari, Andrea C; Tan, Ping-Heng

    2014-01-01

    Graphene and other two-dimensional crystals can be combined to form various hybrids and heterostructures, creating materials on demand with properties determined by the interlayer interaction. This is the case even for a single material, where multilayer stacks with different relative orientation have different optical and electronic properties. Probing and understanding the interface coupling is thus of primary importance for fundamental science and applications. Here we study twisted multilayer graphene flakes with multi-wavelength Raman spectroscopy. We find a significant intensity enhancement of the interlayer coupling modes (C peaks) due to resonance with new optically allowed electronic transitions, determined by the relative orientation of the layers. The interlayer coupling results in a Davydov splitting of the C peak in systems consisting of two equivalent graphene multilayers. This allows us to directly quantify the interlayer interaction, which is much smaller compared with Bernal-stacked interfaces. This paves the way to the use of Raman spectroscopy to uncover the interface coupling of two-dimensional hybrids and heterostructures. PMID:25382099

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

    SciTech Connect

    Chen, Dong; Zhou, Jun; Rippa, Massimo; Petti, Lucia

    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.

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

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Zhou, Jun; Rippa, Massimo; Petti, Lucia

    2015-10-01

    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 ˜107 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.

  9. Enhanced Raman Monitor Project

    NASA Technical Reports Server (NTRS)

    Westenskow, Dwayne

    1996-01-01

    Monitoring of gaseous contaminants stems from the need to ensure a healthy and safe environment. NASA/Ames needs sensors that are able to monitor common atmospheric gas concentrations as well as trace amounts of contaminant gases. To provide an accurate assessment of air quality, a monitoring system would need to be continuous and on-line with full spectrum capabilities, allowing simultaneous detection of all gas components in a sample, including both combustible and non-combustible gases. The system demands a high degree of sensitivity to detect low gas concentrations in the low-ppm and sub-ppm regions. For clean and healthy air ('good' category), criteria established by the EPA requires that contaminant concentrations not exceed 4 ppm of carbon monoxide (CO) in an 8 hour period, 60 ppb of ozone(O3) in a one hour period and 30 ppb of sulfur dioxide (SO2) in a 24 hour period. One step below this is the National Ambient Air Quality Standard ('moderate' category) which requires that contaminant concentrations not exceed 9 ppm of carbon monoxide (CO), 120 ppb of ozone (O3) and 140 ppb of sulfur dioxide (SO2) for their respective time periods. Ideally a monitor should be able to detect the concentrations specified in the 'good' category. To benchmark current abilities of Raman technology in gas phase analysis, laboratory experiments were performed to evaluate the RASCAL II anesthetic gas monitor.

  10. Novel Raman resonance in ladder spin systems

    NASA Astrophysics Data System (ADS)

    Donkov, Alexander; Chubukov, Andrey

    2006-03-01

    We consider Raman intensity in spin S two-leg- spin-ladder, with the goal to understand recent experiments[1,2]. We argue that the Raman intensity has a pseudo-resonance peak whose width is very small at large S. The pseudo-resonance originates from the existence of a local minimum in the magnon excitation spectrum, and is located slightly below twice the magnon energy at the minimum. The physics behind the peak is surprisingly similar to that in the excitonic scenario for the neutron and Raman resonances in a d-wave superconductor. We also consider mid-infrared X-ray scattering in 2D systems and compare the results with recent measurements [3]. [1] A. Gozar et al, Phys. Rev. Lett. 87, 197202 (2001). [2] S. Sugai and M. Suzuki, Phys stat sol (b) 215, 653 (1999). [3] J. P. Hill, G Blumberg et al, [unpublished

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  12. Ultrafast saturation of electronic-resonance-enhanced coherent anti-Stokes Raman scattering and comparison for pulse durations in the nanosecond to femtosecond regime

    NASA Astrophysics Data System (ADS)

    Patnaik, Anil K.; Roy, Sukesh; Gord, James R.

    2016-02-01

    The saturation threshold of a probe pulse in an ultrafast electronic-resonance-enhanced (ERE) coherent anti-Stokes Raman spectroscopy (CARS) configuration is calculated. We demonstrate that while the underdamping condition is a sufficient condition for saturation of ERE-CARS with the long-pulse excitations, a transient gain must be achieved to saturate the ERE-CARS signal for the ultrafast probe regime. We identify that the area under the probe pulse can be used as a definitive parameter to determine the criterion for a saturation threshold for ultrafast ERE-CARS. From a simplified analytical solution and a detailed numerical calculation based on density-matrix equations, the saturation threshold of ERE-CARS is compared for a wide range of probe-pulse durations from the 10-ns to the 10-fs regime. The theory explains both qualitatively and quantitatively the saturation thresholds of resonant transitions and also gives a predictive capability for other pulse duration regimes. The presented criterion for the saturation threshold will be useful in establishing the design parameters for ultrafast ERE-CARS.

  13. Nanoparticle Based Surface-Enhanced Raman Spectroscopy

    SciTech Connect

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

    2005-01-03

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

  14. UV resonance Raman analysis of trishomocubane and diamondoid dimers

    SciTech Connect

    Meinke, Reinhard Thomsen, Christian; Maultzsch, Janina; Richter, Robert; Merli, Andrea; Fokin, Andrey A.; Koso, Tetyana V.; Schreiner, Peter R.; Rodionov, Vladimir N.

    2014-01-21

    We present resonance Raman measurements of crystalline trishomocubane and diamantane dimers containing a C=C double bond. Raman spectra were recorded with excitation energies between 2.33 eV and 5.42 eV. The strongest enhancement is observed for the C=C stretch vibration and a bending mode involving the two carbon atoms of the C=C bond, corresponding to the B{sub 2g} wagging mode of ethylene. This is associated with the localization of the π-HOMO and LUMO and the elongation of the C=C bond length and a pyramidalization of the two sp{sup 2}-hybridized carbon atoms at the optical excitation. The observed Raman resonance energies of the trishomocubane and diamantane dimers are significantly lower than the HOMO-LUMO gaps of the corresponding unmodified diamondoids.

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

    PubMed

    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

  16. Molecular spectroscopy of uranium(IV) bis(ketimido) complexes. rare observation of resonance-enhanced raman scattering from organoactinide complexes and evidence for broken-symmetry excited states.

    PubMed

    Da Re, Ryan E; Jantunen, Kimberly C; Golden, Jeffrey T; Kiplinger, Jaqueline L; Morris, David E

    2005-01-19

    Electronic absorption and resonance-enhanced Raman spectra for ketimido (azavinylidene) complexes of tetravalent uranium, (C(5)Me(5))(2)U[-N=C(Ph)(R)](2) (R = Ph, Me, and CH(2)Ph), have been recorded. The absorption spectra exhibit four broad bands between 13 000 and 24 000 cm(-1). The highest-energy band is assigned to the ketimido-localized p( perpendicular)(N)-->pi(N=C) transition based on comparison to the spectra of (C(5)H(5))(2)Zr[-N=CPh(2)](2) and (C(5)Me(5))(2)Th[-N=CPh(2)](2). Upon excitation into any of these four absorption bands, the (C(5)Me(5))(2)U[-N=C(Ph)(R)](2) complexes exhibit resonance enhancement for several Raman bands attributable to vibrations of the ketimido ligands. Raman bands for both the symmetric and nominally asymmetric N=C stretching bands are resonantly enhanced upon excitation into the p( perpendicular)(N)-->pi(N=C) absorption bands, indicating that the excited state is localized on a single ketimido ligand. Raman excitation profiles for (C(5)Me(5))(2)U[-N=CPh(2)](2) confirm that at least one of the lower-energy electronic absorption bands (E(max) approximately 16300 cm(-1)) is a charge-transfer transition between the U(IV) center and the ketimido ligand(s). The observations of both charge-transfer transitions and resonance enhancement of Raman vibrational bands are exceedingly rare for tetravalent actinide complexes and reflect the strong bonding interactions between the uranium 5f/6d orbitals and those on the ketimido ligands. PMID:15643893

  17. Resonance Raman spectroscopy utilizing tunable deep ultraviolet excitation for materials characterization

    NASA Astrophysics Data System (ADS)

    Chadwick, Christopher Todd

    Resonance Raman spectroscopy offers some key benefits over other spectroscopy methods. In one facet, resonance Raman provides a level of specificity not present in non-resonant Raman scattering. In another facet, resonance Raman can provide increased scattering cross-sections that rival those associated with the intensities of species fluorescence. These features provide mechanisms for improved trace species detection in current Raman remote sensing applications; as well as signal level enhancement in tiny volume regimes, such as those typical in near-field optical microscopy. This dissertation presents three main thrusts that are not well documented in the previous resonance Raman studies. We demonstrate fine resolution (approx 0:1nm) resonance tuning of the excitation wavelength corresponding to sharp absorption bands in liquid benzene and liquid toluene. The Raman spectra for these materials show an appreciable increase in scattering intensity of fundamental vibrational modes and show significant enhancements in scattering intensities for overtone and combination vibrational modes not observed with non-resonant excitation. Resonantly excited fundamental modes are observed to be enhanced by 3 to 5 orders of magnitude over non-resonant excitation; and several resonantly excited overtone modes are observed for both liquid benzene and liquid toluene. We have observed, that for liquid benzene and liquid toluene, the maximum Raman scattering intensity is realized when the excitation wavelength corresponds to that of the vapor phase absorption maximum, not the liquid phase absorption maximum as expected. We present a simple model of the time-dependent energy accumulation in the scattering volume that suggests that the scattering medium is a highly disorganized fluid. The observed Raman scattering intensity originates from this metastable fluid observed during the liquid-vapor phase transition. Using different concentration solutions of liquid benzene in heptane, we

  18. Raman-assisted Rabi resonances in two-mode cavity QED

    SciTech Connect

    Gruenwald, P.; Singh, S. K.; Vogel, W.

    2011-06-15

    The dynamics of a vibronic system in a lossy two-mode cavity is studied, with the first mode being resonant to the electronic transition and the second one being nearly resonant due to Raman transitions. We derive analytical solutions for the dynamics of this system. For a properly chosen detuning of the second mode from the exact Raman resonance, we obtain conditions that are closely related to the phenomenon of Rabi resonance as it is well known in laser physics. Such resonances can be observed in the spontaneous emission spectra, where the spectrum of the second mode in the case of weak Raman coupling is enhanced substantially.

  19. X-ray resonant Raman spectroscopy

    SciTech Connect

    Cowan, P.L.; LeBrun, T.; Deslattes, R.D.

    1995-08-01

    X-ray resonant Raman scattering presents great promise as a high-resolution spectroscopic probe of the electronic structure of matter. Unlike other methods, the technique avoids the loss of energy resolution resulting from the lifetime broadening of short-lived core-excited states. In addition, measurements of polarization and angular anisotropies yield information on the symmetries of electronic states of atoms and molecules. We studied the L{sub 3} edge of xenon, where the lifetime broadening is a major feature of the spectra recorded previously. X-ray fluorescence spectra were taken of both the L{alpha}{sub l,2} and L{beta}{sub 2,15} peaks over a range of energies from 10 eV below the edge to 40 eV above. These spectra show the evolution of resonant Raman scattering into characteristic fluorescence as the photon energy is scanned across the edge, and confirm several features of these spectra such as asymmetries in resonant peak shapes due to the onset of the ionization continuum. These results constitute the most comprehensive study of X-ray resonant Raman scattering to date, and were submitted for publication. Studies of other cases are under way, and new instruments that would match the unique characteristics of the APS - and thus render a new range of experiments possible - are under consideration.

  20. Enhanced Raman scattering of biological molecules

    NASA Astrophysics Data System (ADS)

    Montoya, Joseph R.

    The results presented in this thesis, originate from the aspiration to develop an identification algorithm for Salmonella enterica Serovar Enteritidis (S. enterica), Escherichia coli (E. coli), Bacillus globigii ( B. globigii), and Bacillus megaterium ( B. megaterium) using "enhanced" Raman scattering. We realized our goal, with a method utilizing an immunoassay process in a spectroscopic technique, and the direct use of the enhanced spectral response due to bacterial surface elements. The enhanced Raman signal originates from Surface Enhanced Raman Scattering (SERS) and/or Morphological Dependent Resonances (MDR's). We utilized a modified Lee-Meisel colloidal production method to produce a SERS active substrate, which was applied to a SERS application for the amino acid Glycine. The comparison indicates that the SERS/FRACTAL/MDR process can produce an increase of 107 times more signal than the bulk Raman signal from Glycine. In the extension of the Glycine results, we studied the use of SERS related to S. enterica, where we have shown that the aromatic amino acid contribution from Phenylalanine, Tyrosine, and Tryptophan produces a SERS response that can be used to identify the associated SERS vibrational modes of a S. enterica one or two antibody complexes. The "fingerprint" associated with the spectral signature in conjunction with an enhanced Raman signal allows conclusions to be made: (1) about the orientation of the secondary structure on the metal; (2) whether bound/unbound antibody can be neglected; (3) whether we can lower the detection limit. We have lowered the detection limit of S. enterica to 106 bacteria/ml. We also show a profound difference between S. enterica and E. coli SERS spectra even when there exists non-specific binding on E. coli indicating a protein conformation change induced by the addition of the antigen S. enterica. We confirm TEM imagery data, indicating that the source of the aromatic amino acid SERS response is originating from

  1. Resonance Raman spectroscopic study of fused multiporphyrin linear arrays

    NASA Astrophysics Data System (ADS)

    Jeong, Dae Hong; Jang, Sung Moon; Hwang, In-Wook; Kim, Dongho; Matsuzaki, Yoichi; Tanaka, Kazuyoshi; Tsuda, Akihiko; Nakamura, Takeshi; Osuka, Atsuhiro

    2003-09-01

    For prospective applications as molecular electric wires, triply linked fused porphyrin arrays have been prepared. As expected from their completely flat molecular structures, π-electron delocalization can be extended to the whole array manifested by a continuous redshift of the HOMO-LUMO transition band to infrared region up to a few μm as the number of porphyrin units in the array increases. To gain an insight into the relationship between the molecular structures and electronic properties, we have investigated resonance Raman spectra of fused porphyrin arrays depending on the number of porphyrin pigments in the array. We have carried out the normal mode analysis of fused porphyrin dimer based on the experimental results including Raman frequency shifts of two types of 13C-isotope substituted dimers, Raman enhancement pattern by changing excitation wavelength, and depolarization ratio measurements as well as normal-mode calculations at the B3LYP/6-31G level. In order to find the origins for the resonance Raman mode enhancement mechanism, we have predicted both the excited state geometry changes (A-term) and the vibronic coupling efficiencies (B-term) for the relevant electronic transitions based on the INDO/S-SCI method. A detailed normal mode analysis of the fused dimer allows us to extend successfully our exploration to longer fused porphyrin arrays. Overall, our investigations have provided a firm basis in understanding the molecular vibrations of fused porphyrin arrays in relation to their unique flat molecular structures and rich electronic transitions.

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

    NASA Technical Reports Server (NTRS)

    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.

  3. UV-resonance Raman spectroscopy of amino acids

    NASA Astrophysics Data System (ADS)

    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).

  4. Plasmon enhanced Raman scattering effect for an atom near a carbon nanotube.

    PubMed

    Bondarev, I V

    2015-02-23

    Quantum electrodynamics theory of the resonance Raman scattering is developed for an atom in a close proximity to a carbon nanotube. The theory predicts a dramatic enhancement of the Raman intensity in the strong atomic coupling regime to nanotube plasmon near-fields. This resonance scattering is a manifestation of the general electromagnetic surface enhanced Raman scattering effect, and can be used in designing efficient nanotube based optical sensing substrates for single atom detection, precision spontaneous emission control, and manipulation. PMID:25836436

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

    PubMed

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

    2016-12-01

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

  6. Graphene-Enhanced Raman Scattering from the Adenine Molecules

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  7. Resonance and Variable Temperature Raman Studies of Chloroperoxidase and Methemoglobin.

    NASA Astrophysics Data System (ADS)

    Remba, Ronald David

    1980-12-01

    Raman spectra of the heme proteins chloroperoxidase and methemoglobin, chemically and temperature modified, are obtained for laser excitation near the Soret absorption band. Numerous biochemical and physical results are obtained. The following observations for chloroperoxidase have been made. The scattered intensity for resonance (406.7 nm) excitation is at least twenty times that for near resonance (457.9 nm) excitation. In resonance only totally symmetric modes are enhanced. The positions of marker band I ((TURN) 1370 cm(' -1)) for both the native and reduced enzymes are lower than expected for high-spin heme proteins indicating a strongly electron donating axial ligand. From shifts in spin-sensitive Raman peaks as the temperature is lowered, a high-spin to low-spin transition of the heme iron is inferred. Raman spectra of chloroperoxidase liganded with small ions indicate that there is a second anion binding site near the heme. Photo-dissociation of CO from reduced chloroperoxidase is observed. The position of marker band I in the CO complex indicates that electron density is transferred from the heme onto the CO. The resonance Raman spectra of chloroperoxidase and cytochrome P-450 are nearly identical and are very different from those of horseradish peroxidase and cytochrome c. These results, particularly for the reduced enzymes, indicate that the heme sites in chloroperoxidase and P -450 are essentially the same. Raman spectra of a number of methemoglobins complexed with various small ions are obtained as a function of temperature in the region of spin-sensitive marker band (II) ((TURN) 1500 cm('-1)) for laser excitation near the Soret absorption band. For certain ligands, H(,2)O, N(,3)('-), OCN('-), OH('-) and SCN('-), the iron spin state changes from high spin to low spin with decreasing temperature. The relative spin concentrations are monitored by measuring the Raman intensity ratio, I(,h)/I(,1), of the high-spin and low -spin versions of marker band (II

  8. Nanopillars array for surface enhanced Raman scattering

    SciTech Connect

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

    2011-04-14

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

  9. Resonance Raman spectroscopy of volatile organics -- Carbon tetrachloride

    SciTech Connect

    Barletta, R.E.; Veligdan, J.T.

    1994-09-01

    Volatile organic chemicals are a class of pollutants which are regulated at very low levels by the EPA. Consequently a need exists as a part of site remediation efforts within DOE to develop technologies which will allow for the in situ monitoring of these chemicals. Resonance Raman spectroscopy is a potential technique to accomplish this if the resonance enhancement is sufficiently high. Carbon tetrachloride was selected as a test case. Measurements under resonance conditions at 248 nm showed an enhancement factor of 2 {times} 10{sup 4}. Using this value an estimate of the sensitivity for both in situ and remote monitoring of CCl{sup 4} was made. It was concluded that resonance Raman could be used to detect these chemicals at levels of regulatory interest. Future effort directed towards the development of a suitable probe as well as a field-portable system would be desirable. Such effort could be directed towards the solution of a particular monitoring problem within a DOE waste remediation project. Once developed, however, it should be easily generalized to the analysis of other VOC`s in other environments.

  10. Resonant Raman scattering background in XRF spectra of binary samples

    NASA Astrophysics Data System (ADS)

    Sánchez, Héctor Jorge; Leani, Juan José

    2015-02-01

    In x-ray fluorescence analysis, spectra present singular characteristics produced by the different scattering processes. When atoms are irradiated with incident energy lower and close to an absorption edge, scattering peaks appear due to an inelastic process known as resonant Raman scattering. In this work we present theoretical calculations of the resonant Raman scattering contributions to the background of x-ray fluorescence spectra of binary samples of current technological or biological interest. On one hand, a binary alloy of Fe with traces of Mn (Mn: 0.01%, Fe: 99.99%) was studied because of its importance in the stainless steels industries. On the second hand a pure sample of Ti with V traces (Ti: 99%, V: 1%) was analyzed due to the current relevance in medical applications. In order to perform the calculations the Shiraiwa and Fujino's model was used to calculate characteristic intensities and scattering interactions. This model makes certain assumptions and approximations to achieve the calculations, especially in the case of the geometrical conditions and the incident and take-off beams. For the binary sample studied in this work and the considered experimental conditions, the calculations show that the resonant Raman scattering background is significant under the fluorescent peak, affects the symmetry of the peaks and, depending on the concentrations, overcomes the enhancements contributions (secondary fluorescence).

  11. Wavelength dependent resonance Raman band intensity of broadband stimulated Raman spectroscopy of malachite green in ethanol

    NASA Astrophysics Data System (ADS)

    Cen, Qiongyan; He, Yuhan; Xu, Mei; Wang, Jingjing; Wang, Zhaohui

    2015-03-01

    Resonance broadband stimulated Raman spectroscopy of malachite green in ethanol has been performed. With a tuning picosecond visible laser source and a broadband Raman probe, the Raman gain and loss spectra have been measured simultaneously. By scanning the Raman pump across the first absorption band of the molecule, we found that the resonant Raman bands could be only seen when the pump laser tuned in the range of the red edge of the S1←S0 transition. Dispersive lineshapes of resonant Raman bands have been observed in the Raman loss spectra, while the line shape is normal (same as spontaneous Raman) in the Raman gain spectra. Although, the resonant bands in the loss spectrum are usually stronger than that in the gain spectrum, the band intensities of both loss and gain linearly increase with the pump energy. The relative magnitude of each corresponding resonant band in the Raman loss and gain varies with the pump wavelength. Mode specified Raman excitation profiles have been obtained through broadband stimulated Raman measurement.

  12. Deep ultraviolet Raman spectroscopy: A resonance-absorption trade-off illustrated by diluted liquid benzene

    NASA Astrophysics Data System (ADS)

    Chadwick, C. T.; Willitsford, A. H.; Philbrick, C. R.; Hallen, H. D.

    2015-12-01

    The magnitude of resonance Raman intensity, in terms of the real signal level measured on-resonance compared to the signal level measured off-resonance for the same sample, is investigated using a tunable laser source. Resonance Raman enhancements, occurring as the excitation energy is tuned through ultraviolet absorption lines, are used to examine the 1332 cm-1 vibrational mode of diamond and the 992 cm-1 ring-breathing mode of benzene. Competition between the wavelength dependent optical absorption and the magnitude of the resonance enhancement is studied using measured signal levels as a function of wavelength. Two system applications are identified where the resonance Raman significantly increases the real signal levels despite the presence of strong absorption: characterization of trace species in laser remote sensing and spectroscopy of the few molecules in the tiny working volumes of near-field optical microscopy.

  13. Surface-enhanced hyper-Raman and Raman hyperspectral mapping.

    PubMed

    Gühlke, Marina; Heiner, Zsuzsanna; Kneipp, Janina

    2016-06-01

    We investigate distributions of crystal violet and malachite green on plasmonic surfaces by principal component analysis (PCA) imaging of surface-enhanced hyper-Raman scattering (SEHRS) data. As a two-photon excited Raman scattering process, SEHRS provides chemical structure information based on molecular vibrations, but follows different selection rules than the normal, one-photon excited surface-enhanced Raman scattering (SERS). Therefore, simultaneous hyperspectral mapping using SEHRS excited at 1064 nm and SERS excited at 532 nm improves spatially resolved multivariate discrimination based on complementary vibrational information. The possibility to map distributions of the structurally similar dyes crystal violet and malachite green demonstrates the potential of this approach for multiplex imaging of complex systems. PMID:27166200

  14. Franck-Condon processes in pentacene monolayers revealed in resonance Raman scattering

    NASA Astrophysics Data System (ADS)

    He, Rui; Tassi, Nancy G.; Blanchet, Graciela B.; Pinczuk, Aron

    2011-03-01

    Franck-Condon processes in pentacene monolayers are revealed in resonance Raman scattering from intramolecular vibrations. The Raman intensities from a totally symmetric vibrational mode display resonance enhancement double peaks when incident or scattered photon energies overlap the free exciton (FE) optical emission. The two resonances are of about equal strength. This remarkable symmetry in the resonance Raman profile suggests that Franck-Condon overlap integrals for the respective vibronic transitions have the same magnitude, which could be explained by the small displacement of potential energy curves along the configuration coordinate upon the FE excitation. The interference between scattering amplitudes in the Raman resonance reveals quantum coherence of the symmetry-split states (Davydov doublet) of the lowest intrinsic singlet exciton in pentacene monolayers.

  15. Preventing Raman Lasing in High-Q WGM Resonators

    NASA Technical Reports Server (NTRS)

    Savchenkov, Anatoliy; Matsko, Andrey; Strekalov, Dmitry; Maleki, Lute

    2007-01-01

    A generic design has been conceived to suppress the Raman effect in whispering- gallery-mode (WGM) optical resonators that have high values of the resonance quality factor (Q). Although it is possible to exploit the Raman effect (even striving to maximize the Raman gain to obtain Raman lasing), the present innovation is intended to satisfy a need that arises in applications in which the Raman effect inhibits the realization of the full potential of WGM resonators as frequency-selection components. Heretofore, in such applications, it has been necessary to operate high-Q WGM resonators at unattractively low power levels to prevent Raman lasing. (The Raman-lasing thresholds of WGM optical resonators are very low and are approximately proportional to Q(sup -2)). Heretofore, two ways of preventing Raman lasting at high power levels have been known, but both entail significant disadvantages: A resonator can be designed so that the optical field is spread over a relatively large mode volume to bring the power density below the threshold. For any given combination of Q and power level, there is certain mode volume wherein Raman lasing does not start. Unfortunately, a resonator that has a large mode volume also has a high spectral density, which is undesirable in a typical photonic application. A resonator can be cooled to the temperature of liquid helium, where the Raman spectrum is narrower and, therefore, the Raman gain is lower. However, liquid-helium cooling is inconvenient. The present design overcomes these disadvantages, making it possible to operate a low-spectral-density (even a single-mode) WGM resonator at a relatively high power level at room temperature, without risk of Raman lasing.

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

    SciTech Connect

    Meyer, Matthew W.

    2013-01-01

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

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

    PubMed

    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

  18. Brain metastasis detection by resonant Raman optical biopsy method

    NASA Astrophysics Data System (ADS)

    Zhou, Yan; Liu, Cheng-hui; Cheng, Gangge; Zhou, Lixin; Zhang, Chunyuan; Pu, Yang; Li, Zhongwu; Liu, Yulong; Li, Qingbo; Wang, Wei; Alfano, Robert R.

    2014-03-01

    Resonant Raman (RR) spectroscopy provides an effective way to enhance Raman signal from particular bonds associated with key molecules due to changes on a molecular level. In this study, RR is used for detection of human brain metastases of five kinds of primary organs of lung, breast, kidney, rectal and orbital in ex-vivo. The RR spectra of brain metastases cancerous tissues were measured and compared with those of normal brain tissues and the corresponding primary cancer tissues. The differences of five types of brain metastases tissues in key bio-components of carotene, tryptophan, lactate, alanine and methyl/methylene group were investigated. The SVM-KNN classifier was used to categorize a set of RR spectra data of brain metastasis of lung cancerous tissues from normal brain tissue, yielding diagnostic sensitivity and specificity at 100% and 75%, respectively. The RR spectroscopy may provide new moleculebased optical probe tools for diagnosis and classification of brain metastatic of cancers.

  19. Resonant Raman scattering and luminescence in CuInS{sub 2} crystals

    SciTech Connect

    Wakita, K.; Hirooka, H.; Yasuda, S.; Fujita, F.; Yamamoto, N.

    1998-01-01

    Resonant Raman scattering and luminescence have been examined for CuInS{sub 2} crystals grown by the traveling heater method (THM) and the iodine vapor transport method (IT). Resonant Raman spectra of CuInS{sub 2} have been observed, and the spectra show seven single-phonon peaks and one two-phonon peak. Among them, three single-phonon modes have been found in the low-Raman-shift region because of resonant enhancement of phonon modes. The enhancement of these phonon modes is caused by incoming resonance mediated by bound excitons on the THM crystal, while it is attributed to outgoing resonance due to intermediate states of free excitons on the IT crystal. {copyright} {ital 1998 American Institute of Physics.}

  20. Resonance Raman excitation profiles of lycopene

    NASA Astrophysics Data System (ADS)

    Hoskins, L. C.

    1981-01-01

    The resonance Raman spectrum of lycopene has been examined in acetone solvent and excitation profiles of the three fundamentals ν1, ν2, and ν3 have been determined. The excitation data and the visible spectrum have been analyzed using two-mode and three-mode vibrational models, with the two-mode model involving virtual states of ν1 and ν2 giving the best fit to the data. This mode mixing or Duskinsky effect was not observed for β-carotene. The single-mode and three-mode theories which have been used to explain the corresponding data for β-carotene are shown to be inconsistent with the experimental data of lycopene. Equations for calculating excitation profiles and visible spectra are given.

  1. A new SERS: scattering enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Bixler, Joel N.; Yakovlev, Vladislav V.

    2014-03-01

    Raman spectroscopy is a powerful technique that can be used to obtain detailed chemical information about a system without the need for chemical markers. It has been widely used for a variety of applications such as cancer diagnosis and material characterization. However, Raman scattering is a highly inefficient process, where only one in 1011 scattered photons carry the needed information. Several methods have been developed to enhance this inherently weak effect, including surface enhanced Raman scattering and coherent anti-Stokes Raman scattering. These techniques suffer from drawbacks limiting their commercial use, such as the need for spatial localization of target molecules to a `hot spot', or the need for complex laser systems. Here, we present a simple instrument to enhance spontaneous Raman scattering using elastic light scattering. Elastic scattering is used to substantially increase the interaction volume. Provided that the scattering medium exhibits very low absorption in the spectral range of interest, a large enhancement factor can be attained in a simple and inexpensive setting. In our experiments, we demonstrate an enhancement of 107 in Raman signal intensity. The proposed novel device is equally applicable for analyzing solids, liquids, and gases.

  2. High fidelity nanohole enhanced Raman spectroscopy.

    SciTech Connect

    Bahns, J. T.; Guo, Q.; Gray, S. K.; Jaeger, H. M.; Chen, L.; Montgomery, J. M.; Univ. of Chicago

    2009-01-01

    Surface enhanced Raman spectroscopy (SERS) is a sensitive technique that can even detect single molecules. However, in many SERS applications, the strongly inhomogeneous distribution of intense local fields makes it very difficult for a quantitive assessment of the fidelity, or reproducibility of the signal, which limits the application of SERS. Herein, we report the development of exceptionally high-fidelity hole-enhanced Raman spectroscopy (HERS) from ordered, 2D hexagonal nanohole arrays. We take the fidelity f to be a measure of the percent deviation of the Raman peaks from measurement to measurement. Overall, area averaged fidelities for 12 gold array samples ranged from f {approx} 2-15% for HERS using aqueous R6G molecules. Furthermore, intensity modulations of the enhanced Raman spectra were measured for the first time as a function of polarization angle. The best of these measurements, which focus on static laser spots on the sample, could be consistent with even higher fidelities than the area-averaged results. Nanohole arrays in silver provided supporting polarization measurements and a more complete enhanced Raman fingerprint for phenylalanine molecules. We also carried out finite-difference time-domain calculations to assist in the interpretation of the experiments, identifying the polarization dependence as possibly arising from hole-hole interactions. Our results represent a step toward making quantitative and reproducible enhanced Raman measurements possible and also open new avenues for a large-scale source of highly uniform hot spots.

  3. Recent topics on single-molecule fluctuation analysis using blinking in surface-enhanced resonance Raman scattering: clarification by the electromagnetic mechanism.

    PubMed

    Itoh, Tamitake; Yamamoto, Yuko S

    2016-08-15

    Surface-enhanced Raman scattering (SERS) spectroscopy has become an ultrasensitive tool for clarifying molecular functions on plasmonic metal nanoparticles (NPs). SERS has been used for in situ probing of detailed behaviors of few or single molecules (SMs) at plasmonic NP junctions. SM SERS signals are commonly observed with temporal and spectral changes known as "blinking", which are related to various physical and chemical interactions between molecules and NP junctions. These temporal and spectral changes simultaneously take place, therefore resulting in serious complexities in interpretations of the SM SERS results. Dual contributions of Raman enhancement mechanisms in SERS (i.e., electromagnetic (EM) and chemical enhancements) also make interpretations more difficult. To resolve these issues and reduce the degree of complexities in SM SERS analyses, the present review is focused on the recent studies of probing SM behaviors using SERS exclusively within the framework of the EM mechanism. The EM mechanism is briefly introduced, and several recent topics on SM SERS blinking analysis are discussed in light of the EM mechanism. This review will provide a basis for clarification of complex SERS fluctuations of various molecules. PMID:27241875

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

    PubMed

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

    2016-01-01

    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. PMID:27339882

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

    PubMed Central

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

    2016-01-01

    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. PMID:27339882

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Characterization of the Electrochemical Interface by Surface Enhanced Raman Scattering

    NASA Astrophysics Data System (ADS)

    Roy, Dipankar

    The electronic and structural properties of an enhanced raman sensitive interface are investigated. As a model system, the Ag (polycrystalline) electrode/electrolyte interface is chosen. Electrochemical control of the interface is used to establish and influence the conditions for surface enhanced Raman scattering (SERS). The molecule and site specific electronic component of SERS is studied under experimental control. This resonance is responsible for enhancement beyond that caused by electromagnetic effects at the surface and is promoted by the presence of the so -called "SERS active sites" (surface defect sites of atomic scale roughness). The results suggest that, these sites are positively charged, resonant Raman active Ag clusters, most likely with the identity of Ag(,4)('+). A partial contribution to the observed electronic enhancement comes from the intrinsic resonance of the clusters. At a given SERS sensitive Ag electrode, this contribution is superimposed on that from the photon driven charge transfer excitation (CTE) resonance, provided the latter is operative in that particular case. In SERS of Cl('-) (a prototypical probe) on Ag, the internal resonance of Ag(,4)('+) appears to be the primary source of the electronic enhancement detected. By noting the known importance of Ag(,4)('+) in silver-halide photography, it is possible to explain the "photoactivation effect" in SERS in terms of the Ag(,4)('+) identity of SERS active sites. These observations indicate how, by SERS, it may be possible to bridge the gap between the catalytic and optical aspects of small metal clusters. The chemisorbed anions which coexist with the active sites at a SERS sensitive interface, are tested for their effects in SERS from Cl('-) and I('-) on Ag. Evidence is presented for mutual "depolarization" effect of the adsorbates. Under voltage control of these interfaces, this depolarization process dominates the Stark effect and bond perturbation. The results point out how the

  8. Isotopic gas analysis through Purcell cavity enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Petrak, B.; Cooper, J.; Konthasinghe, K.; Peiris, M.; Djeu, N.; Hopkins, A. J.; Muller, A.

    2016-02-01

    Purcell enhanced Raman scattering (PERS) by means of a doubly resonant Fabry-Perot microcavity (mode volume ≈ 100 μm3 and finesse ≈ 30 000) has been investigated as a technique for isotopic ratio gas analysis. At the pump frequency, the resonant cavity supports a buildup of circulating power while simultaneously enabling Purcell spontaneous emission rate enhancement at the resonant Stokes frequency. The three most common isotopologues of CO2 gas were quantified, and a signal was obtained from 13C16O2 down to a partial pressure of 2 Torr. Due to its small size and low pump power needed (˜10 mW) PERS lends itself to miniaturization. Furthermore, since the cavity is resonant with the emission frequency, future improvements could allow it to serve as its own spectral analyzer and no separate spectroscopic device would be needed.

  9. Resonance Raman spectra of. cap alpha. -copper phthalocyanine

    SciTech Connect

    Bovill, A.J.; McConnell, A.A.; Nimmo, J.A.; Smith, W.E.

    1986-02-13

    Raman spectra of ..cap alpha..-copper phthalocyanine (..cap alpha..-CuPc) were recorded at room temperature and at 10 K with excitation wavelengths between 457 and 714 nm. Resonance enhancement was greatest for modes for which the largest displacements were on either the inner five-membered ring of the isoindole groups or the inner macrocycle and consequently assignment of the bands to modes of the entire molecule was possible by comparison with nickel octaethylporphyrin. Four out of five bands resonant in the Q band region and preresonant near the B band absorption region are totally symmetric modes. B band preresonance occurs more strongly with high-frequency modes. At low temperatures, multimode interactions are reduced and profiles were obtained which can be compared with solution profiles of porphyrins. Both Q/sub x/ and Q/sub y/ 0-0 scattering can be identified and a helper mode is evident. A term enhancement predominates, with B/sub 1g/ and B/sub 2g/ modes enhanced because of a Jahn-Teller distortion of the excited state. The resonance studies, together with electronic absorption spectra and published theoretical studies, confirm that the Q band in ..cap alpha..-CuPc is largely due to an allowed ..pi..-..pi..* transition associated mainly with the macrocycle and inner five-membered rings of the isoindole groups. 25 references, 5 figures, 2 tables.

  10. Cavity-Enhanced Room-Temperature Broadband Raman Memory.

    PubMed

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

    2016-03-01

    Broadband quantum memories hold great promise as multiplexing elements in future photonic quantum information protocols. Alkali-vapor Raman memories combine high-bandwidth storage, on-demand readout, and operation at room temperature without collisional fluorescence noise. However, previous implementations have required large control pulse energies and have suffered from four-wave-mixing noise. Here, we present a Raman memory where the storage interaction is enhanced by a low-finesse birefringent cavity tuned into simultaneous resonance with the signal and control fields, dramatically reducing the energy required to drive the memory. By engineering antiresonance for the anti-Stokes field, we also suppress the four-wave-mixing noise and report the lowest unconditional noise floor yet achieved in a Raman-type warm vapor memory, (15±2)×10^{-3} photons per pulse, with a total efficiency of (9.5±0.5)%. PMID:26991164

  11. Cavity-Enhanced Room-Temperature Broadband Raman Memory

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  12. Transform analysis of the resonance Raman excitation profile of lycopene

    NASA Astrophysics Data System (ADS)

    Hoskins, L. C.

    1992-10-01

    The resonance Raman excitation profiles (RREPs) of the ν 1, ν 2 and ν 3 vibrations of lycopene in acetone, ethyl alcohol, toluene and carbon disulphide solvents have been analyzed using the transform method for calculating resonance Raman excitation profiles. The tests show excellent agreement between the calculated and observed profiles for the ν 2 and ν 3 RREPs, but greater difference between experiment and theory occurs for the ν 1 RREP, especially in carbon disulphide solvent.

  13. Detection Of Biochips By Raman And Surface Enhanced Raman Spectroscopies

    NASA Astrophysics Data System (ADS)

    Kantarovich, Keren; Tsarfati, Inbal; Gheber, Levi A.; Haupt, Karsten; Bar, Ilana

    2010-08-01

    Biochips constitute a rapidly increasing research field driven by the versatility of sensing devices and the importance of their applications in the bioanalytical field, drug development, environmental monitoring, food analysis, etc. Common strategies used for creating biochips and for reading them have extensive limitations, motivating development of miniature biochips and label-free formats. To achieve these goals we combined the nano fountain pen method, for printing microscale features with Raman spectroscopy or surface enhanced Raman spectroscopy (SERS) for reading droplets of synthetic receptors. These receptors include molecularly imprinted polymers (MIPs), which are obtained by polymerization of suitable functional and cross-linking monomers around molecular templates. MIPs are characterized by higher physical and chemical stability than biomacromolecules, and therefore are potentially very suitable as recognition elements for biosensors, or biochips. The monitored bands in the Raman and SERS spectra could be related to the taken up compound, allowing direct detection of the template, i.e., the β-blocking drug propranolol in the imprinted droplets, as well as imaging of individual and multiple dots in an array. This study shows that the combination of nanolithography techniques with SERS might open the possibility of miniaturized arrayed MIP sensors with label-free, specific and quantitative detection.

  14. Human brain cancer studied by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    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.

  15. Theoretical studies of resonance enhanced stimulated raman scattering (RESRS) of frequency doubled Alexandrite laser wavelength in cesium vapor. Progress report, July-December 1987

    SciTech Connect

    Lawandy, N.M.

    1987-01-01

    The third phase of research will focus on the propagation and energy extraction of the pump and SERS beams in a variety of configurations including oscillator structures. In order to address these questions a numerical code capable of allowing for saturation and full transverse beam evolution is required. The method proposed is based on a discretized propagation energy extraction model which uses a Kirchoff integral propagator coupled to the three level Raman model already developed. The model will have the resolution required by diffraction limits and will use the previous density matrix results in the adiabatic following limit. Owing to its large computational requirements, such a code must be implemented on a vector array processor. One code on the Cyber is being tested by using previously understood two-level laser models as guidelines for interpreting the results. Two tests were implemented: the evolution of modes in a passive resonator and the evolution of a stable state of the adiabatically eliminated laser equations. These results show mode shapes and diffraction losses for the first case and relaxation oscillations for the second one. Finally, in order to clarify the computing methodology used to exploit the speed of the Cyber's computational speed, the time it takes to perform both of the computations previously mentioned to run on the Cyber and VAX 730 must be measured. Also included is a short description of the current laser model (CAVITY.FOR) and a flow chart of the test computations.

  16. Resonance Raman spectra of some radiolytically prepared halogen derivatives of para-benzosemiquinone radical anion

    SciTech Connect

    Tripathi, G.N.R.; Schuler, R.H.

    1982-03-01

    The resonance Raman spectra have been obtained on radiolytically and chemically prepared halogen derivatives (chloro-, bromo-, 2.5 dichloro-, tetra chloro-, and tetra bromo-) of p-benzosemiquinone radical anion. Excitation is in the moderately intense absorption band at 430--460 nm. All Raman spectra show a strongly resonance enhanced and polarized line corresponding to a vibrational frequency of 1590--1620 cm/sup -1/ which is assigned to the Wilson phenyl mode 8a (CC stretch). A number of weaker lines are also observed and their assignment discussed. The electronic transitions in resonance are identified as /sup 2/B/sub 3g/--/sup 2/B/sub 1u/ (in D/sub 2h/ point group) in view of the resonance Raman band intensities. This supports the assignment by Harada based on ASMO CI calculations which has recently been in dispute.

  17. Surface enhanced Raman spectroscopy of neurotransmitters

    NASA Astrophysics Data System (ADS)

    McGlashen, Michael L.; Davis, Kevin L.; Morris, Michael D.

    1989-10-01

    The surface-enhanced Raman spectra (SERS) of neurotransmitters in biological matrices and synthetic solutions are described. The effects of protein adsorption on cathecholamine SERS intensity are discussed. Techniques for obtaining dopamine SERS spectra in cerebrospinal fluid and rat brain dialysate are demonstrated. Preliminary SERS of histamine and tel-methylhistamine are presented.

  18. Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency-doubled Alexandrite laser wavelength in cesium vapor. Progress report, January-June 1987

    SciTech Connect

    Lawandy, N.M.

    1987-01-01

    The solutions for the imaginary susceptibility of the Raman field transition with arbitrary relaxation rates and field strengths are examined for three different sets of relaxation rates. These rates correspond to: (1) Far Infrared (FIR) Raman lasers in the diabatic collision regime without consideration of coupled population decay in a closed system, (2) Raman FIR lasers in the diabatic collision regime with coupled population conserving decay, and (3) IR Raman gain in cesium vapor. The model is further expanded to include Doppler broadening and used to predict the peak gain as a function of detuning for a frequency doubled Alexandrite laser-pumped cesium vapor gain cell.

  19. The theory of surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Lombardi, John R.; Birke, Ronald L.

    2012-04-01

    By considering the molecule and metal to form a conjoined system, we derive an expression for the observed Raman spectrum in surface-enhanced Raman scattering. The metal levels are considered to consist of a continuum with levels filled up to the Fermi level, and empty above, while the molecule has discrete levels filled up to the highest occupied orbital, and empty above that. It is presumed that the Fermi level of the metal lies between the highest filled and the lowest unfilled level of the molecule. The molecule levels are then coupled to the metal continuum both in the filled and unfilled levels, and using the solutions to this problem provided by Fano, we derive an expression for the transition amplitude between the ground stationary state and some excited stationary state of the molecule-metal system. It is shown that three resonances contribute to the overall enhancement; namely, the surface plasmon resonance, the molecular resonances, as well as charge-transfer resonances between the molecule and metal. Furthermore, these resonances are linked by terms in the numerator, which result in SERS selection rules. These linked resonances cannot be separated, accounting for many of the observed SERS phenomena. The molecule-metal coupling is interpreted in terms of a deformation potential which is compared to the Herzberg-Teller vibronic coupling constant. We show that one term in the sum involves coupling between the surface plasmon transition dipole and the molecular transition dipole. They are coupled through the deformation potential connecting to charge-transfer states. Another term is shown to involve coupling between the charge-transfer transition and the molecular transition dipoles. These are coupled by the deformation potential connecting to plasmon resonance states. By applying the selection rules to the cases of dimer and trimer nanoparticles we show that the SERS spectrum can vary considerably with excitation wavelength, depending on which plasmon and

  20. Directional surface enhanced Raman scattering on gold nano-gratings

    NASA Astrophysics Data System (ADS)

    Gillibert, Raymond; Sarkar, Mitradeep; Bryche, Jean-François; Yasukuni, Ryohei; Moreau, Julien; Besbes, Mondher; Barbillon, Grégory; Bartenlian, Bernard; Canva, Michael; Lamy de la Chapelle, Marc

    2016-03-01

    Directional plasmon excitation and surface enhanced Raman scattering (SERS) emission were demonstrated for 1D and 2D gold nanostructure arrays deposited on a flat gold layer. The extinction spectrum of both arrays exhibits intense resonance bands that are redshifted when the incident angle is increased. Systematic extinction analysis of different grating periods revealed that this band can be assigned to a propagated surface plasmon of the flat gold surface that fulfills the Bragg condition of the arrays (Bragg mode). Directional SERS measurements demonstrated that the SERS intensity can be improved by one order of magnitude when the Bragg mode positions are matched with either the excitation or the Raman wavelengths. Hybridized numerical calculations with the finite element method and Fourier modal method also proved the presence of the Bragg mode plasmon and illustrated that the enhanced electric field of the Bragg mode is particularly localized on the nanostructures regardless of their size.

  1. Directional surface enhanced Raman scattering on gold nano-gratings.

    PubMed

    Gillibert, Raymond; Sarkar, Mitradeep; Bryche, Jean-François; Yasukuni, Ryohei; Moreau, Julien; Besbes, Mondher; Barbillon, Grégory; Bartenlian, Bernard; Canva, Michael; Chapelle, Marc Lamy de la

    2016-03-18

    Directional plasmon excitation and surface enhanced Raman scattering (SERS) emission were demonstrated for 1D and 2D gold nanostructure arrays deposited on a flat gold layer. The extinction spectrum of both arrays exhibits intense resonance bands that are redshifted when the incident angle is increased. Systematic extinction analysis of different grating periods revealed that this band can be assigned to a propagated surface plasmon of the flat gold surface that fulfills the Bragg condition of the arrays (Bragg mode). Directional SERS measurements demonstrated that the SERS intensity can be improved by one order of magnitude when the Bragg mode positions are matched with either the excitation or the Raman wavelengths. Hybridized numerical calculations with the finite element method and Fourier modal method also proved the presence of the Bragg mode plasmon and illustrated that the enhanced electric field of the Bragg mode is particularly localized on the nanostructures regardless of their size. PMID:26872242

  2. Time-resolved resonance Raman observation of tetrafluoro-p-benzosemiquinone anion radical. [Pulse radiolysis

    SciTech Connect

    Tripathi, G.N.R.; Schuler, R.H.

    1983-08-04

    Time-resolved resonance Raman spectroscopy has been used to examine tetrafluoro-p-benzosemiquinone radical anion produced in the pulse radiolytic oxidation of tetrafluorohydroquinone in aqueous solution. This radical is much more reactive than p-benzosemiquinone and is observed to decay on the millisecond time scale in both Raman and pulse radiolytic experiments. For the Raman experiments excitation was on the red edge of the moderately strong absorption band of this radical at 430 nm. Two resonance-enhanced Raman bands are exhibited at 1556 and 1677 cm/sup -1/ and are assigned to the in-phase CO and symmetrical CC stretch vibrations. These frequencies are considerably higher than the corresponding values of 1435 and 1620 cm/sup -1/ observed in this radical's protonated counterpart. The relatively large increase in the CO stretch frequency, in particular, indicates that fluorination induces a substantial increase in the quinoid character of this radical. 3 figures, 1 table.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Periodontitis diagnostics using resonance Raman spectroscopy on saliva

    NASA Astrophysics Data System (ADS)

    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.

  5. Remote detection of trace effluents using Resonance Raman spectroscopy: Field results and evaluation

    SciTech Connect

    Sedlacek, A.J.; Chen, C.L.

    1995-10-01

    Resonance Raman spectroscopy (RRS) possesses many characteristics that are important for detecting, identifying and monitoring chemical effluents. Raman scattering is a coherent, inelastic, two-photon scattering process where an exciting photon of energy h{nu} 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, thereby providing a unique fingerprint of the molecule. Under resonance enhancement, the Raman scattering cross-sections have been observed to increase up to 6 orders of magnitude above the normal scattering cross-sections, thereby providing the practical basis for a remote chemical sensor. Some of the other advantages that a Raman sensor possesses are: (1) very high selectivity (chemical specific fingerprints), (2) independence of the spectral fingerprint on the excitation wavelength (ability to monitor in the solar blind region), (3) chemical mixture fingerprints are the sum of its individual components (no spectral cross-talk), (4) near independence of the Raman fingerprint to its physical state (very similar spectra for gas, liquid, solid or solutions), (5) no absolute calibration is necessary because all Raman signals observed from a given species can be compared with the Raman signal for N{sub 2}, whose concentration is known very accurately, and (6) insensitivity of the Raman signature to environmental conditions (no quenching, or interference from water vapor). In this presentation, the technology of resonance Raman spectroscopy as applied to the detection of narcotics production activities will be presented along with some recent experimental results.

  6. Plasmonic nanostructures for surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Jiang, Ruiqian

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

  7. Interference-enhanced Raman scattering of F16CuPc thin films

    NASA Astrophysics Data System (ADS)

    Solonenko, D.; Gordan, O. D.; Milekhin, A.; Panholzer, M.; Hingerl, K.; Zahn, D. R. T.

    2016-03-01

    Interference-enhanced Raman scattering (IERS) was observed for thin films of copper(II) hexadecafluorophthalocyanine (F16CuPc) deposited on SiO2 layers on a Si substrate. The enhancement of the Raman scattering originates from the interference of the light in the transparent SiO2 layer. Stripes of SiO2/Si with gradually varying oxide layer thickness were used as IERS substrates for a systematic study of the enhancement parameters. Raman measurements were carried out using three laser lines (325, 514.7, and 632.8 nm) in order to probe the F16CuPc thin films at non-resonant and resonant Raman conditions. Spectroscopic ellipsometry was used to determine both the SiO2 layer and thin film thicknesses. The intensity enhancement of the F16CuPc Raman peaks occurs periodically, corresponding to the alternating interference conditions for the Raman scattered light with increasing SiO2 layer thickness. The enhancement factors were calculated using the optical constants of the layers involved and the geometric parameters. This allows a straightforward application of IERS for optical studies of thin films and interfaces by calculating the dielectric thickness where maximum Raman enhancement is expected.

  8. Surface-enhanced Raman spectroscopy of pterins

    NASA Astrophysics Data System (ADS)

    Smyth, Ciarán A.; Mirza, Inam; Lunney, James G.; McCabe, Eithne M.

    2012-03-01

    Raman spectroscopy is a useful technique in the identification and characterisation of compounds, but in terms of sensitivity its application is limited. With respect to this the discovery of the surface-enhanced Raman scattering (SERS) phenomenon has proved monumental, and much research has been carried out over the past 30 years developing the technique. Pterins are biological compounds that are found in nature in colour pigmentation and in mammalian metabolic pathways. Moreover, they have been identified in abnormal concentrations in cancer patients, suggesting potential applications in cancer diagnostics. SERS is an ideal technique to identify these compounds, and both nanoparticle suspensions and pulsed laser deposited nanoparticle substrates have been used to examine the spectra of xanthopterin, both in aqueous solution and in different pH environments.

  9. 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).

    PubMed

    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

  10. Resonant Raman Scattering as a Probe of Intrinsic Defects in Gallium-Arsenide

    NASA Astrophysics Data System (ADS)

    Berg, Robert Scott

    This thesis presents a series of Raman scattering measurements performed on GaAs samples that have been irradiated with either high energy electrons or neutrons. The irradiation creates fairly high concentrations (10('17) - 10('18) cm(' -3)) of intrinsic defects. It is demonstrated that Raman scattering can give useful information about such defects. One important result of this work is the observation of new and relatively sharp peaks in the Raman spectra of the irradiated samples. These are attributed to vibrational modes of a specific point defect created by the irradiation. On the basis of annealing experiments it is concluded that one of thes modes is most likely associated with an As vacancy. The observed polarization dependence suggests that this can be a "breathing" vibration of the atoms surrounding the vacancy. In addition, experiments were performed that measured the lineshape of the enhancement of the Raman cross section of both the intrinsic and extrinsic modes near the band gap of GaAs using a tunable near infra-red laser. It was observed that the enhancement of the defect introduced modes was strong relative to the enhancement of the allowed TO phonon, which itself exhibits a strong enhancement. The observed enhancement lineshape can be explained by assuming that the scattering involving the defect induced modes occurs via a fourth order process. During this process quasi-momentum conservation is relaxed when electrons or holes scatter elastically from defects. On the basis of this model it is concluded that the strong resonant enhancement occurs when the vibrational modes involved have a component that is well localized around a defect. Thus resonant Raman scattering has greater sensitivity to motion within the first few lattice constants surrounding a point defect and is well suited to provide microscopic information about such defects. Another important conclusion is that the strong enhancement of the Raman cross section of the defect induced

  11. Structural resonances in the Raman spectrum of glass microsphere

    NASA Astrophysics Data System (ADS)

    Wang, Ji-You; Xu, Xiao xuan; Zhang, Cun zhou

    2000-10-01

    Structural resonances have been found in the Raman spectrum of an optically levitated TiBa glass microsphere. The observed resonances could be assigned by using the well-known Lorenz-Mie Formalism. It was found that the diameter of the TiBa glass microsphere is 24.490micrometers , and the refractive index of TiBa glass is 1.895 at about 645nm.

  12. Resonance Raman spectra of carotenoid molecules: influence of methyl substitutions.

    PubMed

    Macernis, Mindaugas; Galzerano, Denise; Sulskus, Juozas; Kish, Elizabeth; Kim, Young-Hun; Koo, Sangho; Valkunas, Leonas; Robert, Bruno

    2015-01-01

    We report here the resonance Raman spectra and the quantum chemical calculations of the Raman spectra for β-carotene and 13,13'-diphenyl-β-carotene. The first aim of this approach was to test the robustness of the method used for modeling β-carotene, and assess whether it could accurately predict the vibrational properties of derivatives in which conjugated substituents had been introduced. DFT calculations, using the B3LYP functional in combination with the 6-311G(d,p) basis set, were able to accurately predict the influence of two phenyl substituents connected to the β-carotene molecule, although these deeply perturb the vibrational modes. This experimentally validated modeling technique leads to a fine understanding of the origin of the carotenoid resonance Raman bands, which are widely used for assessing the properties of these molecules, and in particular in complex media, such as binding sites provided by biological macromolecules. PMID:25476500

  13. Resonance Raman Studies of Azulene and the Permanganate Ion.

    NASA Astrophysics Data System (ADS)

    Khodadoost, Baback

    This dissertation will present resonance Raman studies of the azulene molecule and the permanganate ion. Experimental measurements of the optical absorption spectra and the resonance Raman excitation profiles will be used along with the recently developed transform analysis. In the first part we have extended the frequency range of the previously measured resonance Raman profiles of azulene in solution. We have also measured, for the first time, profiles of two new Raman lines. Using transform techniques, we have calculated resonance Raman profile line shapes directly from our measured optical absorption spectra and the excited state vibrational frequencies. Our overall good profile line shape fits suggest that our model assumptions are basically correct for all the modes studied. Stokes loss analysis based on the good line shape fits indicates that possible deviations from these assumptions may be different for different modes. In the second part we have measured the visible absorption spectra of the permanganate ion with potassium perchlorate used as the host material as a function of pressure. These measurements indicate a blue shift of the absorption. The frequency of the breathing mode in the excited state increases with the pressure. From our absorption measurements we have also inferred a decrease in the Stokes loss parameter for this mode. We have also measured room temperature resonance Raman excitation profiles for the fundamental and the first two harmonics of the breathing mode, both at atmospheric and high pressures. Our Raman measurements indicate a linear increase in the ground state frequency of the breathing mode as a function of pressure. The use of the transform technique which relates absorption to resonance Raman profile line shape produces good agreements with our experimental data in all cases. As previously observed in the low pressure case we show that at high pressures it also is essential to use the excited state frequency in the

  14. Pressure-induced depolarization and resonance in Raman scattering of single-crystalline boron carbide

    SciTech Connect

    Guo Junjie; Zhang Ling; Fujita, Takeshi; Chen Mingwei; Goto, Takashi

    2010-02-01

    We report polarized and resonant Raman scattering of single-crystal boron carbide (B{sub 4}C) at high pressures. Significant intensity enhancements of 270 and 1086 cm{sup -1} Raman bands of B{sub 4}C have been observed at quasihydrostatic pressures higher than approx20 GPa. The pressure-induced intensity change of the 1086 cm{sup -1} band is mainly due to the resonance between excitation energy and electronic transition, whereas the intensity change of 270 cm{sup -1} band is caused by the depolarization effect. Importantly, the first-order phase transition has not been found at high quasihydrostatic pressures and all the Raman intensity changes along with the corresponding high-pressure lattice distortion can be recovered during unloading.

  15. Shape-dependent surface-enhanced Raman scattering in gold-Raman-probe-silica sandwiched nanoparticles for biocompatible applications

    NASA Astrophysics Data System (ADS)

    Li, Ming; Cushing, Scott K.; Zhang, Jianming; Lankford, Jessica; Aguilar, Zoraida P.; Ma, Dongling; Wu, Nianqiang

    2012-03-01

    To meet the requirement of Raman probes (labels) for biocompatible applications, a synthetic approach has been developed to sandwich the Raman-probe (malachite green isothiocyanate, MGITC) molecules between the gold core and the silica shell in gold-SiO2 composite nanoparticles. The gold-MGITC-SiO2 sandwiched structure not only prevents the Raman probe from leaking out but also improves the solubility of the nanoparticles in organic solvents and in aqueous solutions even with high ionic strength. To amplify the Raman signal, three types of core, gold nanospheres, nanorods and nanostars, have been chosen as the substrates of the Raman probe. The effect of the core shape on the surface-enhanced Raman scattering (SERS) has been investigated. The colloidal nanostars showed the highest SERS enhancement factor while the nanospheres possessed the lowest SERS activity under excitation with 532 and 785 nm lasers. Three-dimensional finite-difference time domain (FDTD) simulation showed significant differences in the local electromagnetic field distributions surrounding the nanospheres, nanorods, and nanostars, which were induced by the localized surface plasmon resonance (LSPR). The electromagnetic field was enhanced remarkably around the two ends of the nanorods and around the sharp tips of the nanostars. This local electromagnetic enhancement made the dominant contribution to the SERS enhancement. Both the experiments and the simulation revealed the order nanostars > nanorods > nanospheres in terms of the enhancement factor. Finally, the biological application of the nanostar-MGITC-SiO2 nanoparticles has been demonstrated in the monitoring of DNA hybridization. In short, the gold-MGITC-SiO2 sandwiched nanoparticles can be used as a Raman probe that features high sensitivity, good water solubility and stability, low-background fluorescence, and the absence of photobleaching for future biological applications.

  16. Resonance raman spectroscopy of an ultraviolet-sensitive insect rhodopsin

    SciTech Connect

    Pande, C.; Deng, H.; Rath, P.; Callender, R.H.; Schwemer, J.

    1987-11-17

    The authors present the first visual pigment resonance Raman spectra from the UV-sensitive eyes of an insect, Ascalaphus macaronius (owlfly). This pigment contains 11-cis-retinal as the chromophore. Raman data have been obtained for the acid metarhodopsin at 10/sup 0/C in both H/sub 2/O and D/sub 2/O. The C=N stretching mode at 1660 cm/sup -1/ in H/sub 2/O shifts to 1631 cm/sup -1/ upon deuteriation of the sample, clearly showing a protonated Schiff base linkage between the chromophore and the protein. The structure-sensitive fingerprint region shows similarities to the all-trans-protonated Schiff base of model retinal chromophores, as well as to the octopus acid metarhodopsin and bovine metarhodopsin I. Although spectra measured at -100/sup 0/C with 406.7-nm excitation, to enhance scattering from rhodopsin (lambda/sub max/ 345 nm), contain a significant contribution from a small amount of contaminants (cytochrome(s) and/or accessory pigment) in the sample, the C=N stretch at 1664 cm/sup -1/ suggests a protonated Schiff base linkage between the chromophore and the protein in rhodopsin as well. For comparison, this mode also appears at approx. 1660 cm/sup -1/ in both the vertebrate (bovine) and the invertebrate (octopus) rhodopsins. These data are particularly interesting since the absorption maximum of 345 nm for rhodopsin might be expected to originate from an unprotonated Schiff base linkage. That the Schiff base linkage in the owlfly rhodopsin, like in bovine and in octopus, is protonated suggests that a charged chromophore is essential to visual transduction.

  17. Raman beam combining for laser brightness enhancement

    SciTech Connect

    Dawson, Jay W.; Allen, Graham S.; Pax, Paul H.; Heebner, John E.; Sridharan, Arun K.; Rubenchik, Alexander M.; Barty, Chrisopher B. J.

    2015-10-27

    An optical source capable of enhanced scaling of pulse energy and brightness utilizes an ensemble of single-aperture fiber lasers as pump sources, with each such fiber laser operating at acceptable pulse energy levels. Beam combining involves stimulated Raman scattering using a Stokes' shifted seed beam, the latter of which is optimized in terms of its temporal and spectral properties. Beams from fiber lasers can thus be combined to attain pulses with peak energies in excess of the fiber laser self-focusing limit of 4 MW while retaining the advantages of a fiber laser system of high average power with good beam quality.

  18. Monitoring and trace detection of hazardous waste and toxic chemicals using resonance Raman spectroscopy

    SciTech Connect

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

    1993-04-01

    Raman scattering is a coherent, inelastic, two-photon process, which shifts the frequency of an outgoing photon according to the vibrational structure of the irradiated species, thereby providing a unique fingerprint of the molecule. When involving an allowed electronic transition (resonance Raman), this scattering cross section can be enhanced by 10{sup 4} to 10{sup 6} and provides the basis for a viable technique that can monitor and detect trace quantities of hazardous wastes and toxic chemicals. Resonance Raman spectroscopy (RRS) possesses many of the ideal characteristics for monitoring and detecting of hazardous waste and toxic chemicals. Some of these traits are: (1) very high selectivity (chemical specific fingerprints); (2) independence from the excitation wavelength (ability to monitor in the solar blind region); (3) chemical mixture fingerprints are the sum of its individual components (no spectral cross-talk); (4) near independence of the Raman fingerprint to its physical state (very similar spectra for gas, liquid, solid and solutions -- either bulk or aerosols); and (5) insensitivity of the Raman signature to environmental conditions (no quenching). Data from a few chemicals will be presented which illustrate these features. In cases where background fluorescence accompanies the Raman signals, an effective frequency modulation technique has been developed, which can completely eliminate this interference.

  19. Monitoring and trace detection of hazardous waste and toxic chemicals using resonance Raman spectroscopy

    SciTech Connect

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

    1993-01-01

    Raman scattering is a coherent, inelastic, two-photon process, which shifts the frequency of an outgoing photon according to the vibrational structure of the irradiated species, thereby providing a unique fingerprint of the molecule. When involving an allowed electronic transition (resonance Raman), this scattering cross section can be enhanced by 10[sup 4] to 10[sup 6] and provides the basis for a viable technique that can monitor and detect trace quantities of hazardous wastes and toxic chemicals. Resonance Raman spectroscopy (RRS) possesses many of the ideal characteristics for monitoring and detecting of hazardous waste and toxic chemicals. Some of these traits are: (1) very high selectivity (chemical specific fingerprints); (2) independence from the excitation wavelength (ability to monitor in the solar blind region); (3) chemical mixture fingerprints are the sum of its individual components (no spectral cross-talk); (4) near independence of the Raman fingerprint to its physical state (very similar spectra for gas, liquid, solid and solutions -- either bulk or aerosols); and (5) insensitivity of the Raman signature to environmental conditions (no quenching). Data from a few chemicals will be presented which illustrate these features. In cases where background fluorescence accompanies the Raman signals, an effective frequency modulation technique has been developed, which can completely eliminate this interference.

  20. Shedding Light on the Extinction-Enhancement Duality in Gold Nanostar-Enhanced Raman Spectroscopy**

    PubMed Central

    Li, Ming; Kang, Jeon Woong; Dasari, Ramachandra Rao

    2015-01-01

    Surface-enhanced Raman spectroscopy (SERS) has evolved from an esoteric physical phenomenon to a robust and effective analytical method recently. The need of addressing both the field enhancement and the extinction of nanoparticle suspensions, however, has been underappreciated despite its substantive impact on the sensing performance. A systematic experimental investigation of SERS enhancement and attenuation is performed in suspensions of gold nanostars, which exhibit a markedly different behavior in relation to conventional nanoparticles. The relationship is elucidated between the SERS enhancement and the localized surface plasmon resonance band, and the effect of the concentration of the gold nanostars on the signal propagation is investigated. It is shown that an optimal concentration of gold nanostars exists to maximize the enhancement factor (EF), and the maximum EF occurs when the LSPR band is blue-shifted from the excitation wavelength rather than at the on-resonance position. PMID:25331156

  1. Surface enhanced Raman scattering of light by ZnO nanostructures

    SciTech Connect

    Milekhin, A. G. Yeryukov, N. A.; Sveshnikova, L. L.; Duda, T. A.; Zenkevich, E. I.; Kosolobov, S. S.; Latyshev, A. V.; Himcinski, C.; Surovtsev, N. V.; Adichtchev, S. V.; Feng, Zhe Chuan; Wu, Chia Cheng; Wuu, Dong Sing; Zahn, D. R. T.

    2011-12-15

    Raman scattering (including nonresonant, resonant, and surface enhanced scattering) of light by optical and surface phonons of ZnO nanocrystals and nanorods has been investigated. It has been found that the nonresonant and resonant Raman scattering spectra of the nanostructures exhibit typical vibrational modes, E{sub 2}(high) and A{sub 1}(LO), respectively, which are allowed by the selection rules. The deposition of silver nanoclusters on the surface of nanostructures leads either to an abrupt increase in the intensity (by a factor of 10{sup 3}) of Raman scattering of light by surface optical phonons or to the appearance of new surface modes, which indicates the observation of the phenomenon of surface enhanced Raman light scattering. It has been demonstrated that the frequencies of surface optical phonon modes of the studied nanostructures are in good agreement with the theoretical values obtained from calculations performed within the effective dielectric function model.

  2. Surface enhanced Raman spectroscopy on a flat graphene surface

    PubMed Central

    Xu, Weigao; Ling, Xi; Xiao, Jiaqi; Dresselhaus, Mildred S.; Kong, Jing; Xu, Hongxing; Liu, Zhongfan; Zhang, Jin

    2012-01-01

    Surface enhanced Raman spectroscopy (SERS) is an attractive analytical technique, which enables single-molecule sensitive detection and provides its special chemical fingerprints. During the past decades, researchers have made great efforts towards an ideal SERS substrate, mainly including pioneering works on the preparation of uniform metal nanostructure arrays by various nanoassembly and nanotailoring methods, which give better uniformity and reproducibility. Recently, nanoparticles coated with an inert shell were used to make the enhanced Raman signals cleaner. By depositing SERS-active metal nanoislands on an atomically flat graphene layer, here we designed a new kind of SERS substrate referred to as a graphene-mediated SERS (G-SERS) substrate. In the graphene/metal combined structure, the electromagnetic “hot” spots (which is the origin of a huge SERS enhancement) created by the gapped metal nanoislands through the localized surface plasmon resonance effect are supposed to pass through the monolayer graphene, resulting in an atomically flat hot surface for Raman enhancement. Signals from a G-SERS substrate were also demonstrated to have interesting advantages over normal SERS, in terms of cleaner vibrational information free from various metal-molecule interactions and being more stable against photo-induced damage, but with a comparable enhancement factor. Furthermore, we demonstrate the use of a freestanding, transparent and flexible “G-SERS tape” (consisting of a polymer-layer-supported monolayer graphene with sandwiched metal nanoislands) to enable direct, real time and reliable detection of trace amounts of analytes in various systems, which imparts high efficiency and universality of analyses with G-SERS substrates. PMID:22623525

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  4. Resonance electronic Raman scattering in rare earth crystals

    SciTech Connect

    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.

  5. Cavity-enhanced Raman microscopy of individual carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Hümmer, Thomas; Noe, Jonathan; Hofmann, Matthias S.; Hänsch, Theodor W.; Högele, Alexander; Hunger, David

    2016-07-01

    Raman spectroscopy reveals chemically specific information and provides label-free insight into the molecular world. However, the signals are intrinsically weak and call for enhancement techniques. Here, we demonstrate Purcell enhancement of Raman scattering in a tunable high-finesse microcavity, and utilize it for molecular diagnostics by combined Raman and absorption imaging. Studying individual single-wall carbon nanotubes, we identify crucial structural parameters such as nanotube radius, electronic structure and extinction cross-section. We observe a 320-times enhanced Raman scattering spectral density and an effective Purcell factor of 6.2, together with a collection efficiency of 60%. Potential for significantly higher enhancement, quantitative signals, inherent spectral filtering and absence of intrinsic background in cavity-vacuum stimulated Raman scattering render the technique a promising tool for molecular imaging. Furthermore, cavity-enhanced Raman transitions involving localized excitons could potentially be used for gaining quantum control over nanomechanical motion and open a route for molecular cavity optomechanics.

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

    SciTech Connect

    Vincenti, M. A.; Ceglia, D. de; Grande, M.; Petruzzelli, V.; D'Orazio, A.; Bianco, G. V.; Bruno, G.; Stomeo, T.; De Vittorio, M.; Scalora, M.

    2013-01-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2000-07-01

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

  8. Raman Scattering at Resonant or Near-Resonant Conditions: A Generalized Short-Time Approximation

    NASA Astrophysics Data System (ADS)

    Mohammed, Abdelsalam; Sun, Yu-Ping; Miao, Quan; Ågren, Hans; Gel'mukhanov, Faris

    2012-02-01

    We investigate the dynamics of resonant Raman scattering in the course of the frequency detuning. The dephasing in the time domain makes the scattering fast when the photon energy is tuned from the absorption resonance. This makes frequency detuning to act as a camera shutter with a regulated scattering duration and provides a practical tool of controlling the scattering time in ordinary stationary measurements. The theory is applied to resonant Raman spectra of a couple of few-mode model systems and to trans-1,3,5-hexatriene and guanine-cytosine (G-C) Watson-Crick base pairs (DNA) molecules. Besides some particular physical effects, the regime of fast scattering leads to a simplification of the spectrum as well as to the scattering theory itself. Strong overtones appear in the Raman spectra when the photon frequency is tuned in the resonant region, while in the mode of fast scattering, the overtones are gradually quenched when the photon frequency is tuned more than one vibrational quantum below the first absorption resonance. The detuning from the resonant region thus leads to a strong purification of the Raman spectrum from the contamination by higher overtones and soft modes and purifies the spectrum also in terms of avoidance of dissociation and interfering fluorescence decay of the resonant state. This makes frequency detuning a very useful practical tool in the analysis of the resonant Raman spectra of complex systems and considerably improves the prospects for using the Raman effect for detection of foreign substances at ultra-low concentrations.

  9. Surface Enhanced Raman Spectroscopy on tunable plasmonic substrates

    NASA Astrophysics Data System (ADS)

    Jackson, Joseph

    2004-03-01

    Thirty years after its initial discovery, Surface Enhanced Raman Scattering (SERS) is still not well understood. The relative contributions of electromagnetic fields at the substrate surface, controlled by its nanoscale topology, and chemical effects, which include resonances of the adsorbate molecules or the formation of new resonant states due to substrate-adsorbate complex formation, can vary uncontrollably in any given substrate-adsorbate combination. The first step towards unraveling the mystery of SERS is precise control of the optical near field at the substrate surface. Recently we have shown that systematic variation in the geometry of a dielectric core-metal shell nanoparticle, or nanoshell, allows its plasmon resonance frequency to be controllably tuned. The electromagnetic fields induced by the plasmon resonance in the vicinity of this simple, symmetric geometry can be calculated straightforwardly, and the fabrication of this core-shell nanoparticle has been experimentally realized in a controlled and reproducible manner. This allows us to systematically investigate the relative contributions of electromagnetic and chemical enhancement to the SERS effect. We have recently shown that variation of the core and shell dimensions on isolated nanoshells in solution for the nonresonant molecule para-mercaptoaniline (pMA) yield a SERS response with excellent agreement between theory and experiment [1]. We extend these studies to examine the SERS response on nanoshell aggregate films, addressing the relative contributions of the single nanoparticle plasmon and dimer or higher order aggregate plasmons to the overall SERS response. This system can also be used to examine the relative contribution of resonant or near-resonant adsorbate molecules to the overall SERS response, and to follow molecular assembly events on the nanoparticle substrate surface. [1] J. B. Jackson et al., Appl. Phys. Lett., 82 (2003) 257.

  10. Resonance Raman Scattering of Rhodamine 6G as Calculated Using Time-Dependent Density Functional Theory

    SciTech Connect

    Jensen, Lasse; Schatz, George C.

    2006-03-27

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. In this work, we present the first calculation of the resonance Raman scattering (RRS) spectrum of rhodamine 6G (R6G) which is a prototype molecule in surface-enhanced Raman scattering (SERS). The calculation is done using a recently developed time-dependent density functional theory (TDDFT) method, which uses a short-time approximation to evaluate the Raman scattering cross section. The normal Raman spectrum calculated with this method is in good agreement with experimental results. The calculated RRS spectrum shows qualitative agreement with SERS results at a wavelength that corresponds to excitation of the S1 state, but there are significant differences with the measured RRS spectrum at wavelengths that correspond to excitation of the vibronic sideband of S1. Although the agreement with the experiments is not perfect, the results provide insight into the RRS spectrum of R6G at wavelengths close to the absorption maximum where experiments are hindered due to strong fluorescence. The calculated resonance enhancements are found to be on the order of 105. This indicates that a surface enhancement factor of about 1010 would be required in SERS in order to achieve single-molecule detection of R6G.

  11. Raman resonance in iron-based superconductors: The magnetic scenario

    NASA Astrophysics Data System (ADS)

    Hinojosa, Alberto; Cai, Jiashen; Chubukov, Andrey V.

    2016-02-01

    We perform theoretical analysis of polarization-sensitive Raman spectroscopy on NaFe1 -xCoxAs , EuFe 2 As2 , SrFe2As2 , and Ba (Fe1 -xCox )2As2 , focusing on two features seen in the B1 g symmetry channel (in one Fe unit cell notation): the strong temperature dependence of the static, uniform Raman response in the normal state and the existence of a collective mode in the superconducting state. We show that both features can be explained by the coupling of fermions to pairs of magnetic fluctuations via the Aslamazov-Larkin process. We first analyze magnetically mediated Raman intensity at the leading two-loop order and then include interactions between pairs of magnetic fluctuations. We show that the full Raman intensity in the B1 g channel can be viewed as the result of the coupling of light to Ising-nematic susceptibility via Aslamazov-Larkin process. We argue that the singular temperature dependence in the normal state is the combination of the temperature dependencies of the Aslamazov-Larkin vertex and of Ising-nematic susceptibility. We discuss two scenario for the resonance below Tc. One is the resonance due to development of a pole in the fully renormalized Ising-nematic susceptibility. Another is orbital excitonic scenario, in which spin fluctuations generate attractive interaction between low-energy fermions.

  12. Resonance Raman based skin carotenoid measurements in newborns and infants

    PubMed Central

    Ermakov, Igor V.; Ermakova, Maia R.; Bernstein, Paul S.; Chan, Gary M.; Gellermann, Werner

    2014-01-01

    We describe Resonance Raman based skin carotenoid measurements in newborns and infants. Skin- and serum carotenoid levels correlate with high statistical significance in healthy newborns and infants, and with reduced accuracy also in prematurely born infants, who in general feature very low carotenoid levels and thin transparent skin giving rise to large background absorption effects. Skin carotenoid levels can be easily compared among subjects and/or tracked in longitudinal studies with the highly molecule-specific Raman method. It therefore holds promise as a rapid, non-invasive, carotenoid antioxidant assessment method for newborns and infants in the field of pediatrics. Photograph of an infant’s skin carotenoid measurement via Resonance Raman spectroscopy. The instrument’s fiber-coupled light delivery and collection module is held against the foot, exposing the heel skin to weak 488 nm laser light for 20 seconds. From spectral analysis of the Raman scattered light intensities, which occur in the green wavelength region, the carotenoid levels in the heel skin are obtained in a rapid, non-invasive, and painless fashion. PMID:23193015

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

    PubMed

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

    2016-05-21

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

  14. Surface enhanced Raman scattering in a hollow core microstructured optical fiber.

    PubMed

    Cox, Felicity M; Argyros, Alexander; Large, Maryanne C J; Kalluri, Srinath

    2007-10-17

    Improvement of surface enhanced resonant Raman scattering (SERRS) signals is demonstrated by confining the scattering event to the core of a hollow core microstructured optical fiber. The analyte solution fills the entire microstructure. The pump light is guided in the liquid core and the Raman scattered signal is efficiently collected by the fiber and transmitted to the detector. Rhodamine 6G (210nM) adsorbed on silver nanoparticles in aqueous solution is used as a demonstration system and it was found that it is possible to collect usable Raman signals from the solution filled optical fiber well beyond the detection limit of an equivalent free-space system. PMID:19550638

  15. Acid Cleavable Surface enhanced Raman Tagging for Protein Detection

    PubMed Central

    Zhang, Dongmao; Vangala, Karthikeshwar; Li, Shaoyong; Yanney, Michael; Xia, Hao; Zou, Sige; Sygula, Andrzej

    2010-01-01

    Dye conjugation is a common strategy improving the surface enhanced Raman detection sensitivity of biomolecules. Reported is a proof-of-concept study of a novel surface enhanced Raman spectroscopic tagging strategy termed as acid-cleavable SERS tag (ACST) method. Using Rhodamine B as the starting material, we prepared the first ACST prototype that consisted of, from the distal end, a SERS tag moiety (STM), an acid-cleavable linker, and a protein reactive moiety. Complete acid cleavage of the ACST tags was achieved at a very mild condition that is 1.5% trifluoroacetic acid (TFA) aqueous solution at room temperature. SERS detection of this ACST tagged protein was demonstrated using bovine serum albumin (BSA) as the model protein. While the SERS spectrum of intact ACST-BSA was entirely dominated by the fluorescent signal of STM, quality SERS spectra can be readily obtained with the acid cleaved ACST-BSA conjugates. Separation of the acid cleaved STM from protein further enhances the SERS sensitivity. Current SERS detection sensitivity, achieved with the acid cleaved ACST-BSA conjugate is ~5 nM in terms of the BSA concentration and ~1.5 nM in ACST content. The linear dynamic range of the cleaved ACST-BSA conjugate spans four orders of magnitudes from ~10 nM to ~100 μM in protein concentrations. Further improvement in the SERS sensitivity can be achieved with resonance Raman acquisition. This cleavable tagging strategy may also be used for elimination of protein interference in fluorescence based biomolecule detection. PMID:21109888

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Surface-enhanced Raman spectroscopy of peptides

    NASA Astrophysics Data System (ADS)

    Garrell, Robin L.; Herne, Tonya M.; Ahern, Angela M.; Sullenberger, Eve L.

    1990-07-01

    Surface-enhanced Raman (SER) spectroscopy has been used to probe the adsorption, surface interactions, and orientations of peptides on metal surfaces. Amino acids in homodipeptides give SER spectra with unique features that can be used to characterize the surface interactions of specific functional groups in more complicated peptides. In heterodipeptides, there is a hierarchy of functional group-surface interactions that prescribe their orientation and conformation on metal surfaces. By establishing this hierarchy, it is now possible to predict the interactions that occur between larger peptides and surfaces. Furthermore, the observed trends suggest that it should be possible to control these interactions by varying the solution pH, the charge on the surface, and other parameters of the measurement in order to adsorb species selectively from mixtures of peptides in solution. Potential biomedical applications of this technique will be described.

  18. Surface enhanced Raman scattering spectroscopic waveguide

    DOEpatents

    Lascola, Robert J; McWhorter, Christopher S; Murph, Simona H

    2015-04-14

    A waveguide for use with surface-enhanced Raman spectroscopy is provided that includes a base structure with an inner surface that defines a cavity and that has an axis. Multiple molecules of an analyte are capable of being located within the cavity at the same time. A base layer is located on the inner surface of the base structure. The base layer extends in an axial direction along an axial length of an excitation section. Nanoparticles are carried by the base layer and may be uniformly distributed along the entire axial length of the excitation section. A flow cell for introducing analyte and excitation light into the waveguide and a method of applying nanoparticles may also be provided.

  19. Suppression and enhancement of dye lasing and stimulated Raman scattering from various dye-doped liquid spheres.

    PubMed

    Taniguchi, H; Tomisawa, H

    1994-09-15

    The observation of suppression or enhancement of dye lasing and stimulated Raman scattering (SRS) from various dye-doped liquid droplets, in which SRS from the initial pumping wavelength appeared in shorter and longer wavelengths of various dye fluorescence regions, is reported; SRS from the dye-lasing wavelengths (double resonances) and stimulated resonance Raman scattering of dyes are included. Furthermore, the contribution to SRS of the dye fluorescence (depending on dye concentration and different dyes) and dye-lasing suppression that is due to stimulated resonance Raman scattering is also described. PMID:19855533

  20. Plasmonic dimer antennas for surface enhanced Raman scattering.

    PubMed

    Höflich, Katja; Becker, Michael; Leuchs, Gerd; Christiansen, Silke

    2012-05-11

    Electron beam induced deposition (EBID) has recently been developed into a method to directly write optically active three-dimensional nanostructures. For this purpose a metal-organic precursor gas (here dimethyl-gold(III)-acetylacetonate) is introduced into the vacuum chamber of a scanning electron microscope where it is cracked by the focused electron beam. Upon cracking the aforementioned precursor gas, 3D deposits are realized, consisting of gold nanocrystals embedded in a carbonaceous matrix. The carbon content in the deposits hinders direct plasmonic applications. However, it is possible to activate the deposited nanostructures for plasmonics by coating the EBID structures with a continuous silver layer of a few nanometers thickness. Within this silver layer collective motions of the free electron gas can be excited. In this way, EBID structures with their intriguing precision at the nanoscale have been arranged in arrays of free-standing dimer antenna structures with nanometer sized gaps between the antennas that face each other with an angle of 90°. These dimer antenna ensembles can constitute a reproducibly manufacturable substrate for exploiting the surface enhanced Raman effect (SERS). The achieved SERS enhancement factors are of the order of 10⁴ for the incident laser light polarized along the dimer axes. To prove the signal enhancement in a Raman experiment we used the dye methyl violet as a robust test molecule. In future applications the thickness of such a silver layer on the dimer antennas can easily be varied for tuning the plasmonic resonances of the SERS substrate to match the resonance structure of the analytes to be detected. PMID:22498764

  1. Quantitative resonance Raman spectroscopy of N-acetylpyrrolidine in aqueous solution

    SciTech Connect

    Harhay, G.P.; Hudson, B.S. )

    1993-08-05

    The resonance Raman spectra of aqueous solutions of N-acetylpyrrolidine are determined at seven excitation frequencies from 40 660 to 53 130 cm[sup [minus]1] spanning the first strong absorption band which is broad and diffuse The resonance Raman spectra are dominated by the single amide II[prime]-like vibration at 1485 cm[sup [minus]1] and its overtones of up to five quanta. Absolute resonance Raman cross sections are determined for these fundamental and overtone transitions at each excitation wavelength by reference to an internal standard of sodium perchlorate. A quantitative analysis of these data and the broad absorption spectrum is made on the basis of a model for the electronic excitation that includes the effects of inhomogeneous broadening. The observation of only a single enhanced vibrational normal mode, with the assumption that there is no Duschinsky rotation upon electronic excitation, makes this a particularly simple case for detailed analysis. A reasonably good fit to the experimental data is obtained using standard assumptions of Lorentzian inhomogeneous broadening and A-term (Condom) Raman scattering. In this fitting procedure, the integrated absorption spectrum determines the transition dipole length. 43 refs., 4 figs., 2 tabs.

  2. Enhanced spontaneous Raman scattering using a photonic crystal fiber

    SciTech Connect

    Buric, M.P.; Falk, J.; Chen, K.; Woodruff, S.D.

    2008-07-22

    The output power from spontaneous gas-phase Raman scattering is enhanced using a hollow-core photonic crystal fiber for the gas cell and Stokes light collector, yielding >100 times enhancement over a free-space configuration.

  3. Enhanced Spontaneous Raman Scattering using a Photonic Crystal Fiber

    SciTech Connect

    M.P. Buric; J. Fal; K. Chen; S. Woodruff1

    2007-10-01

    The output power from spontaneous gas-phase Raman scattering is enhanced using a hollow-core photonic crystal fiber for the gas cell and Stokes light collector, yielding >100 times enhancement over a free-space configuration.

  4. Raman Spectroscopy.

    ERIC Educational Resources Information Center

    Gerrard, Donald L.

    1984-01-01

    Reviews literature on Raman spectroscopy from late 1981 to late 1983. Topic areas include: instrumentation and sampling; liquids and solutions; gases and matrix isolation; biological molecules; polymers; high-temperature and high-pressure studies; Raman microscopy; thin films and surfaces; resonance-enhanced and surface-enhanced spectroscopy; and…

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

    PubMed

    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

  6. Multimodality Raman and photoacoustic imaging of surface-enhanced-Raman-scattering-targeted tumor cells

    NASA Astrophysics Data System (ADS)

    Shi, Wei; Paproski, Robert J.; Shao, Peng; Forbrich, Alexander; Lewis, John D.; Zemp, Roger J.

    2016-02-01

    A multimodality Raman and photoacoustic imaging system is presented. This system has ultralow background and can detect tumor cells labeled with modified surface-enhanced-Raman-scattering (SERS) nanoparticles in vivo. Photoacoustic imaging provides microvascular context and can potentially be used to guide magnetic trapping of circulating tumor cells for SERS detection in animal models.

  7. Towards improved precision in the quantification of surface-enhanced Raman scattering (SERS) enhancement factors: a renewed approach.

    PubMed

    Sivanesan, Arumugam; Adamkiewicz, Witold; Kalaivani, Govindasamy; Kamińska, Agnieszka; Waluk, Jacek; Hołyst, Robert; Izake, Emad L

    2015-01-21

    This paper demonstrates a renewed procedure for the quantification of surface-enhanced Raman scattering (SERS) enhancement factors with improved precision. The principle of this method relies on deducting the resonance Raman scattering (RRS) contribution from surface-enhanced resonance Raman scattering (SERRS) to end up with the surface enhancement (SERS) effect alone. We employed 1,8,15,22-tetraaminophthalocyanato-cobalt(II) (4α-Co(II)TAPc), a resonance Raman- and electrochemically redox-active chromophore, as a probe molecule for RRS and SERRS experiments. The number of 4α-Co(II)TAPc molecules contributing to RRS and SERRS phenomena on plasmon inactive glassy carbon (GC) and plasmon active GC/Au surfaces, respectively, has been precisely estimated by cyclic voltammetry experiments. Furthermore, the SERS substrate enhancement factor (SSEF) quantified by our approach is compared with the traditionally employed methods. We also demonstrate that the present approach of SSEF quantification can be applied for any kind of different SERS substrates by choosing an appropriate laser line and probe molecule. PMID:25374971

  8. Electrochemical Tip-Enhanced Raman Spectroscopy.

    PubMed

    Zeng, Zhi-Cong; Huang, Sheng-Chao; Wu, De-Yin; Meng, Ling-Yan; Li, Mao-Hua; Huang, Teng-Xiang; Zhong, Jin-Hui; Wang, Xiang; Yang, Zhi-Lin; Ren, Bin

    2015-09-23

    Interfacial properties are highly important to the performance of some energy-related systems. The in-depth understanding of the interface requires highly sensitive in situ techniques that can provide fingerprint molecular information at nanometer resolution. We developed an electrochemical tip-enhanced Raman spectroscopy (EC-TERS) by introduction of the light horizontally to the EC-STM cell to minimize the optical distortion and to keep the TERS measurement under a well-controlled condition. We obtained potential-dependent EC-TERS from the adsorbed aromatic molecule on a Au(111) surface and observed a substantial change in the molecule configuration with potential as a result of the protonation and deprotonation of the molecule. Such a change was not observable in EC-SERS (surface-enhanced), indicating EC-TERS can more faithfully reflect the fine interfacial structure than EC-SERS. This work will open a new era for using EC-TERS as an important nanospectroscopy tool for the molecular level and nanoscale analysis of some important electrochemical systems including solar cells, lithium ion batteries, fuel cells, and corrosion. PMID:26351986

  9. Titanium-enhanced Raman microcavity laser.

    PubMed

    Deka, Nishita; Maker, Ashley J; Armani, Andrea M

    2014-03-15

    Whispering gallery mode microcavities are ideally suited to form microlaser devices because the high circulating intensity within the cavity results in ultralow lasing thresholds. However, to achieve low-threshold Raman lasing in silica devices, it is necessary to have quality factors above 100 million. One approach to circumvent this restriction is to intercalate a sensitizer into the silica, which increases the Raman gain. In the present work, we demonstrate a Raman laser based on a titanium sensitized silica solgel coated toroidal microcavity. By tuning the concentration of the Ti, the Raman efficiency improves over 3× while maintaining sub-mW thresholds. PMID:24690786

  10. ARTICLES: Stimulated Raman scattering in resonant nonequilibrium media

    NASA Astrophysics Data System (ADS)

    Khasanov, O. Kh

    1980-12-01

    An analysis is made of the propagation of a short coherent optical pulse in a three-level resonant medium with an essentially nonequidistant spectrum as a function of the degree of preexcitation of the medium. It is found that in addition to self-induced transparency and resonance scattering, stimulated Raman scattering (Stokes or anti-Stokes) should be observed under certain spatial phase-matching conditions. The area theorem is formulated for all radiation components. An analysis is made of the case of propagation of a resonant electromagnetic pulse of frequency ω in a system of three-level atoms having an equidistant spectrum. Under conditions of preexcitation of the medium at the frequency 2ω by longitudinal acoustic pulses, a scattered transverse acoustic wave at the frequency ω may be observed.

  11. The short-range mechanism of surface enhanced raman scattering

    NASA Astrophysics Data System (ADS)

    Furtak, T. E.; Roy, D.

    1985-07-01

    In addition to the electromagnetic influences which increase the local field at the surface of suitably rough free-electron-like metals, molecule and site specific electronic resonances are also frequently operative. This leads to enhanced scattering beyond that caused by the electromagnetic mechanism alone. The electronic resonances involve charge-transfer excitation between members of an active complex M wAg xCl y(H 2O) z which involves the probe molecule M and, in the electrochemical environment, the constituents of the solution. These complexes allow the resonance to be communicated to Raman transitions in all members of the complex. The stability of the complexes are sensitive to changes in the environment, such as the applied voltage and to the presence of foreign metal ions, through induced changes in y, the number of halide or pseudo-halide ions in the complex. Through analysis of the vibrational signature of the probe molecule under various environmental influences we are able to observe subtle changes in the character of the bonding between that molecule and the rest of the complex. These changes can also be interpreted as indirect results of changes in the value of y.

  12. Surface enhanced coherent anti-stokes Raman scattering on nanostructured gold surfaces.

    PubMed

    Steuwe, Christian; Kaminski, Clemens F; Baumberg, Jeremy J; Mahajan, Sumeet

    2011-12-14

    Coherent anti-Stokes Raman spectroscopy (CARS) is a well-known tool in multiphoton imaging and nonlinear spectroscopy. In this work we combine CARS with plasmonic surface enhancement on reproducible nanostructured surfaces. We demonstrate strong correlation between plasmon resonances and surface-enhanced CARS (SECARS) intensities on our nanostructured surfaces and show that an enhancement of ∼10(5) can be obtained over standard CARS. Furthermore, we find SECARS to be >10(3) times more sensitive than surface-enhanced Raman Spectroscopy (SERS). We also demonstrate SECARS imaging of molecular monolayers. Our work paves the way for reliable single molecule Raman spectroscopy and fast molecular imaging on plasmonic surfaces. PMID:22074256

  13. Surface enhanced Raman spectroscopy of individual rhodamine 6G molecules on large Ag nanocrystals

    SciTech Connect

    Michaels, A.M.; Nirmal, M.; Brus, L.E.

    1999-11-03

    To explore the relationship between local electromagnetic field enhancement and the large SERS (surface enhanced Raman scattering) enhancement that enables the observation of single molecule Raman spectra, they measure both resonant Rayleigh scattering spectra and rhodamine 6G Raman spectra from single Ag particles. The apparatus combines the techniques of dark-field optical microscopy for resonant Rayleigh measurements, and grazing incidence Raman spectroscopy. The Rayleigh spectra show that the citrate-reduced Ag colloid is extremely heterogeneous. Only the larger particles, in part created by salt induced aggregation, show a large SERS effect. In agreement with the work of Nie and Emory, a few nanocrystals show huge single molecule R6G SERS intensities. While all SERS active particles have some resonant Rayleigh scattering at the 514.5 nm laser wavelength, there is no correlation between the resonant Rayleigh spectra and the SERS intensity. A model is discussed in which huge SERS intensities result from single chemisorbed molecules interacting with ballistic electrons in optically excited large Ag particles. This model is a natural consequence of the standard local electromagnetic field model for SERS and the high surface sensitivity of plasmon dephasing in the noble metals.

  14. Resonance Raman Spectroscopy of Armchair Single-Walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Haroz, Erik; Rice, William; Lu, Benjamin; Hauge, Robert; Magana, Donny; Doorn, Stephen; Nikolaev, Pasha; Arepalli, Sivaram; Kono, Junichiro

    2009-03-01

    We performed resonance Raman spectroscopy studies of metallic single-walled carbon nanotubes (SWNTs), including armchair SWNTs from (6,6) through (10,10). The measurements were carried out with excitation of 440-850 nm on aqueous ensemble samples of SWNTs enriched in metallic species. From this, we generated Raman excitation profiles (REPs) of the radial breathing mode and compare the REPs of armchairs and other metallic species. Additionally, we measured REPs of the G-band mode and observed how the Breit-Wigner-Fano line shape of the G^- peak evolves in peak position, width and intensity relative to the G^+ peak as different metallic nanotubes are excited. By combining these studies with absorption and photoluminescence excitation spectroscopy studies, we present a comprehensive examination of the optical signatures of metallic SWNTs.

  15. Single-site surface-enhanced Raman scattering beyond spectroscopy

    NASA Astrophysics Data System (ADS)

    Takase, Mai; Yasuda, Satoshi; Murakoshi, Kei

    2016-04-01

    Recent progress in the observation of surface-enhanced Raman scattering (SERS) is reviewed to examine the possibility of finding a novel route for the effective photoexcitation of materials. The importance of well-controlled SERS experiments on a single molecule at a single site is discussed based on the difference in the information obtained from ensemble SERS measurements using multiple active sites with an uncontrolled number of molecules. A single-molecule SERS observation performed at a mechanically controllable breaking junction with a simultaneous conductivity measurement provides clear evidence of the drastic changes both in the intensity and in the Raman mode selectivity of the electromagnetic field generated by localized surface plasmon resonance. Careful control of the field at a few-nanometer-wide gap of a metal nanodimer results in the modification of the selection rule of electronic excitation of an isolated single-walled carbon nanotube. The examples shown in this review suggest that a single-site SERS observation could be used as a novel tool to find, develop, and implement applications of plasmon-induced photoexcitation of materials.

  16. Surface-enhanced Raman scattering (SERS) study of anthocyanidins

    NASA Astrophysics Data System (ADS)

    Zaffino, Chiara; Russo, Bianca; Bruni, Silvia

    2015-10-01

    Anthocyanins are an important class of natural compounds responsible for the red, purple and blue colors in a large number of flowers, fruits and cereal grains. They are polyhydroxy- and polymethoxy-derivatives of 2-phenylbenzopyrylium (flavylium) salts, which are present in nature as glycosylated molecules. The aim of the present study is to assess the identification of anthocyanidins, i.e. anthocyanins without the glycosidic moiety, by means of surface-enhanced Raman spectroscopy (SERS), a very chemically-specific technique which is moreover sensitive to subtle changes in molecular structures. These features can lead to elect SERS, among the spectroscopic tools currently at disposal of scientists, as a technique of choice for the identification of anthocyanidins, since: (1) anthocyanidins structurally present the same benzopyrylium moiety and differentiate only for the substitution pattern on their phenyl ring, (2) different species are present in aqueous solution depending on the pH. It will be demonstrated that, while resonance Raman spectra of anthocyanidins are very similar to one another, SER spectra show greater differences, leading to a further step in the identification of such important compounds in diluted solutions by means of vibrational spectroscopy. Moreover, the dependence on the pH of the six most common anthocyanidins, i.e. cyanidin, delphinidin, pelargonidin, peonidin, malvidin and petunidin, is studied. To the best of the authors' knowledge, a complete SERS study of such important molecules is reported in the present work for the first time.

  17. Study of single walled carbon nanotube functionalization by means of surface enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Ceponkus, Justinas; Velicka, Martynas; Pucetaite, Milda; Sablinskas, Valdas

    2015-09-01

    Raman spectroscopy is known to provide information about the quality of the single walled carbon nanotubes (SWCNT). The information is based on the intensity ratio of D and G spectral modes and the frequency of RBM modes. However due to resonance nature of Raman spectrum of the nanotubes this method is not suitable to detect functionalization of the nanotubes. Surface enhanced Raman spectroscopy (SERS) is known to enhance the Raman bands up to fourteen orders of magnitude. Preferable adsorption sites for small silver nanoparticles are expected to be the functional groups of SWCNT; therefore SERS technique allows detecting small amounts of functional groups despite strong resonance Raman from backbone of SWCNT. In this study functionalized nanotubes were dispersed in silver colloid and dried on the standard silver plate for Raman measurements. Spectra of SWCNT without colloid in the spectral range between 50 and 1800 cm-1 exhibit only four main spectral features: G, D, and RBM modes between 200 and 400 cm-1. Spectra of SWCNT with the colloid exhibit several additional spectral bands which do not belong to the colloid. These bands attributed to vibrations of C-O, C-C and O-H from the functional groups and the carbon atom of the SWCNT attached to the corresponding group. The bands associated with the vibrations involving O atom is an indication that silver nanoparticles interact with the functional group attached to SWCNT.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  19. Molecular selectivity of graphene-enhanced Raman scattering.

    PubMed

    Huang, Shengxi; Ling, Xi; Liang, Liangbo; Song, Yi; Fang, Wenjing; Zhang, Jin; Kong, Jing; Meunier, Vincent; Dresselhaus, Mildred S

    2015-05-13

    Graphene-enhanced Raman scattering (GERS) is a recently discovered Raman enhancement phenomenon that uses graphene as the substrate for Raman enhancement and can produce clean and reproducible Raman signals of molecules with increased signal intensity. Compared to conventional Raman enhancement techniques, such as surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS), in which the Raman enhancement is essentially due to the electromagnetic mechanism, GERS mainly relies on a chemical mechanism and therefore shows unique molecular selectivity. In this paper, we report graphene-enhanced Raman scattering of a variety of different molecules with different molecular properties. We report a strong molecular selectivity for the GERS effect with enhancement factors varying by as much as 2 orders of magnitude for different molecules. Selection rules are discussed with reference to two main features of the molecule, namely its molecular energy levels and molecular structures. In particular, the enhancement factor involving molecular energy levels requires the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies to be within a suitable range with respect to graphene's Fermi level, and this enhancement effect can be explained by the time-dependent perturbation theory of Raman scattering. The enhancement factor involving the choice of molecular structures indicates that molecular symmetry and substituents similar to that of the graphene structure are found to be favorable for GERS enhancement. The effectiveness of these factors can be explained by group theory and the charge-transfer interaction between molecules and graphene. Both factors, involving the molecular energy levels and structural symmetry of the molecules, suggest that a remarkable GERS enhancement requires strong molecule-graphene coupling and thus effective charge transfer between the molecules and graphene. These conclusions are further

  20. Surface-Enhanced Raman Spectroscopy Sensors From Nanobiosilica With Self-Assembled Plasmonic Nanoparticles

    PubMed Central

    Ren, Fanghui; Campbell, Jeremy; Rorrer, Gregory L.; Wang, Alan X.

    2014-01-01

    We present an innovative surface-enhanced Raman spectroscopy (SERS) sensor based on a biological-plasmonic hybrid nanostructure by self-assembling silver (Ag) nanoparticles into diatom frustules. The photonic-crystal-like diatom frustules provide a spatially confined electric field with enhanced intensity that can form hybrid photonic-plasmonic modes through the optical coupling with Ag nanoparticles. The experimental results demonstrate 4–6× and 9–12× improvement of sensitivities to detect the Raman dye for resonance and nonresonance SERS sensing, respectively. Such low-cost and high-sensitivity SERS sensors have significant potentials for label-free biosensing. PMID:25309113

  1. Mechanical Coupling in Gold Nanoparticles Supermolecules Revealed by Plasmon-Enhanced Ultralow Frequency Raman Spectroscopy.

    PubMed

    Girard, A; Gehan, H; Crut, A; Mermet, A; Saviot, L; Margueritat, J

    2016-06-01

    Acoustic vibrations of assemblies of gold nanoparticles were investigated using ultralow frequency micro-Raman scattering and finite element simulations. When exciting the assemblies resonantly with the surface plasmon resonance of electromagnetically coupled nanoparticles, Raman spectra present an ultralow frequency band whose frequency lies below the lowest Raman active Lamb mode of single nanoparticles that was observed. This feature was ascribed to a Raman vibration mode of gold nanoparticle "supermolecules", that is, nanoparticles mechanically coupled by surrounding polymer molecules. Its measured frequency is inversely proportional to the nanoparticle diameter and sensitive to the elastic properties of the interstitial polymer. The latter dependence as well as finite element simulations suggest that this mode corresponds to the out-of-phase semirigid translation (l = 1 Lamb mode) of each nanoparticle of a dimer inside the matrix, activated by the mechanical coupling between the nanoparticles. These observations were permitted only thanks to the resonant excitation with the coupling plasmon excitation, leading to an enhancement up to 10(4) of the scattering by these vibrations. This enhanced ultralow frequency Raman scattering thus opens a new route to probe the local elastic properties of the surrounding medium. PMID:27176093

  2. The study of near-resonance Raman scattering of AlInN/AlN/GaN heterostructure

    NASA Astrophysics Data System (ADS)

    Liu, Yanli; Yang, Lianhong; Chen, Dunjun; Zhang, Li; Lu, Hai; Zhang, Rong; Zheng, Youdou

    2015-07-01

    The visible and ultraviolet (UV) Raman scattering of an AlInN/AlN/GaN heterostructure were measured under z (x, _) z bar configuration at room temperature. Compared with the visible Raman spectrum, three new peaks at 609, 700, and 840 cm-1 occurred in the UV Raman spectrum and were verified to result from the resonance enhanced Raman effect. The near-resonance Raman scattering is stimulated by the electron transition process between the valence band and subband of triangular quantum well located at the interface of AlN/GaN because this transition process has a near equal energy with the 325 nm excitation light. According to the calculated dispersion relations of interface phonon modes in the AlInN/AlN/GaN heterostructure and the 2DEG-related resonance enhanced effect, these new Raman peaks were mainly attributed to the interface phonon modes and disorder-activated mode. The contributions from the bulk phonon modes of AlN and AlInN layers play a very minor role.

  3. Molecular imaging with surface-enhanced Raman spectroscopy nanoparticle reporters

    PubMed Central

    Jokerst, Jesse V.; Pohling, Christoph; Gambhir, Sanjiv S.

    2013-01-01

    Molecular imaging scans cellular and molecular targets in living subjects through the introduction of imaging agents that bind to these targets and report their presence through a measurable signal. The picomolar sensitivity, signal stability, and high multiplexing capacity of Raman spectroscopy satisfies important needs within the field of molecular imaging, and several groups now utilize Raman and surface-enhanced Raman spectroscopy to image molecular targets in small animal models of human disease. This article details the role of Raman spectroscopy in molecular imaging, describes some substrates and imaging agents used in animal models, and illustrates some examples. PMID:24293809

  4. Monitoring LED-induced carotenoid increase in grapes by Transmission Resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Gonzálvez, Alicia G.; Martínez, Nerea L.; Telle, Helmut H.; Ureña, Ángel González

    2013-02-01

    Transmission Resonance Raman (TRR) spectroscopy combines increased signal-to-noise ratio with enhanced analytical sensibility. TRR was applied to directly monitor, without any sample preparation, the enhancement of β-carotene content in table grapes when they are irradiated by low power UV-LEDs. It was shown that, with respect to control samples, the carotenoid content in the grapes increased about five-fold, using UV-LED irradiation doses being two orders of magnitude lower than the maximum limit allowed by United States Food and Drug Administration. These promising results may pave the way for the development of easy, non-invasive techniques to improve food quality.

  5. Strongly enhanced Raman scattering of graphene by a single gold nanorod

    SciTech Connect

    He, Yingbo; Shen, Hongming; Cheng, Yuqing; Lu, Guowei Gong, Qihuang

    2015-08-03

    Individual gold nanorods (AuNRs) and monolayer graphene hybrid system is investigated experimentally. Surface enhanced Raman scattering (SERS) signal of the graphene is observed due to a single AuNR with enhancement factor up to ∼1000-fold. The SERS intensity is strongly polarization dependent and the enhancement effect varies with the detuning between the excitation laser and the AuNR resonance. The SERS effect is highest when the resonant wavelength of the AuNRs matches well with the excitation light. By correlating the scattering and photoluminescence, it is demonstrated that the conventional background in SERS ascribes to the photon emission of metallic nanostructures.

  6. Hadronic resonances enhanced by thresholds

    NASA Astrophysics Data System (ADS)

    Caramés, T. F.; Valcarce, A.

    2016-07-01

    We present a neat example of a meson-baryon system where the vicinity of two different thresholds enhances the binding of a hadronic resonance, a pentaquark. As a consequence the pattern of states may change when moving among different flavor sectors, what poses a warning on naive extrapolations to heavy flavor sectors based on systematic expansions. For this purpose we simultaneously analyze the N D bar and NB two-hadron systems looking for possible bound states or resonances. When a resonance is controlled by a coupled-channel effect, going to a different flavor sector may enhance or diminish the binding. This effect may, for example, generate significant differences between the charmonium and bottomonium spectra above open-flavor thresholds or pentaquark states in the open-charm and open-bottom sectors.

  7. Resonance Raman spectroscopic studies of enzymesubstrate intermediates at 5 K

    NASA Astrophysics Data System (ADS)

    Kim, Munsok; Carey, Paul R.

    1991-01-01

    A simple and versatile system for resonance Raman (RR) spectroscopic analysis of enzymesubstrate complexes at liquid helium temperatures is described. The system allows us to record high-quality RR spectra for dithioacyl papain intermediates (MeO-Phe-Gly- and MeO-Gly-Gly-Phe-Gly-C (dbnd S)S-papain) in ice matrices at 5 K. Based on established structure-spectra correlations, it is concluded that the active-site conformation of the intermediates about the φ', ψ' glycinic linkages and cysteine-25 side chain is B-G+-PH both in ice matrices at 5 K and in solution at room temperature.

  8. Resonant impulsive-stimulated Raman scattering on malachite green

    SciTech Connect

    Chesnoy, J.; Mokhtari, A.

    1988-10-01

    We have studied in the femtosecond regime the transient dynamics of dichroism (anisotropic absorption), birefringence, and frequency shift induced by an intense femtosecond pump beam in the dye malachite green in solution. Vibrational quantum beats were observed superimposed on the saturated absorption and dispersion signals and quantitatively explained in terms of impulsive-stimulated Raman scattering close to an electronic resonance. The selectivity for observation of the vibrations in the two electronic states is described for the different experimental schemes. We discuss the access to vibrational and electronic dynamics in both ground and excited electronic states and compare the possibilities to those of previous techniques.

  9. Metallic nanoparticle arrays: a common substrate for both surface-enhanced Raman scattering and surface-enhanced infrared absorption.

    PubMed

    Le, Fei; Brandl, Daniel W; Urzhumov, Yaroslav A; Wang, Hui; Kundu, Janardan; Halas, Naomi J; Aizpurua, Javier; Nordlander, Peter

    2008-04-01

    Nanoshell arrays have recently been found to possess ideal properties as a substrate for combining surface enhanced raman scattering (SERS) and surface enhanced infrared absorption (SEIRA) spectroscopies, with large field enhancements at the same spatial locations on the structure. For small interparticle distances, the multipolar plasmon resonances of individual nanoshells hybridize and form red-shifted bands, a relatively narrow band in the near-infrared (NIR) originating from quadrupolar nanoshell resonances enhancing SERS, and a very broadband in the mid-infrared (MIR) arising from dipolar resonances enhancing SEIRA. The large field enhancements in the MIR and at longer wavelengths are due to the lightning-rod effect and are well described with an electrostatic model. PMID:19206602

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

    NASA Astrophysics Data System (ADS)

    Ghamsari, Behnood G.; Berini, Pierre

    2016-07-01

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

  11. Surface and waveguide collection of Raman emission in waveguide-enhanced Raman spectroscopy.

    PubMed

    Wang, Zilong; Zervas, Michalis N; Bartlett, Philip N; Wilkinson, James S

    2016-09-01

    We demonstrate Raman spectroscopy on a high index thin film tantalum pentoxide waveguide and compare collection of Raman emission from the waveguide end with that from the waveguide surface. Toluene was used as a convenient model analyte, and a 40-fold greater signal was collected from the waveguide end. Simulations of angular and spatial Raman emission distributions showed good agreement with experiments, with the enhancement resulting from efficient collection of power from dipoles near the surface into the high-index waveguide film and substrate, combined with long interaction length. The waveguide employed was optimized at the excitation wavelength but not at emission wavelengths, and full optimization is expected to lead to enhancements comparable to surface-enhanced Raman spectroscopy in robust low-cost metal-free and nanostructure-free chips. PMID:27607994

  12. Ultrafast and nonlinear surface-enhanced Raman spectroscopy.

    PubMed

    Gruenke, Natalie L; Cardinal, M Fernanda; McAnally, Michael O; Frontiera, Renee R; Schatz, George C; Van Duyne, Richard P

    2016-04-21

    Ultrafast surface-enhanced Raman spectroscopy (SERS) has the potential to study molecular dynamics near plasmonic surfaces to better understand plasmon-mediated chemical reactions such as plasmonically-enhanced photocatalytic or photovoltaic processes. This review discusses the combination of ultrafast Raman spectroscopic techniques with plasmonic substrates for high temporal resolution, high sensitivity, and high spatial resolution vibrational spectroscopy. First, we introduce background information relevant to ultrafast SERS: the mechanisms of surface enhancement in Raman scattering, the characterization of plasmonic materials with ultrafast techniques, and early complementary techniques to study molecule-plasmon interactions. We then discuss recent advances in surface-enhanced Raman spectroscopies with ultrafast pulses with a focus on the study of molecule-plasmon coupling and molecular dynamics with high sensitivity. We also highlight the challenges faced by this field by the potential damage caused by concentrated, highly energetic pulsed fields in plasmonic hotspots, and finally the potential for future ultrafast SERS studies. PMID:26848784

  13. Multiphonon resonant Raman scattering in MoS{sub 2}

    SciTech Connect

    Gołasa, K. Grzeszczyk, M.; Wysmołek, A.; Babiński, A.; Leszczyński, P.; Faugeras, C.; Nicolet, A. A. L.; Potemski, M.

    2014-03-03

    Optical emission spectrum of a resonantly (λ = 632.8 nm) excited molybdenum disulfide (MoS{sub 2}) is studied at liquid helium temperature. More than 20 peaks in the energy range spanning up to 1400 cm{sup −1} from the laser line, which are related to multiphonon resonant Raman scattering processes, are observed. The attribution of the observed lines involving basic lattice vibrational modes of MoS{sub 2} and both the longitudinal (LA(M)) and the transverse (TA(M) and/or ZA(M)) acoustic phonons from the vicinity of the high-symmetry M point of the MoS{sub 2} Brillouin zone is proposed.

  14. Cold atom Raman spectrography using velocity-selective resonances.

    PubMed

    Fatemi, Fredrik K; Terraciano, Matthew L; Bashkansky, Mark; Dutton, Zachary

    2009-07-20

    We have studied velocity-selective resonances in the presence of a uniform magnetic field and shown how they can be used for rapid, single-shot assessment of the ground state magnetic sublevel spectrum in a cold atomic vapor. Cold atoms are released from a magneto-optical trap in the presence of a small bias magnetic field ( approximately 300 mG) and exposed to a laser field comprised of two phase-locked counterpropagating beams connecting the two ground state hyperfine manifolds. An image of the expanded cloud shows the velocity-selected resonances as distinct features, each corresponding to specific magnetic sublevel, in a direct, intuitive manner. We demonstrate the technique with both 87Rb and 85Rb, and show the utility of the technique by optically pumping into particular magnetic sublevels. The results are shown to agree with a theoretical model, and are compared to traditional Raman spectroscopy. PMID:19654701

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

    SciTech Connect

    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).

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

    SciTech Connect

    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. Surface-enhanced Raman scattering (SERS) dosimeter and probe

    DOEpatents

    Vo-Dinh, Tuan

    1995-01-01

    A dosimeter and probe for measuring exposure to chemical and biological compounds is disclosed. The dosimeter or probe includes a collector which may be analyzed by surface-enhanced Raman spectroscopy. The collector comprises a surface-enhanced Raman scattering-active material having a coating applied thereto to improve the adsorption properties of the collector. The collector may also be used in automated sequential devises, in probe array devices.

  18. Surface-enhanced Raman scattering (SERS) dosimeter and probe

    DOEpatents

    Vo-Dinh, T.

    1995-03-21

    A dosimeter and probe for measuring exposure to chemical and biological compounds is disclosed. The dosimeter or probe includes a collector which may be analyzed by surface-enhanced Raman spectroscopy. The collector comprises a surface-enhanced Raman scattering-active material having a coating applied thereto to improve the adsorption properties of the collector. The collector may also be used in automated sequential devices, in probe array devices. 10 figures.

  19. UV resonance Raman study of model complexes of the Cu B site of cytochrome c oxidase

    NASA Astrophysics Data System (ADS)

    Nagano, Yasutomo; Liu, Jin-Gang; Naruta, Yoshinori; Kitagawa, Teizo

    2005-02-01

    A newly designed model complex for the CuB site of cytochrome c oxidase (CcO), that is, Cu coordinated by two free imidazoles and an imidazole covalently linked to p-cresol [CuIIBIAIPBr]Br, (BIAIP =2-[4-[[Bis(1-methyl-1H-imidazol-2-ylmethyl)amino]methyl]-1H-imidazol-1-yl]-4-methylphenol), and related molecules have been investigated with absorption and ultraviolet resonance Raman (UVRR) spectroscopy employing the excitation wavelengths between 220 and 290 nm. Attention was focused on the electron delocalization through the cross-linkage between the phenol and imidazole rings, and the influences by the coordination of CuII to imidazole. In addition to the ν8a and ν8b modes of p-cresol, a number of Raman bands involving vibrations of the imidazole moiety have been intensity-enhanced despite Raman excitation in resonance with the π-π* transition of phenol, indicating appreciable mixing of the π systems of imidazole and phenol rings. Furthermore, two kinds of imidazoles seem to be differential; one is the imidazole linked to p-cresol which yielded Raman bands at 1249, 1191, and 1141 cm-1 for protonated CuII-BIAIP, and the other is one not linked to p-cresol, which yielded an intense band at 1488 cm-1 band. Raman enhancement of the latter mode seems to be caused by preresonance to the lowest π-π* transition of imidazole via the A-term mechanism. The Raman excitation profile (REP) of ν8a mode for the deprotonated phenol of the CuII-complex revealed a weak local maximum corresponding to the La band around 240 nm. Raman enhancement by the La band was relatively weaker for the CuII-complex than for the ZnII-complex and metal-free ligand, suggesting the more extensive mixing of π systems of p-cresol-imidazole through the cross-linkage for the Cu II-complex.

  20. Chemical mechanism of surface-enhanced Raman scattering via charge transfer in fluorenone–Ag complex

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Li, Yafei; Wu, Shiwei; Song, Peng; Xia, Lixin

    2016-06-01

    The intermolecular interaction between fluorenone (FN) and silver surfaces was investigated experimentally and theoretically. The structural, electronic and optical properties of the FN–Ag complex indicate that the carbonyl group O atom in FN molecules is the adsorbed position site to attach the silver substrate through the weak bond O…Ag. The analysis of vibrational modes and Raman activity of the largely enhanced Raman peaks using two FN–Ag4-x (x  =  l, s) complex models reveals that only the a1 vibrational modes with C 2v symmetry are selectively enhanced, from the point view of the change of dipole moment and polarizability induced by the interaction between FN and Ag4 substrate. Furthermore, the direct visualized evidence of the surface-enhanced Raman scattering (SERS) chemical enhancement mechanism for the FN–Ag complex is presented. The results reveal that only the intermolecular charge transfer with π–π transition characterization between FN and an Ag4 cluster facilitates the resonance Raman process and is directly responsible for chemical enhancement of Raman scattering of the FN–Ag complex.

  1. Chemical mechanism of surface-enhanced Raman scattering via charge transfer in fluorenone-Ag complex.

    PubMed

    Wang, Jing; Li, Yafei; Wu, Shiwei; Song, Peng; Xia, Lixin

    2016-06-01

    The intermolecular interaction between fluorenone (FN) and silver surfaces was investigated experimentally and theoretically. The structural, electronic and optical properties of the FN-Ag complex indicate that the carbonyl group O atom in FN molecules is the adsorbed position site to attach the silver substrate through the weak bond O…Ag. The analysis of vibrational modes and Raman activity of the largely enhanced Raman peaks using two FN-Ag4-x (x  =  l, s) complex models reveals that only the a1 vibrational modes with C 2v symmetry are selectively enhanced, from the point view of the change of dipole moment and polarizability induced by the interaction between FN and Ag4 substrate. Furthermore, the direct visualized evidence of the surface-enhanced Raman scattering (SERS) chemical enhancement mechanism for the FN-Ag complex is presented. The results reveal that only the intermolecular charge transfer with π-π transition characterization between FN and an Ag4 cluster facilitates the resonance Raman process and is directly responsible for chemical enhancement of Raman scattering of the FN-Ag complex. PMID:27147706

  2. Carotenoid Analysis of Halophilic Archaea by Resonance Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Marshall, Craig P.; Leuko, Stefan; Coyle, Candace M.; Walter, Malcolm R.; Burns, Brendan P.; Neilan, Brett A.

    2007-08-01

    Recently, halite and sulfate evaporate rocks have been discovered on Mars by the NASA rovers, Spirit and Opportunity. It is reasonable to propose that halophilic microorganisms could have potentially flourished in these settings. If so, biomolecules found in microorganisms adapted to high salinity and basic pH environments on Earth may be reliable biomarkers for detecting life on Mars. Therefore, we investigated the potential of Resonance Raman (RR) spectroscopy to detect biomarkers derived from microorganisms adapted to hypersaline environments. RR spectra were acquired using 488.0 and 514.5 nm excitation from a variety of halophilic archaea, including Halobacterium salinarum NRC-1, Halococcus morrhuae, and Natrinema pallidum. It was clearly demonstrated that RR spectra enhance the chromophore carotenoid molecules in the cell membrane with respect to the various protein and lipid cellular components. RR spectra acquired from all halophilic archaea investigated contained major features at approximately 1000, 1152, and 1505 cm-1. The bands at 1505 cm-1 and 1152 cm-1 are due to in-phase C=C (ν1 ) and C-C stretching ( ν2 ) vibrations of the polyene chain in carotenoids. Additionally, in-plane rocking modes of CH3 groups attached to the polyene chain coupled with C-C bonds occur in the 1000 cm-1 region. We also investigated the RR spectral differences between bacterioruberin and bacteriorhodopsin as another potential biomarker for hypersaline environments. By comparison, the RR spectrum acquired from bacteriorhodopsin is much more complex and contains modes that can be divided into four groups: the C=C stretches (1600-1500 cm-1), the CCH in-plane rocks (1400-1250 cm-1), the C-C stretches (1250-1100 cm-1), and the hydrogen out-of-plane wags (1000-700 cm-1). RR spectroscopy was shown to be a useful tool for the analysis and remote in situ detection of carotenoids from halophilic archaea without the need for large sample sizes and complicated extractions, which are

  3. Tip-enhanced Raman spectroscopy and near-field polarization

    NASA Astrophysics Data System (ADS)

    Saito, Yuika; Mino, Toshihiro; Verma, Prabhat

    2015-12-01

    Tip-enhanced Raman spectroscopy (TERS) is a powerful tool for High-resolution Raman spectroscopy. In this method, a metal coated nano-tip acts as a plasmonic antenna to enhance the originally weak Raman scattering from a nanometric volume of a sample. The technique enables to detect Raman scattering light from nano-scale area and also enhance the light intensity with combination of near-filed light and localized surface plasmon generated at a metallized tip apex. Nowadays TERS is used to investigate various nano-scale samples, for examples, carbon nanotubes, graphenes DNA and biomaterials. As the TERS developed, there is high demand to investigate the properties of near-field light e.g. polarization properties. We have analyzed the polarization properties of near-field light in TERS and successfully realized the quantitative nano-imaging by visible light.

  4. Raman and surface-enhanced Raman spectroscopy for renal condition monitoring

    NASA Astrophysics Data System (ADS)

    Li, Jingting; Li, Ming; Du, Yong; Santos, Greggy M.; Mohan, Chandra; Shih, Wei-Chuan

    2016-03-01

    Non- and minimally-invasive techniques can provide advantages in the monitoring and clinical diagnostics in renal diseases. Although renal biopsy may be useful in establishing diagnosis in several diseases, it is an invasive approach and impractical for longitudinal disease monitoring. To address this unmet need, we have developed two techniques based on Raman spectroscopy. First, we have investigated the potential of diagnosing and staging nephritis by analyzing kidney tissue Raman spectra using multivariate techniques. Secondly, we have developed a urine creatinine sensor based on surface-enhanced Raman spectroscopy with performance near commercial assays which require relatively laborious sample preparation and longer time.

  5. Probing the spatial extension of light trapping-induced enhanced Raman scattering in high-density Si nanowire arrays

    NASA Astrophysics Data System (ADS)

    Bontempi, Nicolò; Salmistraro, Marco; Ferroni, Matteo; Depero, Laura E.; Alessandri, Ivano

    2014-11-01

    This paper reports an experimental investigation of surface-enhanced Raman scattering in high-density Si nanowire arrays obtained by electroless etching. A direct relationship between light trapping capabilities of Si nanowires and enhanced Raman scattering was demonstrated. Optimized arrays allowed for a remarkable increase of Raman sensitivity in comparison to reference planar samples. As a result, the detection limit of molecular probes under resonant excitation (e.g. methylene blue) can be extended by three orders of magnitude. In addition, continuous ultrathin films, that cannot be analyzed in conventional Raman experiments, are made detectable. In the case of anatase thin films, the detection limit of 5 nm was reached. Raman spectra of Si/TiO2 core/shell heterostructures demonstrate that the enhanced field resulting from surface multiple scattering is characterized by a large spatial extension (about fifty nanometers), making these materials a potential alternative to plasmonic metals for SERS experiments.

  6. A comparative study of Raman enhancement in capillaries

    NASA Astrophysics Data System (ADS)

    Eftekhari, Fatemeh; Irizar, Juan; Hulbert, Laila; Helmy, Amr S.

    2011-06-01

    This work reports on the comparative studies of Raman enhancement in liquid core waveguides (LCWs). The theoretical considerations that describe Raman enhancement in LCWs is adapted to analyze and compare the performance of hollow core photonic crystal fibers (HCPCFs) to conventional Teflon capillary tubes. The optical losses in both platforms are measured and used to predict their performance for different lengths. The results show that for an optimal waveguide length, two orders of magnitude enhancement in the Raman signal can be achieved for aqueous solutions using HCPCFs. This length, however, cannot be achieved using normal capillary effects. By integrating the interface of the fluidic pump and the HCPCF into a microfluidic chip, we are able to control fluid transport and fill longer lengths of HCPCFs regardless of the viscosity of the sample. The long-term stability and reproducibility of Raman spectra attained through this platform are demonstrated for naphthalenethiol, which is a well-studied organic compound. Using the HCPCF platform, the detection limit of normal Raman scattering in the range of micro-molars has been achieved. In addition to the higher signal-to-noise ratio of the Raman signal from the HCPCF-platform, more Raman modes of naphthalenethiol are revealed using this platform.

  7. Cavity-enhanced Raman microscopy of individual carbon nanotubes

    PubMed Central

    Hümmer, Thomas; Noe, Jonathan; Hofmann, Matthias S.; Hänsch, Theodor W.; Högele, Alexander; Hunger, David

    2016-01-01

    Raman spectroscopy reveals chemically specific information and provides label-free insight into the molecular world. However, the signals are intrinsically weak and call for enhancement techniques. Here, we demonstrate Purcell enhancement of Raman scattering in a tunable high-finesse microcavity, and utilize it for molecular diagnostics by combined Raman and absorption imaging. Studying individual single-wall carbon nanotubes, we identify crucial structural parameters such as nanotube radius, electronic structure and extinction cross-section. We observe a 320-times enhanced Raman scattering spectral density and an effective Purcell factor of 6.2, together with a collection efficiency of 60%. Potential for significantly higher enhancement, quantitative signals, inherent spectral filtering and absence of intrinsic background in cavity-vacuum stimulated Raman scattering render the technique a promising tool for molecular imaging. Furthermore, cavity-enhanced Raman transitions involving localized excitons could potentially be used for gaining quantum control over nanomechanical motion and open a route for molecular cavity optomechanics. PMID:27402165

  8. Cavity-enhanced Raman microscopy of individual carbon nanotubes.

    PubMed

    Hümmer, Thomas; Noe, Jonathan; Hofmann, Matthias S; Hänsch, Theodor W; Högele, Alexander; Hunger, David

    2016-01-01

    Raman spectroscopy reveals chemically specific information and provides label-free insight into the molecular world. However, the signals are intrinsically weak and call for enhancement techniques. Here, we demonstrate Purcell enhancement of Raman scattering in a tunable high-finesse microcavity, and utilize it for molecular diagnostics by combined Raman and absorption imaging. Studying individual single-wall carbon nanotubes, we identify crucial structural parameters such as nanotube radius, electronic structure and extinction cross-section. We observe a 320-times enhanced Raman scattering spectral density and an effective Purcell factor of 6.2, together with a collection efficiency of 60%. Potential for significantly higher enhancement, quantitative signals, inherent spectral filtering and absence of intrinsic background in cavity-vacuum stimulated Raman scattering render the technique a promising tool for molecular imaging. Furthermore, cavity-enhanced Raman transitions involving localized excitons could potentially be used for gaining quantum control over nanomechanical motion and open a route for molecular cavity optomechanics. PMID:27402165

  9. Molecule-surface interactions probed by optimized surface-enhanced coherent Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Voronine, Dmitri; Sinyukov, Alexander; Hua, Xia; Zhang, Guowan; Yang, Wenlong; Wang, Kai; Jha, Pankaj; Welch, George; Sokolov, Alexei; Scully, Marlan

    2012-06-01

    Nanoscale molecular sensing is carried out using a time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy with optimized laser pulse configurations. This novel technique combines the advantages of an improved spectral resolution, suppressed non-resonant background and near-field surface enhancement of the Raman signal. We detect two species of pyridine in a vicinity of aggregated gold nanoparticles and measure their vibrational dephasing times which reveal the effects of surface environment and molecule-surface interactions on the ultrafast molecular dynamics. This technique may be applied to a variety of artificial and biological systems and complex molecular mixtures and has a potential for nanophotonic sensing applications.

  10. Surface-enhanced Raman spectroscopy of creatinine in silver colloid

    NASA Astrophysics Data System (ADS)

    Wang, Yue; Chen, Jiesi; Wu, Yanan; Chen, Yanping; Pan, Jianji; Lei, Jinping; Chen, Yongjian; Sun, Liqing; Feng, Shangyuan; Chen, Rong

    2011-11-01

    Surface enhanced Raman spectroscopy (SERS) technology has already made great progress in bio-molecule detection. It can make the target molecules strongly absorbed onto the surface of metal nanoparticles, and then the Raman signal of its own has been greatly enhanced through physical and chemical enhancement mechanisms. We report the SERS spectra of creatinine in silver colloid, and study the silver colloid enhanced effects on the Raman scattering of creatinine. We can also find that creatinine concentration is linearly related to its SERS peak intensity and the detection limit of creatinine silver sol is found to be 10 mg/dl. In conclusion, we can observe that the silver colloid has very good enhanced effects for the creatinine. The potential applications of SERS in quantitative measurement of the creatinine liquor are demonstrated. The result shows that the SERS approach would provide a unique and fast test method for creatinine detection.

  11. Surface-enhanced Raman spectroscopy of creatinine in silver colloid

    NASA Astrophysics Data System (ADS)

    Wang, Yue; Chen, Jiesi; Wu, Yanan; Chen, Yanping; Pan, Jianji; Lei, Jinping; Chen, Yongjian; Sun, Liqing; Feng, Shangyuan; Chen, Rong

    2012-03-01

    Surface enhanced Raman spectroscopy (SERS) technology has already made great progress in bio-molecule detection. It can make the target molecules strongly absorbed onto the surface of metal nanoparticles, and then the Raman signal of its own has been greatly enhanced through physical and chemical enhancement mechanisms. We report the SERS spectra of creatinine in silver colloid, and study the silver colloid enhanced effects on the Raman scattering of creatinine. We can also find that creatinine concentration is linearly related to its SERS peak intensity and the detection limit of creatinine silver sol is found to be 10 mg/dl. In conclusion, we can observe that the silver colloid has very good enhanced effects for the creatinine. The potential applications of SERS in quantitative measurement of the creatinine liquor are demonstrated. The result shows that the SERS approach would provide a unique and fast test method for creatinine detection.

  12. The confinement induced resonance in spin-orbit coupled cold atoms with Raman coupling

    PubMed Central

    Zhang, Yi-Cai; Song, Shu-Wei; Liu, Wu-Ming

    2014-01-01

    The confinement induced resonance provides an indispensable tool for the realization of the low-dimensional strongly interacting quantum system. Here, we investigate the confinement induced resonance in spin-orbit coupled cold atoms with Raman coupling. We find that the quasi-bound levels induced by the spin-orbit coupling and Raman coupling result in the Feshbach-type resonances. For sufficiently large Raman coupling, the bound states in one dimension exist only for sufficiently strong attractive interaction. Furthermore, the bound states in quasi-one dimension exist only for sufficient large ratio of the length scale of confinement to three dimensional s-wave scattering length. The Raman coupling substantially changes the confinement-induced resonance position. We give a proposal to realize confinement induced resonance through increasing Raman coupling strength in experiments. PMID:24862314

  13. Resonance Raman Spectroscopy of Purple Membrane from Halobacterium Halobium.

    NASA Astrophysics Data System (ADS)

    Argade, Pramod Vasant

    Purple membrane from the halophilic bacteria, Halobacterium halobium, contains the protein, bacteriorhodopsin, which functions as a light transducing proton pump. Understanding the molecular mechanism underlying the functioning of bacteriorhodopsin is a key problem in membrane biophysics. After absorbing a photon, this protein cycles through a series of characteristic intermeidate states and pumps H('+) ions across the membrane. In this way, the energy of the absorbed photon is stored in the electrochemical potential gradient formed across the membrane. This energy is subsequently available for metabolism by the bacterium. Bacteriorhodopsin consists of a retinal chromophore (which is responsible for the purple color) bound to the protein, bacterioopsin, whose sequence is known and consists of 248 amino acid residues. There is evidence that conformational changes in the chromophore may contribute to the proton pumping action. Resonance Raman light scattering provides a selective tool to monitor the conformational changes in the chromophore during the proton pumping cycle. This dissertation consists of applying resonance Raman light scattering in conjunction with a variety of newly developed experimental techniques to gain information about the mode of action of bacteriorhodopsin. By selective isotopic labelling of (epsilon)-amino nitrogen of the lysine residues of the protein, the site of attachment of the chromophore with the protein was verified by in situ measurements. Also, a model proposing a secondary interaction of the chromophore with a lysine residue other than the binding site of the chromophore was tested using this method. Furthermore, by selective isotopic labelling of only a part of the protein the location of the lysine on the protein to which the chromophore is bound, was found by in situ measurements to be the fragment consisting of amino acid residues 72 through 248 of the protein. This is inconsistent with the previously reported binding site at

  14. Al-doped MgB2 materials studied using electron paramagnetic resonance and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Bateni, Ali; Erdem, Emre; Repp, Sergej; Weber, Stefan; Somer, Mehmet

    2016-05-01

    Undoped and aluminum (Al) doped magnesium diboride (MgB2) samples were synthesized using a high-temperature solid-state synthesis method. The microscopic defect structures of Al-doped MgB2 samples were systematically investigated using X-ray powder diffraction, Raman spectroscopy, and electron paramagnetic resonance. It was found that Mg-vacancies are responsible for defect-induced peculiarities in MgB2. Above a certain level of Al doping, enhanced conductive properties of MgB2 disappear due to filling of vacancies or trapping of Al in Mg-related vacancy sites.

  15. Power Budget Analysis for Waveguide-Enhanced Raman Spectroscopy.

    PubMed

    Wang, Zilong; Pearce, Stuart J; Lin, Yung-Chun; Zervas, Michalis N; Bartlett, Philip N; Wilkinson, James S

    2016-08-01

    Waveguide-enhanced Raman spectroscopy (WERS) is emerging as an attractive alternative to plasmonic surface-enhanced Raman spectroscopy approaches as it can provide more reproducible quantitative spectra on a robust chip without the need for nanostructured plasmonic materials. Realizing portable WERS systems with high sensitivity using low-cost laser diodes and compact spectrometers requires a detailed analysis of the power budget from laser to spectrometer chip. In this paper, we describe theoretical optimization of planar waveguides for maximum Raman excitation efficiency, demonstrate WERS for toluene on a silicon process compatible high index contrast tantalum pentoxide waveguide, measure the absolute conversion efficiency from pump power to received power in an individual Raman line, and compare this with a power budget analysis of the complete system including collection with an optical fiber and interfacing to a compact spectrometer. Optimized 110 nm thick Ta2O5 waveguides on silica substrates excited at a wavelength of 637 nm are shown experimentally to yield overall system power conversion efficiency of ∼0.5 × 10(-12) from the pump power in the waveguide to the collected Raman power in the 1002 cm(-1) Raman line of toluene, in comparison with a calculated efficiency of 3.9 × 10(-12) Collection efficiency is dictated by the numerical and physical apertures of the spectral detection system but may be improved by further engineering the spatial and angular Raman scattering distributions. PMID:27301326

  16. Surface-enhanced Raman microspectroscopy at electrode surfaces

    SciTech Connect

    Hembree D.M. Jr.; Oswald, J.C.; Smyrl, N.R.

    1987-02-01

    Surface-enhanced Raman microspectroscopy has been developed as a technique for characterizing processes occurring at the electrode/electrolyte interface. A spectroelectrochemical cell was designed to obtain Raman spectra of electrochemical species with the use of microscope optics, which allowed unambiguous placement of laser focus at the electrode surface with spatial resolution on the order of 1 ..mu..m. It was also possible to visually inspect the surface morphology of the electrode with the use of the Raman microscope in the reflected-light mode. The capabilities of the spectroelectrochemical cell were demonstrated by observation of surface-enhanced Raman scattering (SERS) for a variety of model systems (pyridine, pyridinium ion, potassium cyanide) with the use of silver, copper, and nickel electrodes. The electrochemical behavior of a commercially important gold electroplating process is also reported.

  17. Resonance Raman studies of bathorhodopsin: evidence for a protonated Schiff base linkage.

    PubMed

    Eyring, G; Mathies, R

    1979-01-01

    A dual beam pump/probe technique has been used with a 585-nm probe wavelength to obtain maximal resonance enhancement of the Raman lines of bathorhodopsin in a photostationary steady-state mixture at -160 degrees C. These studies show that bathorhodopsin has a protonated Schiff base vibration at 1657 cm(-1) which shifts upon deuteration to 1625 cm(-1). Within our experimental error (+/-2 cm(-1)) these frequencies are identical to those observed in rhodopsin and isorhodopsin. These effects show that the strength of the C=N bond and the degree of protonation of the Schiff base nitrogen are the same in bathorhodopsin, rhodopsin, and isorhodopsin. The implication of these results for the structure of the retinal chromophore in bathorhodopsin are discussed. The resonance Raman spectrum of pure bathorhodopsin has been generated by accurately subtracting the residual contributions of rhodopsin and isorhodopsin from spectra of the low temperature photostationary mixture. Bathorhodopsin is found to have lines at 853, 875, 920, 1006, 1166, 1210, 1278, 1323, 1536, and 1657 cm(-1). Also, by using an intensified vidicon detector, we have observed Raman scattering from bathorhodopsin at room temperature by generating a photostationary steady state with pulsed laser excitation. At room temperature the three characteristic lines of bathorhodopsin are found at 858, 873, and 920 cm(-1). The fact that the frequencies of these bathorhodopsin lines are nearly identical at both temperatures implies that the retinal conformation in bathorhodopsin formed at -160 degrees C is the same as that formed at room temperature. PMID:284349

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

    PubMed

    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

  19. Origin invariance in vibrational resonance Raman optical activity.

    PubMed

    Vidal, Luciano N; Egidi, Franco; Barone, Vincenzo; Cappelli, Chiara

    2015-05-01

    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. PMID:25956084

  20. Origin invariance in vibrational resonance Raman optical activity

    NASA Astrophysics Data System (ADS)

    Vidal, Luciano N.; Egidi, Franco; Barone, Vincenzo; Cappelli, Chiara

    2015-05-01

    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.

  1. Origin invariance in vibrational resonance Raman optical activity

    SciTech Connect

    Vidal, Luciano N. Cappelli, Chiara; Egidi, Franco; Barone, Vincenzo

    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.

  2. Large Format Surface-Enhanced Raman Spectroscopy Substrate Optimized for Enhancement and Uniformity.

    PubMed

    Kanipe, Katherine N; Chidester, Philip P F; Stucky, Galen D; Moskovits, Martin

    2016-08-23

    Gratings have been widely investigated both theoretically and experimentally as surface-enhanced Raman spectroscopy (SERS) substrates, exhibiting, under appropriate circumstances, increased far-field extinctions and near-field intensities over those of an appropriately equivalent number of isolated particles. When the grating order transitions from evanescent to radiative, narrow resonance peaks are observed in the extinction spectrum whose properties can be manipulated by controlling the grating's geometric parameters. Here we report the application of the architectural principles of grating fabrication using a square two-dimensional array of gold-coated nanostructures that achieves SERS enhancements of 10(7) uniformly over areas of square centimeters. The high-performance grating substrates were fabricated using commonly available foundry-based techniques that have been chosen for their applicability to large-scale wafer processing. Additionally, we restricted ourselves to a parametric regime that optimizes SERS performance in a repeatable and reproducible manner. PMID:27482725

  3. Gain enhancement in a XeCl-pumped Raman amplifier

    SciTech Connect

    Rifkin, J.; Bernt, M.L.; MacPherson, D.C.; Carlsten, J.L.

    1988-08-01

    A comparison of the theoretical predictions of a multimode broadband model with the experimentally measured gain enhancement in a Raman amplifier is presented. The results show that the multimode theory with fixed and totally random phases is in agreement with the data obtained from an excimer-laser-pumped Raman amplifier. Additionally, this theory indicates that the correlated gain can be larger than the gain for a monochromatic laser, as might be expected for a model with amplitude modulation.

  4. Temperature dependence of resonance Raman spectra of carotenoids

    NASA Astrophysics Data System (ADS)

    Andreeva, A.; Apostolova, I.; Velitchkova, M.

    2011-04-01

    To understand the mechanism of the photoprotective and antioxidative functions of carotenoids, it is essential to have a profound knowledge of their excited electronic and vibronic states. In the present study we investigate the most powerful antioxidants: β-carotene and lutein by means of resonance Raman spectroscopy. The aim was to study in detail their Raman spectra in solution at room temperature and their changes as a function of temperature. To measure the spectra in their natural environment pyridine has been used as a solvent. It has been chosen because of its polarizability ( n = 1.5092) which is close to that of membrane lipids and proteins. The temperature dependence of the most intensive ν1 band in the range from 77 K to 295 K at 514.5 nm excitation has been obtained. It was found that in pyridine the C dbnd C stretching frequency, its intensity, line shape, and line width are very sensitive to the temperature (the sensitivity being different for the two studied carotenoids). The observed linear temperature dependence of the C dbnd C stretching frequency is explained by a mechanism involving changes of the vibronic coupling and the extent of π-electron delocalization. The different behavior of the temperature-induced broadening of the ν1 band and its intensity for the two studied carotenoids can be associated with the different nature of their solid matrices: glassy for β-carotene and crystalline-like for lutein, owing to their different chemical structures.

  5. Residual pesticide detection on food with particle-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Ranjan, Bikas; Huang, LiChuan; Masui, Kyoko; Saito, Yuika; Verma, Prabhat

    2014-08-01

    Modern farming relies highly on pesticides to protect agricultural food items from insects for high yield and better quality. Increasing use of pesticide has raised concern about its harmful effects on human health and hence it has become very important to detect even small amount of pesticide residues. Raman spectroscopy is a suitable nondestructive method for pesticide detection, however, it is not very effective for low concentration of pesticide molecules. Here, we report an approach based on plasmonic enhancement, namely, particle enhanced Raman spectroscopy (PERS), which is rapid, nondestructive and sensitive. In this technique, Raman signals are enhanced via the resonance excitation of localized plasmons in metallic nanoparticles. Gold nanostructures are promising materials that have ability to tune surface plasmon resonance frequency in visible to near-IR, which depends on shape and size of nanostructures. We synthesized gold nanorods (GNRs) with desired shape and size by seed mediated growth method, and successfully detected very tiny amount of pesticide present on food items. We also conformed that the detection of pesticide was not possible by usual Raman spectroscopy.

  6. Enhanced Raman Scattering on In-plane Anisotropic Layered Materials

    SciTech Connect

    Liang, Liangbo; Meunier, Vincent; Sumpter, Bobby G.; Ling, Xi; Lin, Jingjing; Zhang, Shuqing; Mao, Nannan; Zhang, Na; Tong, Lianming; Zhang, Jin

    2015-11-19

    Surface-enhanced Raman scattering (SERS) on two-dimensional (2D) layered materials has provided a unique platform to study the chemical mechanism (CM) of the enhancement due to its natural separation from electromagnetic enhancement. The CM stems from the basic charge interactions between the substrate and molecules. Despite the extensive studies of the energy alignment between 2D materials and molecules, an understanding of how the electronic properties of the substrate are explicitly involved in the charge interaction is still unclear. Lately, a new group of 2D layered materials with anisotropic structure, including orthorhombic black phosphorus (BP) and triclinic rhenium disulphide (ReS2), has attracted great interest due to their unique anisotropic electrical and optical properties. Herein, we report a unique anisotropic Raman enhancement on few-layered BP and ReS2 using copper phthalocyanine (CuPc) molecules as a Raman probe, which is absent on isotropic graphene and h-BN. According to detailed Raman tensor analysis and density functional theory calculations, anisotropic charge interactions due to the anisotropic carrier mobilities of the 2D materials are responsible for the angular dependence of the Raman enhancement. Our findings not only provide new insights into the CM process in SERS, but also open up new avenues for the exploration and application of the electronic properties of anisotropic 2D layered materials.

  7. Enhanced Raman Scattering on In-plane Anisotropic Layered Materials

    DOE PAGESBeta

    Liang, Liangbo; Meunier, Vincent; Sumpter, Bobby G.; Ling, Xi; Lin, Jingjing; Zhang, Shuqing; Mao, Nannan; Zhang, Na; Tong, Lianming; Zhang, Jin

    2015-11-19

    Surface-enhanced Raman scattering (SERS) on two-dimensional (2D) layered materials has provided a unique platform to study the chemical mechanism (CM) of the enhancement due to its natural separation from electromagnetic enhancement. The CM stems from the basic charge interactions between the substrate and molecules. Despite the extensive studies of the energy alignment between 2D materials and molecules, an understanding of how the electronic properties of the substrate are explicitly involved in the charge interaction is still unclear. Lately, a new group of 2D layered materials with anisotropic structure, including orthorhombic black phosphorus (BP) and triclinic rhenium disulphide (ReS2), has attractedmore » great interest due to their unique anisotropic electrical and optical properties. Herein, we report a unique anisotropic Raman enhancement on few-layered BP and ReS2 using copper phthalocyanine (CuPc) molecules as a Raman probe, which is absent on isotropic graphene and h-BN. According to detailed Raman tensor analysis and density functional theory calculations, anisotropic charge interactions due to the anisotropic carrier mobilities of the 2D materials are responsible for the angular dependence of the Raman enhancement. Our findings not only provide new insights into the CM process in SERS, but also open up new avenues for the exploration and application of the electronic properties of anisotropic 2D layered materials.« less

  8. Enhanced Raman Scattering on In-Plane Anisotropic Layered Materials.

    PubMed

    Lin, Jingjing; Liang, Liangbo; Ling, Xi; Zhang, Shuqing; Mao, Nannan; Zhang, Na; Sumpter, Bobby G; Meunier, Vincent; Tong, Lianming; Zhang, Jin

    2015-12-16

    Surface-enhanced Raman scattering (SERS) on two-dimensional (2D) layered materials has provided a unique platform to study the chemical mechanism (CM) of the enhancement due to its natural separation from electromagnetic enhancement. The CM stems from the charge interactions between the substrate and molecules. Despite the extensive studies of the energy alignment between 2D materials and molecules, an understanding of how the electronic properties of the substrate are explicitly involved in the charge interaction is still unclear. Lately, a new group of 2D layered materials with anisotropic structures, including orthorhombic black phosphorus (BP) and triclinic rhenium disulfide (ReS2), has attracted great interest due to their unique anisotropic electrical and optical properties. Herein, we report a unique anisotropic Raman enhancement on few-layered BP and ReS2 using copper phthalocyanine (CuPc) molecules as a Raman probe, which is absent on isotropic graphene and h-BN. According to detailed Raman tensor analysis and density functional theory calculations, anisotropic charge interactions between the 2D materials and molecules are responsible for the angular dependence of the Raman enhancement. Our findings not only provide new insights into the CM process in SERS, but also open up new avenues for the exploration and application of the electronic properties of anisotropic 2D layered materials. PMID:26583533

  9. Surface-enhanced Raman scattering as a higher-order Raman process

    NASA Astrophysics Data System (ADS)

    Mueller, Niclas S.; Heeg, Sebastian; Reich, Stephanie

    2016-08-01

    We propose to understand surface-enhanced Raman scattering (SERS) as a higher-order Raman process that contains the plasmonic excitation. The SERS amplitudes are calculated with third- and fourth-order perturbation theory. Treating the plasmonic excitation as a quasiparticle, we derive analytic expressions for all coupling matrix elements. This leads to a general theory of plasmonic enhancement in SERS that can be applied to arbitrary plasmonic nanostructures. We obtain the plasmon eigenvectors of a gold nanosphere and a nanosphere dimer. They are used to calculate the enhancement of the Raman cross section of a molecule coupled to the dipole plasmon mode. The enhancement of the cross section is up to three orders of magnitude stronger than predicted by the theory of electromagnetic enhancement. The difference is most pronounced in vacuum and decreases with increasing dielectric constant of the embedding medium. The predictions from understanding SERS as a higher-order Raman process agree well with recent experiments; they highlight the dominance of plasmonic enhancement in SERS.

  10. Double resonance Raman modes in monolayer and few-layer MoTe2

    NASA Astrophysics Data System (ADS)

    Guo, Huaihong; Yang, Teng; Yamamoto, Mahito; Zhou, Lin; Ishikawa, Ryo; Ueno, Keiji; Tsukagoshi, Kazuhito; Zhang, Zhidong; Dresselhaus, Mildred S.; Saito, Riichiro

    2015-05-01

    We study the second-order Raman process of mono- and few-layer MoTe2, by combining ab initio density functional perturbation calculations with experimental Raman spectroscopy using 532, 633, and 785 nm excitation lasers. The calculated electronic band structure and the density of states show that the resonance Raman process occurs at the M point in the Brillouin zone, where a strong optical absorption occurs due to a logarithmic Van Hove singularity of the electronic density of states. The double resonance Raman process with intervalley electron-phonon coupling connects two of the three inequivalent M points in the Brillouin zone, giving rise to second-order Raman peaks due to the M -point phonons. The calculated vibrational frequencies of the second-order Raman spectra agree with the observed laser-energy-dependent Raman shifts in the experiment.