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Sample records for absorption resonance raman

  1. 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.

  2. Atmospheric absorption versus deep ultraviolet (pre-)resonance in Raman lidar measurements

    NASA Astrophysics Data System (ADS)

    Hallen, Hans D.; Willitsford, Adam H.; Neely, Ryan R.; Chadwick, C. Todd; Philbrick, C. Russell

    2016-05-01

    The Raman scattering of several liquids and solid materials has been investigated near the deep ultraviolet absorption features corresponding to the electron energy states of the chemical species present. It is found to provide significant enhancement, but is always accompanied by absorption due to that or other species along the path. We investigate this trade-off for water vapor, although the results for liquid water and ice will be quantitatively very similar. An optical parametric oscillator (OPO) was pumped by the third harmonic of a Nd:YAG laser, and the output frequency doubled to generate a tunable excitation beam in the 215-600 nm range. We use the tunable laser excitation beam to investigate pre-resonance and resonance Raman spectroscopy near an absorption band of ice. A significant enhancement in the Raman signal was observed. The A-term of the Raman scattering tensor, which describes the pre-resonant enhancement of the spectra, is also used to find the primary observed intensities as a function of incident beam energy, although a wide resonance structure near the final-state-effect related absorption in ice is also found. The results suggest that use of pre-resonant or resonant Raman LIDAR could increase the sensitivity to improve spatial and temporal resolution of atmospheric water vapor measurements. However, these shorter wavelengths also exhibit higher ozone absorption. These opposing effects are modeled using MODTRAN for several configurations relevant for studies of boundary layer water and in the vicinity of clouds. Such data could be used in studies of the measurement of energy flow at the water-air and cloud-air interface, and may help with understanding some of the major uncertainties in current global climate models.

  3. Conformational study of the chromophore of C-phycocyanin by resonance raman and electronic absorption spectroscopy.

    NASA Astrophysics Data System (ADS)

    Margulies, L.; Toporowicz, M.

    1988-05-01

    The conformation of the chromophore of C-phycocyanin (PC) was investigated by using electronic absorption and resonance Raman spectroscopy, and theoretical calculations. Using an A-dihydrobilindione as model compound, the syn, syn, syn conformation was established for the isolated chromophore in solution. For the native PC, the best results were obtained by considering the syn, syn, anti conformation, although the possibility of having a syn, anti, anti conformation could not be excluded.

  4. Interpretation of unusual absorption bandwidths and resonance Raman intensities in excited state mixed valence.

    PubMed

    Lockard, Jenny V; Valverde, Guadalupe; Neuhauser, Daniel; Zink, Jeffrey I; Luo, Yun; Weaver, Michael N; Nelsen, Stephen F

    2006-01-12

    Excited state mixed valence (ESMV) occurs in molecules in which the ground state has a symmetrical charge distribution but the excited state possesses two or more interchangeably equivalent sites that have different formal oxidation states. Although mixed valence excited states are relatively common in both organic and inorganic molecules, their properties have only recently been explored, primarily because their spectroscopic features are usually overlapped or obscured by other transitions in the molecule. The mixed valence excited state absorption bands of 2,3-di-p-anisyl-2,3-diazabicyclo[2.2.2]octane radical cation are well-separated from others in the absorption spectrum and are particularly well-suited for detailed analysis using the ESMV model. Excited state coupling splits the absorption band into two components. The lower energy component is broader and more intense than the higher energy component. The absorption bandwidths are caused by progressions in totally symmetric modes, and the difference in bandwidths is caused by the coordinate dependence of the excited state coupling. The Raman intensities obtained in resonance with the high and low energy components differ significantly from those expected based on the oscillator strengths of the bands. This unexpected observation is a result of the excited state coupling and is explained by both the averaging of the transition dipole moment orientation over all angles for the two types of spectroscopies and the coordinate-dependent coupling. The absorption spectrum is fit using a coupled two-state model in which both symmetric and asymmetric coordinates are included. The physical meaning of the observed resonance Raman intensity trends is discussed along with the origin of the coordinate-dependent coupling. The well-separated mixed valence excited state spectroscopic components enable detailed electronic and resonance Raman data to be obtained from which the model can be more fully developed and tested.

  5. Nonadiabaticity in a Jahn-Teller system probed by absorption and resonance Raman scattering.

    PubMed

    Pae, K; Hizhnyakov, V

    2013-03-14

    A theory of absorption and resonance Raman scattering of impurity centers in crystals with E⊗e-type Jahn-Teller effect in the excited state is presented. The vibronic interaction with non-totally symmetric local or pseudolocal modes and with a continuum of bath modes (phonons) is considered. A number of specific quantum effects, such as the nonadiabaticity-induced enhancement of the Raman scattering at high-energy excitation, the size effect of the final state, the interference of different channels of scattering, the Fermi resonances in the conical intersection, and others, were shown to become apparent in the calculated spectra. The vibronic interaction with phonons essentially determines the structure of the spectra.

  6. Absorption and resonance Raman spectra of Pb2, Pb3 and Pb4 in xenon matrices

    NASA Technical Reports Server (NTRS)

    Stranz, D. D.; Khanna, R. K.

    1980-01-01

    Lead metal was vaporized and trapped in solid xenon at 12K. Electronic absorption and resonance Raman spectra were recorded of the resulting matrix, which was shown to contain Pb2, Pb3, and possibly Pb4 molecular species. The vibrational frequency for Pb2 is determined to be 108/cm for the ground state, with a dissociation energy of 82000/cm. Ad3h symmetry is indicated for the Pb3 species, with nu sub 1=117/cm and nu sub 2 = 96 /cm. The existence of Pb4 is suggested by a fundamental and overtone of 111/cm spacing.

  7. Absorption and resonance Raman study of the pyromellitic diahydride anion via density functional theory

    NASA Astrophysics Data System (ADS)

    Andruniow, T.; Pawlikowski, M.

    2000-05-01

    The electronic structure of the low-energy states of the pyromellitic diahydride (PMDA) anion is investigated in terms of the VWN (Vosco-Wilk-Nusair) the BP (Becke-Perdew) and the B3LYP density functional (DF) methods employed with 6-31G * basis sets. All the methods are shown to reproduce correctly the absorption and resonance Raman spectra in the region corresponding to the low-energy 1 2Au→1 2B3g transition. The discrepancies between the theory and experiment are attributed to a (weak) Dushinsky effect predominately due to a mixing of the ν3=1593 cm -1 and ν4=1342 cm -1 vibrations in the 1 2B3 g state of the PMDA radical.

  8. Electronic absorption and resonance Raman spectra of large linear carbon clusters isolated in solid argon.

    PubMed

    Szczepanski, J; Fuller, J; Ekern, S; Vala, M

    2001-03-15

    Neutral and anionic carbon clusters have been generated via a laser-induced graphite-based plasma and deposited in a solid argon matrix. Anionic clusters were formed from neutral clusters by using crossed electron/carbon cluster beams. Thermal annealing (to 36 K) resulted in the aggregation of the smaller carbon species, leading to the formation of long chain neutral and anionic clusters. Spectroscopic measurements in the ultraviolet, visible, near-infrared and infrared regions revealed a series of bands attributable to a homologous set of odd-numbered C5-C29 neutral clusters and even-numbered C6(-)-C36- anionic clusters. Good agreement is found for the band positions of carbon chains containing odd C15-C21 neutrals and even C6(-)-C22- anions, with species previously identified by Maier and coworkers using mass selection or laser vaporization, followed by neon matrix isolation. Resonance Raman frequencies for the neutral C17, C21 and C23 species are shown to be consistent with the above attributions. Density functional theory calculations agree well with the observed bands. It is found that certain low frequency Raman stretching frequencies decrease in a predictable way with increasing chain length. Comparison of the 0(0)0 absorption transitions of the even C18(-)-C36- anionic clusters with the 'unidentified' infrared (UIR) interstellar emission bands suggests that the electronic emission from specific long chain carbon anions may contribute to the some of the UIR bands.

  9. Resonance Raman and vibronic absorption spectra with Duschinsky rotation from a time-dependent perspective: Application to β-carotene

    NASA Astrophysics Data System (ADS)

    Banerjee, Shiladitya; Kröner, Dominik; Saalfrank, Peter

    2012-12-01

    The time-dependent approach to electronic spectroscopy, as popularized by Heller and co-workers in the 1980s, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption and resonance Raman spectra of β-carotene, with and without a solvent. Two-state models, the harmonic and the Condon approximations are used in order to do so. A new code has been developed which includes excited state displacements, vibrational frequency shifts, and Duschinsky rotation, i.e., mode mixing, for both non-adiabatic spectroscopies. It is shown that Duschinsky rotation has a pronounced effect on the resonance Raman spectra of β-carotene. In particular, it can explain a recently found anomalous behaviour of the so-called ν1 peak in resonance Raman spectra [N. Tschirner, M. Schenderlein, K. Brose, E. Schlodder, M. A. Mroginski, C. Thomsen, and P. Hildebrandt, Phys. Chem. Chem. Phys. 11, 11471 (2009)], 10.1039/b917341b, which shifts with the change in excitation wavelength.

  10. Resonance Raman and temperature-dependent electronic absorption spectra of cavity and noncavity models of the hydrated electron

    PubMed Central

    Casey, Jennifer R.; Larsen, Ross E.; Schwartz, Benjamin J.

    2013-01-01

    Most of what is known about the structure of the hydrated electron comes from mixed quantum/classical simulations, which depend on the pseudopotential that couples the quantum electron to the classical water molecules. These potentials usually are highly repulsive, producing cavity-bound hydrated electrons that break the local water H-bonding structure. However, we recently developed a more attractive potential, which produces a hydrated electron that encompasses a region of enhanced water density. Both our noncavity and the various cavity models predict similar experimental observables. In this paper, we work to distinguish between these models by studying both the temperature dependence of the optical absorption spectrum, which provides insight into the balance of the attractive and repulsive terms in the potential, and the resonance Raman spectrum, which provides a direct measure of the local H-bonding environment near the electron. We find that only our noncavity model can capture the experimental red shift of the hydrated electron’s absorption spectrum with increasing temperature at constant density. Cavity models of the hydrated electron predict a solvation structure similar to that of the larger aqueous halides, leading to a Raman O–H stretching band that is blue-shifted and narrower than that of bulk water. In contrast, experiments show the hydrated electron has a broader and red-shifted O–H stretching band compared with bulk water, a feature recovered by our noncavity model. We conclude that although our noncavity model does not provide perfect quantitative agreement with experiment, the hydrated electron must have a significant degree of noncavity character. PMID:23382233

  11. Resonance Raman spectroscopy.

    PubMed

    Robert, Bruno

    2009-01-01

    Resonance Raman spectroscopy may yield precise information on the conformation of, and on the interactions assumed by, the chromophores involved in the first steps of the photosynthetic process, whether isolated in solvents, embedded in soluble or membrane proteins, or, as shown recently, in vivo. By making use of this technique, it is possible, for instance, to relate the electronic properties of these molecules to their structure and/or the physical properties of their environment, or to determine subtle changes of their conformation associated with regulatory processes. After a short introduction to the physical principles that govern resonance Raman spectroscopy, the information content of resonance Raman spectra of chlorophyll and carotenoid molecules is described in this review, together with the experiments which helped in determining which structural parameter each Raman band is sensitive to. A selection of applications of this technique is then presented, in order to give a fair and precise idea of which type of information can be obtained from its use in the field of photosynthesis.

  12. Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory

    SciTech Connect

    Silverstein, Daniel W.; Govind, Niranjan; van Dam, Hubertus J. J.; Jensen, Lasse

    2013-12-10

    A parallel implementation of analytical time-dependent density functional theory gradients is presented for the quantum chemistry program NWChem. The implementation is based on the Lagrangian approach developed by Furche and Ahlrichs. To validate our implementation, we first calculate the Stokes shifts for a range of organic dye molecules using a diverse set of exchange-correlation functionals (traditional density functionals, global hybrids, and range-separated hybrids) followed by simulations of the one-photon absorption and resonance Raman scattering spectrum of the phenoxyl radical, the well-studied dye molecule rhodamine 6G, and a molecular host–guest complex (TTFcCBPQT4+). The study of organic dye molecules illustrates that B3LYP and CAM-B3LYP generally give the best agreement with experimentally determined Stokes shifts unless the excited state is a charge transfer state. Absorption, resonance Raman, and fluorescence simulations for the phenoxyl radical indicate that explicit solvation may be required for accurate characterization. For the host–guest complex and rhodamine 6G, it is demonstrated that absorption spectra can be simulated in good agreement with experimental data for most exchange-correlation functionals. Finally, however, because one-photon absorption spectra generally lack well-resolved vibrational features, resonance Raman simulations are necessary to evaluate the accuracy of the exchange-correlation functional for describing a potential energy surface.

  13. 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

    2016-02-04

    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.

  14. 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.

  15. Resonance Raman intensity analysis of the excited state proton transfer dynamics of 2-nitrophenol in the charge-transfer band absorption

    SciTech Connect

    Wang Yaqiong; Wang Huigang; Zhang Shuqiang; Pei Kemei; Zheng Xuming; Lee Phillips, David

    2006-12-07

    Resonance Raman spectra were obtained for 2-nitrophenol in cyclohexane solution with excitation wavelengths in resonance with the charge-transfer (CT) proton transfer band absorption. These spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion along more than 15 normal modes: the nominal CCH bend+CC stretch {nu}{sub 12} (1326 cm{sup -1}), the nominal CCC bend {nu}{sub 23} (564 cm{sup -1}), the nominal CO stretch+NO stretch+CC stretch {nu}{sub 14} (1250 cm{sup -1}), the nominal CCH bend+CC stretch+COH bend {nu}{sub 15} (1190 cm{sup -1}); the nominal CCH bend+CC stretch {nu}{sub 17} (1134 cm{sup -1}), the nominal CCC bend+CC stretch {nu}{sub 22} (669 cm{sup -1}), the nominal CCN bend {nu}{sub 27} (290 cm{sup -1}), the nominal NO{sub 2} bend+CC stretch {nu}{sub 21} (820 cm{sup -1}), the nominal CCO bend+CNO bend {nu}{sub 25} (428 cm{sup -1}), the nominal CC stretch {nu}{sub 7} (1590 cm{sup -1}), the nominal NO stretch {nu}{sub 8} (1538 cm{sup -1}), the nominal CCC bend+NO{sub 2} bend {nu}{sub 20} (870 cm{sup -1}), the nominal CC stretch {nu}{sub 6} (1617 cm{sup -1}), the nominal COH bend+CC stretch {nu}{sub 11} (1382 cm{sup -1}), nominal CCH bend+CC stretch {nu}{sub 9} (1472 cm{sup -1}). A preliminary resonance Raman intensity analysis was done and the results for 2-nitrophenol were compared to previously reported results for nitrobenzene, p-nitroaniline, and 2-hydroxyacetophenone. The authors briefly discuss the differences and similarities in the CT-band absorption excitation of 2-nitrophenol relative to those of nitrobenzene, p-nitroaniline, and 2-hydroxyacetophenone.

  16. Resonant Femtosecond Stimulated Raman Spectra: Theory and Simulations.

    PubMed

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

    2016-05-19

    We present a description of resonant femtosecond stimulated Raman spectra, which is based on the solution of the nonperturbative equation of motion of the chromophore in the laser fields. The theory is applicable for arbitrary shapes and durations of the Raman pulses, accounts for excited-state absorption, and describes nonstationary preparation of the system by an actinic pulse. The method is illustrated by the calculation of femtosecond stimulated Raman spectra of a model system with a conical intersection.

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

    PubMed

    Ma, HuiLi; Zhao, Yi; Liang, WanZhen

    2014-03-07

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

  18. SOUL in mouse eyes is a new hexameric heme-binding protein with characteristic optical absorption, resonance Raman spectral, and heme-binding properties.

    PubMed

    Sato, Emiko; Sagami, Ikuko; Uchida, Takeshi; Sato, Akira; Kitagawa, Teizo; Igarashi, Jotaro; Shimizu, Toru

    2004-11-09

    SOUL is specifically expressed in the retina and pineal gland and displays more than 40% sequence homology with p22HBP, a heme protein ubiquitously expressed in numerous tissues. SOUL was purified as a dimer in the absence of heme from the Escherichia coli expression system but displayed a hexameric structure upon heme binding. Heme-bound SOUL displayed optical absorption and resonance Raman spectra typical of 6-coordinate low-spin heme protein, with one heme per monomeric unit for both the Fe(III) and Fe(II) complexes. Spectral data additionally suggest that one of the axial ligands of the Fe(III) heme complex is His. Mutation of His42 (the only His of SOUL) to Ala resulted in loss of heme binding, confirming that this residue is an axial ligand of SOUL. The K(d) value of heme for SOUL was estimated as 4.8 x 10(-9) M from the association and dissociation rate constants, suggesting high binding affinity. On the other hand, p22HBP was obtained as a monomer containing one heme per subunit, with a K(d) value of 2.1 x 10(-11) M. Spectra of heme-bound p22HBP were different from those of SOUL but similar to those of heme-bound bovine serum albumin in which heme bound to a hydrophobic cavity with no specific axial ligand coordination. Therefore, the heme-binding properties and coordination structure of SOUL are distinct from those of p22HBP, despite high sequence homology. The physiological role of the new heme-binding protein, SOUL, is further discussed in this report.

  19. Dephasing and resonance electronic Raman scattering

    NASA Astrophysics Data System (ADS)

    Koningstein, J. A.

    1988-05-01

    The intensity of the resonance electronic Raman spectrum of terbium aluminum garnet is discussed in terms of radiative, non-radiative and pure electronic dephasing processes which govern the width of the resonating excited electronic state. As a result of fast electronic dephasing in comparison to the other processes, the enhancement of the intensity of the electronic Raman band of the terbium ion is suppressed.

  20. 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.

  1. Not-so-resonant, resonant absorption

    NASA Astrophysics Data System (ADS)

    Brunel, F.

    1987-07-01

    When an intense electromagnetic wave is incident obliquely on a sharply bounded overdense plasma, strong energy absorption can be accounted for by the electrons that are dragged into the vacuum and sent back into the plasma with velocities v~=vosc. This mechanism is more efficient than usual resonant absorption for vosc/ω>L, with L being the density gradient length. In the very high-intensity CO2-laser-target interaction, this mechanism may account for most of the energy absorption.

  2. Resonance Raman spectroscopy study of protonated porphyrin

    NASA Astrophysics Data System (ADS)

    Gorski, A.; Starukhin, A.; Stavrov, S.; Gawinkowski, S.; Waluk, J.

    2017-02-01

    Resonance Raman microscopy was used to study the resonance Raman scattering of the diacid (diprotonated form) of free-base porphyrin (21H,23H-porphine) in a crystal powder and KBr pellets. Intensive lines in the spectral range between 100 ÷ 1000 cm- 1 have been detected and assigned as spectral manifestation of out-of-plane modes. The Raman spectra were simulated by means of DFT methods and compared with the experimental data. It is evident from experimental and theoretical results that the activation of out-of-plane modes arises from saddle distortion of the porphyrin macrocycle upon formation of its diprotonated form.

  3. Surface-enhanced resonance Raman scattering from methylviologen at a silver electrode: Evidence for two distinct adsorption interactions

    SciTech Connect

    Feng, Qiao; Yue, W.; Cotton, T.M. )

    1990-03-08

    The electronic absorption and resonance Raman spectra of methylviologen radical cation (MV{sup {sm bullet}+}) and fully reduced methylviologen (MV{sup 0}) have been characterized. The enhancement of Raman and resonance Raman (RR) scattering from the dication and its reduction products at polished and roughened silver electrodes was also investigated.

  4. 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.

  5. 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.

  6. Resonance raman and absorption studies of the configurations of photochromic 3-alkyl-substituted 1,5-diphenylformazans: steric effect of the substituent

    NASA Astrophysics Data System (ADS)

    Hiura, Hidefumi; Takahashi, Hiroaki

    1989-09-01

    Resonance Raman spectra reveal that 3-alkyl-substituted 1,5-diphenylformazans exist as one of the following three isomeric species in the solid state: the yellow isomer has the trans- anti-s- trans configuration with respect to the NN, CN and CN bonds of the formazan skeleton, the red isomer has the trans- syn-s- trans configuration and the other red isomer has the trans- syn-s- cis configuration. The relative stabilities of these isomers are determined by the bulkiness of the substituent. When the substituent is small, the fully extended trans- anti-s- trans configuration is most stable. However, when the substituent is large, the partially folded trans- syn-s- trans configuration becomes stable and when the substituent is very bulky, the more folded trans- syn-s cis configuration is most stable. In solution these isomers are in equilibrium, the relative abundance being dependent on the nature of the solvent as well as on the bulkiness of the substituent.

  7. 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.

  8. 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).

  9. 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.

  10. 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.

  11. 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.

  12. Multiconfigurational Effects in Theoretical Resonance Raman Spectra

    PubMed Central

    Ma, Yingjin

    2017-01-01

    Abstract We analyze resonance Raman spectra of the nucleobase uracil in the short‐time approximation calculated with multiconfigurational methods. We discuss the importance of static electron correlation by means of density‐matrix renormalization group self‐consistent field (DMRG‐SCF) calculations. Our DMRG‐SCF results reveal that a minimal active orbital space that leads to a qualitatively correct description of the resonance Raman spectrum of uracil should encompass parts of the σ/σ* bonding/anti‐bonding orbitals of the pyrimidine ring. We trace these findings back to the considerable entanglement between the σ/σ* bonding/anti‐bonding as well as valence π/π* orbitals in the excited‐state electronic structure of uracil, which indicates non‐negligible non‐dynamical correlation effects that are less pronounced in the electronic ground state. PMID:27933695

  13. Resonance Raman spectroscopy in twisted bilayer graphene

    NASA Astrophysics Data System (ADS)

    Righi, A.; Venezuela, P.; Chacham, H.; Costa, S. D.; Fantini, C.; Ruoff, R. S.; Colombo, L.; Bacsa, W. S.; Pimenta, M. A.

    2013-12-01

    In this work we study the Raman spectra of twisted bilayer graphene samples, with different twisting angles, by changing the incident laser energy between 2.54 and 4.14 eV. The spectra exhibit a number of extra peaks, classified in different families, each one associated with bilayer graphenes with different twisting rotational angles. We theoretically analyze the laser energy dependence of these extra peaks considering a set of discrete wavevectors within the interior of the Brillouin zone of graphene, which activate special double-resonance Raman processes. Our result show a nice qualitative agreement between the experimental and simulated spectra, demonstrating that these extra peaks are indeed ascribed to an umklapp double-resonance process in graphene systems.

  14. 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.

  15. Perspective: Two-dimensional resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    Two-dimensional resonance Raman (2DRR) spectroscopy has been developed for studies of photochemical reaction mechanisms and structural heterogeneity in complex systems. The 2DRR method can leverage electronic resonance enhancement to selectively probe chromophores embedded in complex environments (e.g., a cofactor in a protein). In addition, correlations between the two dimensions of the 2DRR spectrum reveal information that is not available in traditional Raman techniques. For example, distributions of reactant and product geometries can be correlated in systems that undergo chemical reactions on the femtosecond time scale. Structural heterogeneity in an ensemble may also be reflected in the 2D spectroscopic line shapes of both reactive and non-reactive systems. In this perspective article, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of triiodide and myoglobin. We also address key differences between the signal generation mechanisms for 2DRR and off-resonant 2D Raman spectroscopies. Most notably, it has been shown that these two techniques are subject to a tradeoff between sensitivity to anharmonicity and susceptibility to artifacts. Overall, recent experimental developments and applications of the 2DRR method suggest great potential for the future of the technique.

  16. Resonant Raman Scattering Studies of Iii-V Semiconductor Microstructures

    NASA Astrophysics Data System (ADS)

    Delaney, Malcolm Emil

    1991-02-01

    Raman spectroscopy, an inelastic light scattering technique, explores III-V semiconductors by conveying crystal lattice structural information and by probing carrier dynamics both directly and via the electron-phonon interaction. We have examined three physical systems accentuating three aspects of Raman utility. Al_{rm x}Ga_{rm 1-x} As alloy work emphasizes electronic behavior, migration enhanced epitaxy (MEE) studies highlight structural results, and a phonon-assisted lasing project underscores electron -phonon interaction. The disorder-induced frequency difference between the dipole-forbidden and dipole-allowed longitudinal optic (LO) modes in Al_{rm x} Ga_{rm 1-x}As alloys has been investigated as a function of laser photon energy, aluminum mole fraction x, and the indirect versus direct nature of the electronic band gap. For the indirect gap alloy, the intermediate resonant state is an X-valley electron effectively localized because of its short inelastic lifetime. Raman scattering via this state is described by a calculation of the Raman susceptibility that considers the random alloy potential generated by local concentration fluctuations. MEE is a new growth technology that can order these materials in two spatial directions. In a GaSb/AlSb system we show Raman evidence of this ordering via observation of zone folded acoustic modes and compare to AlAs/GaAs results. In other work resonant Raman documents the effects on the dipole-forbidden interface mode of a periodic corrugation introduced in AlAs barrier GaAs single quantum wells. Finally, we investigate "phonon-assisted" lasing in photopumped quantum well heterostructure lasers. Resonant Raman is the natural choice to probe this system purported to have an enhanced electron-phonon interaction. For both the AlGaAs/GaAs and AlGaAs/GaAs/InGaAs structures examined, we provide evidence that indicates first order "phonon -assisted" lasing is actually renormalized band gap luminescence filtered by absorption from

  17. Insights into Protein Structure and Dynamics by Ultraviolet and Visible Resonance Raman Spectroscopy.

    PubMed

    López-Peña, Ignacio; Leigh, Brian S; Schlamadinger, Diana E; Kim, Judy E

    2015-08-11

    Raman spectroscopy is a form of vibrational spectroscopy based on inelastic scattering of light. In resonance Raman spectroscopy, the wavelength of the incident light falls within an absorption band of a chromophore, and this overlap of excitation and absorption energy greatly enhances the Raman scattering efficiency of the absorbing species. The ability to probe vibrational spectra of select chromophores within a complex mixture of molecules makes resonance Raman spectroscopy an excellent tool for studies of biomolecules. In this Current Topic, we discuss the type of molecular insights obtained from steady-state and time-resolved resonance Raman studies of a prototypical photoactive protein, rhodopsin. We also review recent efforts in ultraviolet resonance Raman investigations of soluble and membrane-associated biomolecules, including integral membrane proteins and antimicrobial peptides. These examples illustrate that resonance Raman is a sensitive, selective, and practical method for studying the structures of biological molecules, and the molecular bonding, geometry, and environments of protein cofactors, the backbone, and side chains.

  18. Negative refraction with low absorption using Raman transitions with magnetoelectric coupling

    SciTech Connect

    Sikes, D. E.; Yavuz, D. D.

    2010-07-15

    We suggest a scheme for obtaining negative refraction that does not require the simultaneous presence of an electric-dipole and a magnetic-dipole transition near the same transition frequency. The key idea of the scheme is to obtain a strong electric response by using far-off-resonant Raman transitions. We propose to use a pair of electric-dipole Raman transitions and utilize magneto-electric cross coupling to achieve a negative index of refraction without requiring negative permeability. The interference of the two Raman transitions allows tunable negative refraction with low absorption.

  19. The resonance Raman excitation profile of lutein

    NASA Astrophysics Data System (ADS)

    Hoskins, L. C.

    The resonance Raman excitation profiles for the ν 1, ν 2 and ν 3 vibrations of lutein in acetone, toluene and carbon disulfide solvents have been measured. The results are interpreted in terms of a three-mode vibrational theory which includes both homogeneous and inhomogeneous broadening effects. Excellent agreement between calculated and observed excitation profiles and visible spectra was found in acetone and toluene, but the results in carbon disulfide indicate a possible breakdown in the three-mode model. The major broadening mechanism is homogeneous, with about a 25% contribution from inhomogeneous broadening.

  20. The resonance Raman excitation profile of fucoxanthin

    NASA Astrophysics Data System (ADS)

    Ballard, L. J.; Glasgow, L. A.; Hoskins, L. C.; Krohe, T.

    1989-01-01

    The resonance Raman excitation profiles (RREPs) of the ν 1 and ν 2 vibrations of fucoxanthin in acetone and toluene solvents have been studied. Fucoxanthin, which is a predominant pigment in marine seaweed and phytoplankton, has several structural differences from carotenoids for which excitation profiles have been determined. The RREPs for fucoxanthin are interpreted in terms of a two-mode model and show a B2 value which is approximately 20% lower than for carotenoids like β-carotene and lutein which occur in higher plants. Excellent fits between experimental data and the theoretical model were observed in both solvents.

  1. 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.

  2. Super-Resonant Intracavity Coherent Absorption

    NASA Astrophysics Data System (ADS)

    Malara, P.; Campanella, C. E.; Giorgini, A.; Avino, S.; de Natale, P.; Gagliardi, G.

    2016-07-01

    The capability of optical resonators to extend the effective radiation-matter interaction length originates from a multipass effect, hence is intrinsically limited by the resonator’s quality factor. Here, we show that this constraint can be overcome by combining the concepts of resonant interaction and coherent perfect absorption (CPA). We demonstrate and investigate super-resonant coherent absorption in a coupled Fabry-Perot (FP)/ring cavity structure. At the FP resonant wavelengths, the described phenomenon gives rise to split modes with a nearly-transparent peak and a peak whose transmission is exceptionally sensitive to the intracavity loss. For small losses, the effective interaction pathlength of these modes is proportional respectively to the ratio and the product of the individual finesse coefficients of the two resonators. The results presented extend the conventional definition of resonant absorption and point to a way of circumventing the technological limitations of ultrahigh-quality resonators in spectroscopy and optical sensing schemes.

  3. 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.

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

    SciTech Connect

    Saito, M. D’Amico, F.; Bencivenga, F.; Cucini, R.; Gessini, A.; Principi, E.; Masciovecchio, C.

    2014-06-28

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

  5. Study of the configurations of 3-aryl-substituted 1,5-diphenylformazans by resonance Raman and absorption spectroscopy: steric and conjugation effects of the substituent

    NASA Astrophysics Data System (ADS)

    Hiura, Hidefumi; Takahashi, Hiroaki

    1989-09-01

    3-Aryl-substituted 1,5-diphenylformazans exist as one of the following two isomeric species in the solid state; the yellow isomer having the trans-anti-s- trans configuration with respect to the NN, CN and CN bonds of the formazan skeleton and the red isomer having the trans-syn-s- cis configuration. The other red isomer having the trans-syn-s- trans configuration, which exists when the substituent is an alkyl group, is not detected. Two effects are considered to be operative in determining the relative stabilities of these configurations: (1) the resonance energy arising from the conjugation between the π-electron systems of the formazan skeleton and the aryl substituent, and (2) the steric repulsion between the formazan skeleton and the groups (or atoms) attached to the ortho positions of the aryl substituent. In solutions, these two isomers are in equilibrium, their relative populations being dependent on the nature of the solvent as well as on the bulkiness of the groups attached to the ortho positions of the aryl substituent.

  6. Resonant Raman spectroscopy of twisted multilayer graphene

    NASA Astrophysics Data System (ADS)

    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

    2014-11-01

    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.

  7. 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.

  8. Observation of the Auger resonant Raman effect

    SciTech Connect

    Brown, G.S.; Chen, M.H.; Crasemann, B.; Ice, G.E.

    1980-11-01

    Monochromatized synchrotron radiation near the photoionization threshold was used to produce the (2p/sub 3/2/) vacancy state in atomic Xe. Deexcitation of the state through L/sub 3/-M/sub 4/M/sub 5/(/sup 1/G/sub 4/) Auger-electron emission was measured. The 5d spectator-electron Auger satellite was observed. The satellite energy exhibits linear dispersion. The observed width of the /sup 1/G diagram line decreases by approx. 40% when the exciting photon energy reaches the vicinity of the Xe L/sub 3/ binding energy. This radiationless process can thus be construed as the Auger analog of the x-ray resonant Raman effect. The /sup 1/G diagram line is shifted by -+3 eV due to post-collision interaction; this shift varies with excitation energy.

  9. Ultrasensitive fiber enhanced UV resonance Raman sensing of drugs.

    PubMed

    Frosch, Torsten; Yan, Di; Popp, Jürgen

    2013-07-02

    Fiber enhanced UV resonance Raman spectroscopy is introduced for chemical selective and ultrasensitive analysis of drugs in aqueous media. The application of hollow-core optical fibers provides a miniaturized sample container for analyte flow and efficient light-guiding, thus leading to strong light-analyte interactions and highly improved analytical sensitivity with the lowest sample demand. The Raman signals of the important antimalaria drugs chloroquine and mefloquine were strongly enhanced utilizing deep UV and electronic resonant excitation augmented by fiber enhancement. An experimental design was developed and realized for reproducible and quantitative Raman fiber sensing, thus the enhanced Raman signals of the pharmaceuticals show excellent linear relationship with sample concentration. A thorough model accounts for the different effects on signal performance in resonance Raman fiber sensing, and conclusions are drawn how to improve fiber enhanced Raman spectroscopy (FERS) for chemical selective analysis with picomolar sensitivity.

  10. Coherent control through near-resonant Raman transitions

    SciTech Connect

    Dai Xingcan; Lerch, Eliza-Beth W.; Leone, Stephen R.

    2006-02-15

    The phase of an electronic wave function is shown to play an important role in coherent control experiments. By using a pulse shaping system with a femtosecond laser, we explore the phase relationships among resonant and off-resonant Raman transitions in Li{sub 2} by measuring the phases of the resulting wave packets, or quantum beats. Specific pixels in a liquid-crystal spatial light modulator are used to isolate the resonant and off-resonant portions of the Raman transitions in Li{sub 2}. The off-resonant Raman transitions have an approximately 90 degree sign phase shift with respect to the resonant Raman transition, and there is an approximately 180 degree sign phase shift between the blue-detuned and the red-detuned off-resonant Raman transitions. Calculations using second-order time-dependent perturbation theory for the electronic transitions agree with the experimental results for the laser pulse intensities used here. Interferences between the off-resonant Raman transitions as a function of detuning are used to demonstrate coherent control of the Raman quantum wave packet.

  11. Relaxation mechanism of β-carotene from S2 (1Bu(+)) state to S1 (2Ag(-)) state: femtosecond time-resolved near-IR absorption and stimulated resonance Raman studies in 900-1550 nm region.

    PubMed

    Takaya, Tomohisa; Iwata, Koichi

    2014-06-12

    Carotenoids have two major low-lying excited states, the second lowest (S2 (1Bu(+))) and the lowest (S1 (2Ag(-))) excited singlet states, both of which are suggested to be involved in the energy transfer processes in light-harvesting complexes. Studying vibrational dynamics of S2 carotenoids requires ultrafast time-resolved near-IR Raman spectroscopy, although it has much less sensitivity than visible Raman spectroscopy. In this study, the relaxation mechanism of β-carotene from the S2 state to the S1 state is investigated by femtosecond time-resolved multiplex near-IR absorption and stimulated Raman spectroscopy. The energy gap between the S2 and S1 states is estimated to be 6780 cm(-1) from near-IR transient absorption spectra. The near-IR stimulated Raman spectrum of S2 β-carotene show three bands at 1580, 1240, and 1050 cm(-1). When excess energy of 4000 cm(-1) is added, the S1 C═C stretch band shows a large upshift with a time constant of 0.2 ps. The fast upshift is explained by a model that excess energy generated by internal conversion from the S2 state to the S1 state is selectively accepted by one of the vibronic levels of the S1 state and is redistributed among all the vibrational modes.

  12. Continuous-wave deep ultraviolet sources for resonance Raman explosive sensing

    NASA Astrophysics Data System (ADS)

    Yellampalle, Balakishore; Martin, Robert; Sluch, Mikhail; McCormick, William; Ice, Robert; Lemoff, Brian

    2015-05-01

    A promising approach to stand-off detection of explosive traces is using resonance Raman spectroscopy with Deepultraviolet (DUV) light. The DUV region offers two main advantages: strong explosive signatures due to resonant and λ- 4 enhancement of Raman cross-section, and lack of fluorescence and solar background. For DUV Raman spectroscopy, continuous-wave (CW) or quasi-CW lasers are preferable to high peak powered pulsed lasers because Raman saturation phenomena and sample damage can be avoided. In this work we present a very compact DUV source that produces greater than 1 mw of CW optical power. The source has high optical-to-optical conversion efficiency, greater than 5 %, as it is based on second harmonic generation (SHG) of a blue/green laser source using a nonlinear crystal placed in an external resonant enhancement cavity. The laser system is extremely compact, lightweight, and can be battery powered. Using two such sources, one each at 236.5 nm and 257.5 nm, we are building a second generation explosive detection system called Dual-Excitation-Wavelength Resonance-Raman Detector (DEWRRED-II). The DEWRRED-II system also includes a compact dual-band high throughput DUV spectrometer, and a highly-sensitive detection algorithm. The DEWRRED technique exploits the DUV excitation wavelength dependence of Raman signal strength, arising from complex interplay of resonant enhancement, self-absorption and laser penetration depth. We show sensor measurements from explosives/precursor materials at different standoff distances.

  13. 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.

  14. 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.

  15. 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.

  16. Measurement of sex steroids and analogs with a fiber optic probe using pulsed ultraviolet resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Schulze, H. Georg; Greek, L. Shane; Blades, Michael W.; Bree, Alan V.; Gorzalka, Boris B.; Turner, Robin F. B.

    1997-05-01

    Resonance Raman spectroscopy, performed via an optical fiber probe, can be used in aqueous samples to detect a wide variety of chemical species in situ. It offers a potentially rapid, on-site alternative to the high performance chromatography/mass spectrometry methods currently considered definitive for the detection of sex steroids in human urine. As a first step in the development of a resonance Raman instrument for the rapid detection of sex steroids in biological samples, it had to be shown that these substances, their analogs, and the major components of human urine can be differentiated on the basis of their resonance Raman spectra. A fiber-optic linked Raman and tunable ultraviolet resonance Raman system was assembled with custom designed optical fiber probes. The ultraviolet absorption spectra of some sex steroids, analogs, and components of human urine were measured in order to determine feasible excitation light frequencies. We present here for the first time the UV resonance Raman spectra of these substances obtained via our novel fiber probes. These results indicate that some of the steroids tested can be differentiated from each other and from the major components of human urine on the basis of their resonance Raman spectra.

  17. Interferences in and lifetime measurement of a resonance electronic Raman effect using tunable pulsed laser techniques

    NASA Astrophysics Data System (ADS)

    Nicollin, D.; Koningstein, J. A.

    1980-07-01

    The excitation profile for the intensity of electronic Raman transitions of terbium aluminum garnet (TbAlG) in the spectral range of 483.0-680.0 nm is reported. The electronic Raman transitions take place between the crystal field levels of the split 7F 6 ground manifold of TbAlG with shifts of 73 cm -1 and 83 cm -1 and the electronic Raman process is induced with tunable pulsed and fixed wavelength cw lasers. The tunability of the former was employed to obtain detailed information of the behaviour of the Raman intensity if the wavelength of the exciting source is tuned throughout the region of 483.0-490.0 nm where 5Da 4 ← 7F 6 absorptions of TbAlG occur and the data reveal the occurrence of interference effects. We also report measurements of the shape of the pulse — due to resonance enhanced electronic Raman scattered light — in real time. These studies reveal that the lifetime of the resonating state (which is responsible for the enhancement of the Raman intensity) as determined from the tailing end of the said pulse is within experimental error equal to the lifetime τ = 33.5 ± 1 μs of this state measured in a direct way from the intensity decay of an appropriate fluorescence transition of TbAlG.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2006-02-01

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

  20. Absolute determination of cross sections for resonant Raman scattering on silicon

    NASA Astrophysics Data System (ADS)

    Müller, Matthias; Beckhoff, Burkhard; Ulm, Gerhard; Kanngießer, Birgit

    2006-07-01

    We studied the resonant Raman scattering of x rays in the vicinity of the K absorption edge of silicon. The investigation was carried out at the plane grating monochromator beamline for undulator radiation of the PTB laboratory at BESSY II in Berlin. Cross sections were determined absolutely for a wide energy range of incident photons with small relative uncertainties employing calibrated instrumentation avoiding any reference samples. The experimentally determined values differ clearly from the theoretical ones found in the literature.

  1. Ab initio calculation of resonance Raman cross sections based on excited state geometry optimization.

    PubMed

    Gaff, J F; Franzen, S; Delley, B

    2010-11-04

    A method for the calculation of resonance Raman cross sections is presented on the basis of calculation of structural differences between optimized ground and excited state geometries using density functional theory. A vibrational frequency calculation of the molecule is employed to obtain normal coordinate displacements for the modes of vibration. The excited state displacement relative to the ground state can be calculated in the normal coordinate basis by means of a linear transformation from a Cartesian basis to a normal coordinate one. The displacements in normal coordinates are then scaled by root-mean-square displacement of zero point motion to calculate dimensionless displacements for use in the two-time-correlator formalism for the calculation of resonance Raman spectra at an arbitrary temperature. The method is valid for Franck-Condon active modes within the harmonic approximation. The method was validated by calculation of resonance Raman cross sections and absorption spectra for chlorine dioxide, nitrate ion, trans-stilbene, 1,3,5-cycloheptatriene, and the aromatic amino acids. This method permits significant gains in the efficiency of calculating resonance Raman cross sections from first principles and, consequently, permits extension to large systems (>50 atoms).

  2. 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.

  3. 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.

  4. UV resonance Raman analysis of trishomocubane and diamondoid dimers.

    PubMed

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

    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 B2g 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(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.

  5. β-Carotene Revisited by Transient Absorption and Stimulated Raman Spectroscopy.

    PubMed

    Quick, Martin; Kasper, Marc-André; Richter, Celin; Mahrwald, Rainer; Dobryakov, Alexander L; Kovalenko, Sergey A; Ernsting, Nikolaus P

    2015-12-21

    β-Carotene in n-hexane was examined by femtosecond transient absorption and stimulated Raman spectroscopy. Electronic change is separated from vibrational relaxation with the help of band integrals. Overlaid on the decay of S1 excited-state absorption, a picosecond process is found that is absent when the C9 -methyl group is replaced by ethyl or isopropyl. It is attributed to reorganization on the S1 potential energy surface, involving dihedral angles between C6 and C9 . In Raman studies, electronic states S2 or S1 were selected through resonance conditions. We observe a broad vibrational band at 1770 cm(-1) in S2 already. With 200 fs it decays and transforms into the well-known S1 Raman line for an asymmetric C=C stretching mode. Low-frequency activity (<800 cm(-1) ) in S2 and S1 is also seen. A dependence of solvent lines on solute dynamics implies intermolecular coupling between β-carotene and nearby n-hexane molecules.

  6. Electron heating due to resonant absorption

    SciTech Connect

    Mizuno, K.; Spielman, R.B.; DeGroot, J.S.; Bollen, W.M.

    1980-01-01

    Intense, p-polarized microwaves (v/sub os//v/sub eo-/<1) are incident on an imhomogeneous plasma (10/sup 2/resonant absorption near the critical surface (where the plasma frequency equals microwave frequency). Suprathermal electrons are heated by resonantly driven electrostatic field to produce a hot Maxwellian distribution. Most of the heated electrons flow towards the overdense region and are absorbed by the anode at the far end of the overdense region. At high power (v/sub os//v/sub eo-/>0.2), strong heating of thermal electrons, large amplitude ion acoustic turbulence, and a self-consistent dc electric field are observed near the critical surface. This dc electric field is enhanced by applying a weak magnetic field (..omega../sub ce//..omega../sub o/ approx. = 10/sup -2/).

  7. Characterization of photosynthetic reaction centers by surface-enhanced resonance Raman scattering

    NASA Astrophysics Data System (ADS)

    Chumanov, George D.; Cotton, Therese M.; Zhou, Chengli; Gaul, Dale; Picorel, Rafael; Seibert, Michael

    1993-06-01

    Surface-enhanced Resonance Raman scattering (SERRS) spectra were obtained for the reaction center complexes of the photosynthetic bacterium Rhodobacter sphaeroides (RC) and from photosystem II (PSII) of spinach, adsorbed on Ag and Au surfaces. These preliminary results demonstrate the considerable potential of this technique for selectively exciting resonance Raman scattering from reaction center components within their distinct absorption bands. Because of the high sensitivity afforded by SERRS, spectra could be measured from a single monolayer of reaction centers adsorbed on a metal surface. The surface-sensitivity provides new information indicating the topology of the PSII reaction center 47 kD light-harvesting protein complex. The activity of the PSII reaction center complex adsorbed on metal surfaces was monitored by photochemical reduction of cyt b-559. Measurement of fluorescence emission was shown to be a new and sensitive method for monitoring the structural and functional integrity of the PSII reaction center complex on the metal surface.

  8. 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.

  9. Laser engines operating by resonance absorption.

    PubMed

    Garbuny, M; Pechersky, M J

    1976-05-01

    The coherence properties and power levels of lasers available at present lend themselves to the remote operation of mechanical engines by resonance absorption in a working gas. Laser radiation is capable of producing extremely high temperatures in a gas. Limits to the achievable temperatures in the working gas of an engine are imposed by the solid walls and by loss of resonance absorption due to thermal saturation, bleaching, and dissociation. However, it is shown that by proper control of the laser beam in space, time, and frequency, as well as by choice of the absorbing gas, these limits are to a great extent removed so that very high temperatures are indeed attainable. The working gas is largely monatomic, preferably helium with the addition of a few volume percent of an absorber. Such a gas mixture, internally heated, permits an optimization of the expansion ratio, with resulting thermal efficiencies and work ratios, not achievable in conventional engines. A relationship between thermal efficiency and work ratio is derived that is quite general for the optimization condition. The performance of laser piston engines, turbines, and the Stirling cycle based on these principles is discussed and compared with conventional engine operation. Finally, a brief discussion is devoted to the possibility and concepts for the direct conversion of selective vibrational or electronic excitation into mechanical work, bypassing the translational degrees of freedom.

  10. Pre-Resonance Raman Spectroscopy-Based Explosives Detector

    NASA Astrophysics Data System (ADS)

    Gupta, S.; Kumar, A.; Gambhir, V.; Reddy, M. N.

    2017-01-01

    A pre-resonance Raman spectroscopy based explosives detection system has been developed using UV laser at wavelength 266 nm having pulse energy of 30 mJ and repetition rate of 20 Hz. A 4-inch UV-enhanced collection optics and back-thinned UV-enhanced charged coupled device (CCD) coupled spectrometer has been used for analysis of the Raman signal. Spectral peak matching software has been developed indigenously for identification of explosives. A compact, tripod mounted and man-portable Raman system is developed for field applications. The system has capability to detect explosives and explosive derivatives over a range up to 40 m and has a sensitivity of 0.1% weight/volume.

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

    SciTech Connect

    Patuwo, Michael Y.; Lee, Soo-Y.

    2013-12-21

    We present the time-frame calculated photoabsorption spectrum (ABS), spontaneous Raman excitation profile (REP), femtosecond stimulated Raman spectroscopy (FSRS) spectrum, and femtosecond stimulated Raman excitation profile (FSREP) results of a two-mode and three-mode, three-electronic-states model Hamiltonians containing conical intersections (CIs) along its two upper diabatic electronic states, e{sub 1} (dark) and e{sub 2} (bright), with and without coupling (nonadiabatic dynamics) along an asymmetric mode. For every electronic state in each model, there is one coupling mode and the rest of the modes are symmetric tuning modes. The CI appears in the Hamiltonian as off-diagonal entries to the potential term that couple the two upper states, in the form of a linear function of the coupling mode. We show that: (a) the ABS, REP, and FSREP for Stokes and anti-Stokes lines contain similar information about the e{sub 1} and e{sub 2} vibrational bands, (b) the FSRS spectra feature narrow stationary peaks and broader moving peaks contributed by the different resonant components of the third-order polarization terms from perturbation theory, and (c) a relatively strong and narrow stationary band of the allowed first overtone of the asymmetric coupling mode is observed in the Stokes FSREP in the e{sub 1} energy region with coupling to e{sub 2}.

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

    PubMed

    Patuwo, Michael Y; Lee, Soo-Y

    2013-12-21

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

  13. Resonant Raman studies of compositional and size dispersion of CdS1-xSex nanocrystals in a glass matrix

    NASA Astrophysics Data System (ADS)

    Azhniuk, Yu M.; Milekhin, A. G.; Gomonnai, A. V.; Lopushansky, V. V.; Yukhymchuk, V. O.; Schulze, S.; Zenkevich, E. I.; Zahn, D. R. T.

    2004-12-01

    Resonant Raman scattering spectra of glass-embedded CdS1-xSex nanocrystals are measured and complemented with TEM and optical absorption as well as photoluminescence data. The selectivity of the resonant Raman process not only for the size, but also for the composition of nanocrystals within the ensemble, is directly observed in the dependence of phonon band frequency, linewidth and shape on the excitation wavelength.

  14. Tissue Oxygenation Monitoring using Resonance Raman Spectroscopy during Hemorrhage

    DTIC Science & Technology

    2013-12-27

    saturation measurements using resonance Raman intravital micros- copy. Am J Physiol Heart Circ Physiol. 2005;289:H488 H495. 14. Ward KR, Ivatury RR, Barbee...Nighswander-Rempel SP, Kupriyanov VV, Shaw RA. Relative contribu- tions of hemoglobin and myoglobin to near-infrared spectroscopic images of cardiac tissue...DC, Shapiro NI. The microcirculation image quality score: development and preliminary evaluation of a proposed approach to grading quality of image

  15. Excited state structures and decay dynamics of 1,3-dimethyluracils in solutions: resonance Raman and quantum mechanical calculation study.

    PubMed

    Li, Ming-Juan; Liu, Ming-Xia; Zhao, Yan-Ying; Pei, Ke-Mei; Wang, Hui-Gang; Zheng, Xuming; Fang, Wei Hai

    2013-10-03

    The resonance Raman spectroscopic study of the excited state structural dynamics of 1,3-dimethyluracil (DMU), 5-bromo-1,3-dimethyluracil (5BrDMU), uracil, and thymine in water and acetonitrile were reported. Density functional theory calculations were carried out to help elucidate the ultraviolet electronic transitions associated with the A-, and B-band absorptions and the vibrational assignments of the resonance Raman spectra. The effect of the methylation at N1, N3 and C5 sites of pyrimidine ring on the structural dynamics of uracils in different solvents were explored on the basis of the resonance Raman intensity patterns. The relative resonance Raman intensities of DMU and 5BrDMU are computed at the B3LYP-TD level. Huge discrepancies between the experimental resonance Raman intensities and the B3LYP-TD predicted ones were observed. The underlying mechanism was briefly discussed. The decay channel through the S1((1)nπ*)/S2((1)ππ*) conical intersection and the S1((1)nπ*)/T1((3)ππ*) intersystem crossing were revealed by using the CASSCF(8,7)/6-31G(d) level of theory calculations.

  16. A resonance Raman spectroscopic study of the quadruplex form of polyriboinosinic acid.

    PubMed

    Wheeler, V; Jollès, B; Miskovsky, P; Chinsky, L

    1996-08-01

    The four stranded form of polyriboinosinic acid, or poly(rl), formed under conditions of high ionic strength, has been studied principally by resonance Raman spectroscopy excited in the ultraviolet absorbent band of the hypoxanthine residues. UV Absorption and circular dichroism studies were made, principally in order to verify the presence of the quadruplex form at the low concentrations of poly(rl) used, and a trial experiment with the structural probe Tb3+ was also performed. Experimental evidence is found for highly stacked metastable forms present at low concentrations of polynucleotide, which are destroyed by heating in favor of the two well known forms.

  17. 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.

  18. Graphene as a substrate to suppress fluorescence in resonance Raman spectroscopy.

    PubMed

    Xie, Liming; Ling, Xi; Fang, Yuan; Zhang, Jin; Liu, Zhongfan

    2009-07-29

    We have measured resonance Raman spectra with greatly suppressed fluorescence (FL) background from rhodamine 6G (R6G) and protoporphyrin IX (PPP) adsorbed on graphene. The FL suppression is estimated to be approximately 10(3) times for R6G. The successful observation of resonance Raman peaks demonstrates that graphene can be used as a substrate to suppress FL in resonance Raman spectroscopy (RRS), which has potential applications in low-concentration detection and RRS study of fluorescent molecules.

  19. Subwavelength single layer absorption resonance antireflection coatings.

    PubMed

    Huber, S P; van de Kruijs, R W E; Yakshin, A E; Zoethout, E; Boller, K-J; Bijkerk, F

    2014-01-13

    We present theoretically derived design rules for an absorbing resonance antireflection coating for the spectral range of 100 - 400 nm, applied here on top of a molybdenum-silicon multilayer mirror (Mo/Si MLM) as commonly used in extreme ultraviolet lithography. The design rules for optimal suppression are found to be strongly dependent on the thickness and optical constants of the coating. For wavelengths below λ ∼ 230 nm, absorbing thin films can be used to generate an additional phase shift and complement the propagational phase shift, enabling full suppression already with film thicknesses far below the quarter-wave limit. Above λ ∼ 230 nm, minimal absorption (k < 0.2) is necessary for low reflectance and the minimum required layer thickness increases with increasing wavelength slowly converging towards the quarter-wave limit.As a proof of principle, SixCyNz thin films were deposited that exhibit optical constants close to the design rules for suppression around 285 nm. The thin films were deposited by electron beam co-deposition of silicon and carbon, with N+ ion implantation during growth and analyzed with variable angle spectroscopic ellipsometry to characterize the optical constants. We report a reduction of reflectance at λ = 285 nm, from 58% to 0.3% for a Mo/Si MLM coated with a 20 nm thin film of Si0.52C0.16N0.29.

  20. Photodissociation dynamics of dimethylnitrosamine studied by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Lenderink, Egbert; Wiersma, Douwe A.

    1994-02-01

    The initial molecular dynamics in the dissociative S 1 (n, π *) state of dimethylnitrosamine (DMN) is investigated using resonance Raman spectroscopy. We find that photochemical N-N bond cleavage in DMN proceeds via a bent conformation around the amine N atom, which supports the outcome of ab initio and classical trajectory calculations [M. Persico, I. Cacelli and A. Ferretti, J. Chem. Phys. 94 (1991) 5508]. Additional information is obtained about the other motions that accompany the photodissociation: a stretch of the N-N bond and a change of the NNO angle.

  1. Determination of resonance Raman cross-sections for use in biological SERS sensing with femtosecond stimulated Raman spectroscopy.

    PubMed

    Silva, W Ruchira; Keller, Emily L; Frontiera, Renee R

    2014-08-05

    Surface-enhanced Raman spectroscopy (SERS) is a promising technique for in vivo bioanalyte detection, but accurate characterization of SERS biosensors can be challenging due to difficulties in differentiating resonance and surface enhancement contributions to the Raman signal. Here, we quantitate the resonance Raman cross-sections for a commonly used near-infrared SERS dye, 3,3'-diethylthiatricarbocyanine (DTTC). It is typically challenging to measure resonance Raman cross-sections for fluorescent dye molecules due to the overwhelming isoenergetic fluorescence signal. To overcome this issue, we used etalon-based femtosecond stimulated Raman spectroscopy, which is intrinsically designed to acquire a stimulated Raman signal without strong fluorescence or interference from signals resulting from other four-wave mixing pathways. Using this technique, we found that the cross-sections for most of the resonantly enhanced modes in DTTC exceed 10(-25) cm(2)/molecule. These cross-sections lead to high signal magnitude SERS signals from even weakly enhancing SERS substrates, as much of what appears to be a SERS signal is actually coming from the intrinsically strong resonance Raman signal. Our work will lead to a more accurate determination of SERS enhancement factors and SERS substrate characterization in the biologically relevant near-infrared region, ultimately leading to a more widespread use of SERS for biosensing and bioimaging applications.

  2. Enhancing absorption properties of composite nanosphere and nanowire arrays by localized surface plasmon resonance shift

    NASA Astrophysics Data System (ADS)

    Tang, Xiaobing; Zhou, Leping; Du, Xiaoze; Yang, Yongping

    Nanoparticles with nonmetallic core and metallic shell can improve the spectral solar absorption efficiency for traditional working fluids, due to the localized surface plasmon resonance (LSPR) effect exists at the surfaces of these core-shell composite nanoparticles. In this work, the effect of geometry and material, and hence the LSPR effect, on the optical absorption properties of core-shell nanostructures was numerically demonstrated by the finite difference time domain method. The nanostructures were formed by varying the inner and outer radii of the composite nanospheres and nanowires and by changing the particle spacing for their arrays. The result indicates that varying the inner radius itself can tune the absorption efficiency factors of the nanostructures monotonously, while an optimal outer radius may exist for maximizing the absorption efficiency factors. It also shows that varying the inner radius itself can widen the absorption spectrums for the arrays, but the absorptance tends to increase with decreasing inner radius or particle spacing. Meanwhile, the second absorption peaks may be observed for nanowires or nanosphere/nanowire arrays, which can be tuned by the resonance shifts induced by the change of either inner or outer radius and hence the LSPR effect. The coupled LSPR effect under studied can be efficiently utilized for tuning the optical absorption properties of nanoparticles used in many applications including photothermal conversion, and perspective also exists for many other applications including surface-enhanced Raman spectroscopy (SERS) enhancement.

  3. 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.

  4. 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.

  5. Unusual Raman spectra of para-nitroaniline by sequential Fermi resonances.

    PubMed

    Xia, Jiarui; Zhu, Ling; Feng, Yanting; Li, Yongqing; Zhang, Zhenglong; Xia, Lixin; Liu, Liwei; Ma, Fengcai

    2014-01-01

    In this communication, we report the unusual Raman spectra of para-nitroaniline (PNA) by sequential Fermi resonances. The combinational mode 1292 cm(-1) in the experimental Raman spectrum indirectly gains the initial spectral weight at 1392 cm(-1) by three sequential Fermi resonances. These Fermi resonances result in the strong interaction between the donor group of NH2 and the acceptor group of NO2. Our theoretical calculations provide reasonable interpretation for the abnormal Raman spectra of PNA. Experimental surface enhanced Raman scattering (SERS) spectrum of PNA further confirmed our conclusion, where the strongest Raman peak at 1292 cm(-1) is very weak, while the Raman peak at 1392 cm(-1) becoming the strongest Raman peak, which is consistent with the theoretical simulations.

  6. Resonance Raman Scattering Studies of Gallium - - Aluminum-Arsenide Superlattices.

    NASA Astrophysics Data System (ADS)

    Gant, Thomas Andrew

    We have made resonance Raman scattering studies of folded LA phonons and quantized LO phonons in several GaAs-AlAs superlattices. The motivation for this work was to study the electronic structure and the electron -phonon interaction in these structures. The samples were not intentionally doped. The Raman spectra of optic phonons were usually taken at a temperature of 10 K or less. The folded acoustic phonon work was taken at temperatures ranging from 200-300 K in order to enhance the scattering by the thermal factor. Two samples in particular have received very close attention: sample 2292 (50 A GaAs- 20 A AlAs) and sample 3250 (20 A GaAs- 50 A AlAs). In sample 2292 we have made resonance studies of the folded LA phonons and the GaAs -like confined LO_2 mode near the second heavy hole exciton. The results on the folded acoustic phonons show a very strong resonance enhancement for the second order folded phonons, but very little for the first order. An interference between two different scattering channels (the n = 1 light hole and the n = 2 heavy hole subbands) seems to be responsible for this effect. The resonance profile for the LO_2 confined optic phonon in sample 2292 shows 4 peaks in the region from 1.8 eV to 2.05 eV. We have studied the dependence of this resonance profile on the power density. A higher power density was achieved by using the same laser power with a tighter focus. At the higher power density the peak at 1.93 eV (formerly the strongest peak present) vanished. This "bleaching" effect is related to screening due to the higher carrier density. In sample 3250 we have studied the polarization dependence of the resonance profiles of four peaks (LO _2, LO_4, LO_6, and an interface mode) near the lowest direct gap. The A_1 symmetry confined LO modes are seen in both polarized and depolarized geometries, in violation of the usual selection rule (polarized). A mechanism is proposed to explain this result, which has been previously observed by other

  7. 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.

  8. 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.

  9. 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

  10. Polarization control of intermediate state absorption in resonance-mediated multi-photon absorption process

    NASA Astrophysics Data System (ADS)

    Xu, Shuwu; Huang, Yunxia; Yao, Yunhua; Jia, Tianqing; Ding, Jingxin; Zhang, Shian; Sun, Zhenrong

    2015-07-01

    We theoretically and experimentally demonstrate the control of the intermediate state absorption in an (n + m) resonance-mediated multi-photon absorption process by the polarization-modulated femtosecond laser pulse. An analytical solution of the intermediate state absorption in a resonance-mediated multi-photon absorption process is obtained based on the time-dependent perturbation theory. Our theoretical results show that the control efficiency of the intermediate state absorption by the polarization modulation is independent of the laser intensity when the transition from the intermediate state to the final state is coupled by the single-photon absorption, but will be affected by the laser intensity when this transition is coupled by the non-resonant multi-photon absorption. These theoretical results are experimentally confirmed via a two-photon fluorescence control in (2 + 1) resonance-mediated three-photon absorption of Coumarin 480 dye and a single-photon fluorescence control in (1 + 2) resonance-mediated three-photon absorption of IR 125 dye.

  11. Resonance enhancement of electronic Raman scattering from nitrogen defect levels in silicon carbide

    NASA Astrophysics Data System (ADS)

    Burton, J. C.; Long, F. H.; Ferguson, I. T.

    1999-08-01

    Electronic Raman scattering from nitrogen defect levels in SiC is seen to be significantly enhanced with excitation by red (633 nm, 1.98 eV) or near-IR (785 nm, 1.58 eV) laser light at room temperature. Four nitrogen peaks are observed in 6H-SiC (380, 430, 510, and 638 cm-1) and three peaks in 4H-SiC (about 400, 530, and 570 cm-1). The peaks in the 4H-SiC spectrum are seen to shift to lower frequency with increasing nominal doping concentration. Raman spectra taken at low temperature in 6H-SiC reveal differences between wafers and Lely grown platelets by the appearance of several additional peaks. The origin of the resonant enhancement is the near-IR absorption band associated with the green color characteristic of n-type SiC. These results demonstrate that the laser wavelength is a key parameter in the characterization of SiC by Raman scattering.

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

    PubMed

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

    2016-06-17

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

  13. Elucidation of Chemical Reactions by Two-Dimensional Resonance Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Moran, Andrew

    Two-dimensional (2D) Raman spectroscopies were proposed by Mukamel and Loring in1985 as a method for resolving line broadening mechanisms of vibrational motions in liquids. Significant technical issues challenged the development of both five- and seven-pulse 2D Raman spectroscopies. For this reason, 2D Raman experiments were largely abandoned in 2002 following the first demonstrations of 2D infrared spectroscopies (i.e., an alternate approach for obtaining similar information). We have recently shown that 2D Raman experiments conducted under electronically resonant conditions are much less susceptible to the problems encountered in the earlier 2D Raman work, which was carried out off-resonance. In effect, Franck-Condon activity obviates the problematic selection rules encountered under electronically off-resonant conditions. In this presentation, I will discuss applications of 2D resonance Raman spectroscopies to photodissocation reactions of triiodide and myoglobin. It will be shown that vibrational resonances of the reactants and products can be displayed in separate dimensions of a 2D resonance Raman spectrum when the photo-dissociation reaction is fast compared to the vibrational period. Such 2D spectra expose correlations between the nonequilibrium geometry of the reactant and the distribution of vibrational quanta in the product, thereby yielding insight in the photo-dissociation mechanism. Our results suggest that the ability of 2D resonance Raman spectroscopy to detect correlations between reactants and products will generalize to other ultrafast processes such as electron transfer and energy transfer.

  14. Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

    SciTech Connect

    Ravi Kumar, Venkatraman; Rajkumar, Nagappan; Umapathy, Siva

    2015-01-14

    Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-π{sup 1}*; S{sub 1} state) and the shorter (1π-π{sup 1}*; S{sub 2} state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S{sub 2} state relative to the ground state. Raman excitation profiles of PQ (400–1800 cm{sup −1}) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C{sub 2ν} symmetry constraint on the S{sub 2} state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling.

  15. 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.

  16. Broadband absorption through extended resonance modes in random metamaterials

    NASA Astrophysics Data System (ADS)

    Hao, J.; Niemiec, R.; Burgnies, L.; Lheurette, É.; Lippens, D.

    2016-05-01

    The properties of disordered metamaterial absorbers are analyzed on the basis of numerical simulations and experimental characterizations. A broadening of the absorption spectrum is clearly evidenced. This effect is the consequence of both the coupling between nearby resonators leading to the occurrence of extended magnetic resonance modes and the interconnection of elementary particles yielding the definition of resonating clusters. The angular robustness of the absorbing structure under oblique incidence is also demonstrated for a wide domain of angles.

  17. Pre-processing of ultraviolet resonance Raman spectra.

    PubMed

    Simpson, John V; Oshokoya, Olayinka; Wagner, Nicole; Liu, Jing; JiJi, Renee D

    2011-03-21

    The application of UV excitation sources coupled with resonance Raman have the potential to offer information unavailable with the current inventory of commonly used structural techniques including X-ray, NMR and IR analysis. However, for ultraviolet resonance Raman (UVRR) spectroscopy to become a mainstream method for the determination of protein secondary structure content and monitoring protein dynamics, the application of multivariate data analysis methodologies must be made routine. Typically, the application of higher order data analysis methods requires robust pre-processing methods in order to standardize the data arrays. The application of such methods can be problematic in UVRR datasets due to spectral shifts arising from day-to-day fluctuations in the instrument response. Additionally, the non-linear increases in spectral resolution in wavenumbers (increasing spectral data points for the same spectral region) that results from increasing excitation wavelengths can make the alignment of multi-excitation datasets problematic. Last, a uniform and standardized methodology for the subtraction of the water band has also been a systematic issue for multivariate data analysis as the water band overlaps the amide I mode. Here we present a two-pronged preprocessing approach using correlation optimized warping (COW) to alleviate spectra-to-spectra and day-to-day alignment errors coupled with a method whereby the relative intensity of the water band is determined through a least-squares determination of the signal intensity between 1750 and 1900 cm(-1) to make complex multi-excitation datasets more homogeneous and usable with multivariate analysis methods.

  18. Resonance Raman mapping as a tool to monitor and manipulate Si nanocrystals in Si-SiO{sub 2} nanocomposite

    SciTech Connect

    Rani, Ekta; Ingale, Alka A.; Chaturvedi, A.; Joshi, M. P.; Kukreja, L. M.

    2015-10-19

    Specially designed laser heating experiment along with Raman mapping on Si-SiO{sub 2} nanocomposites elucidates the contribution of core and surface/interface in the intermediate frequency range (511–514 cm{sup −1}) Si phonons. The contribution of core to surface/interface increases with the size of Si nanocrystal, which itself increases on laser irradiation. Further, it is found that resonance Raman is crucial to the observance of surface/interface phonons and wavelength dependent Raman mapping can be corroborated with band edges observed in absorption spectra. This understanding can be gainfully used to manipulate and characterize Si-SiO{sub 2} nanocomposite, simultaneously for photovoltaic device applications.

  19. Vibrational relaxation of nascent diiodide ions studied by femtosecond transient resonance impulsive stimulated Raman scattering (TRISRS); experiment and simulation

    NASA Astrophysics Data System (ADS)

    Banin, Uri; Kosloff, Ronnie; Ruhman, Sanford

    1994-06-01

    Impulsive stimulated Raman scattering performed with femtosecond pulses on resonance with an electronic transition, comprises an all time domain Raman technique providing vibrational dynamics of the ground state chromophore. We report the application of this technique to record transient Raman responses of nascent diiodide ions, undergoing rapid vibrational relaxation following triiodide photodissociation in ethanol solution. Like other Fourier spectroscopic methods, this spectroscopy maximizes high simultaneous time and frequency resolution, making it well adapted, and in the present study exclusively capable, for recovering vibrational dynamics of highly excited molecular populations in transition. Master equation simulations of vibrational relaxation, coupled to quantum wave-packet representation of the light-matter interactions, are combined to provide a semi-quantitative analysis of the experimental results. Previous assignment of spectral narrowing of the nascent diiodide absorption to vibrational relaxation is bourn out by simulations. Inherent limitations and fortitudes of the TRISRS method are theoretically investigated and discussed.

  20. Exploring the potential of Raman and resonance Raman spectroscopy for quantitative analysis of duplex DNA

    NASA Astrophysics Data System (ADS)

    Schulze, H. G.; Bass, A.; Addison, C.; Hughesman, C.; So, A. P.; Haynes, C. A.; Blades, M. W.; Turner, R. F. B.

    2005-09-01

    Advances in DNA microarray fabrication technologies, expanding probe libraries, and new bioinformatics methods and resources have firmly established array-based techniques as mainstream bioanalytical tools and the application space is proliferating rapidly. However, the capability of these tools to yield truly quantitative information remains limited, primarily due to problems inherent to the use of fluorescence imaging for reading the hybridized arrays. The obvious advantages of fluorescence are the unrivaled sensitivity and simplicity of the instrumentation. There are disadvantages of this approach, however, such as difficulties in achieving optimal labeling of targets and reproducible signals (due to quenching, resonance energy transfer, photobleaching effects, etc.) that undermine precision. We are exploring alternative approaches, based mainly on Raman and resonance Raman spectroscopy, that in principle permit direct analysis of structural differences between hybridized and unhybridized probes, thereby eliminating the need for labeling the target analytes. We report here on the status of efforts to evaluate the potential of these methods based on a combination of measured data and simulated experiments involving short (12-mer) ssDNA oligomer probes with varying degrees of hybridized target DNA. Preliminary results suggest that it may be possible to determine the fraction of duplex probes within a single register on a DNA microarray from 100% down to 10% (or possibly less) with a precision of +/-2 5%. Details of the methods used, their implementation, and their potential advantages and limitations are presented, along with discussion of the utility of using 2DCOS methods to emphasize small spectral changes sensitive to interstrand H bonding, backbone flexibility, hypochromicity due to base-stacking in duplex structures and solvation effects.

  1. Cyclotron resonance absorption in ionospheric plasma

    NASA Astrophysics Data System (ADS)

    Villalon, Elena

    1991-04-01

    The mode conversion of ordinary polarized electromagnetic waves into electrostatic cyclotron waves in the inhomogeneous ionospheric plasma is investigated. Near resonance the warm plasma dispersion relation is a function of the angle theta between the geomagnetic field and the density gradient and of the wave frequency omega, which lies between the electron cyclotron frequency and its doubling. The differential equations describing the electric field amplitudes near the plasma resonance are studied, including damping at the second gyroharmonic. The energy transmission coefficients and power absorbed by the cyclotron waves are calculated. The vertical penetration of the plasma wave amplitudes is estimated using a WKB analysis of the wave equation.

  2. Carbonyl-functionalized quaterthiophenes: a study of the vibrational Raman and electronic absorption/emission properties guided by theoretical calculations.

    PubMed

    Aragó, Juan; Ponce Ortiz, Rocío; Nieto-Ortega, Belén; Hernández, Víctor; Casado, Juan; Facchetti, Antonio; Marks, Tobin J; Viruela, Pedro M; Ortí, Enrique; López Navarrete, Juan T

    2012-01-16

    This work investigates the evolution of the molecular, vibrational, and optical properties within a family of carbonyl-functionalized quaterthiophenes: 5,5'''-diheptanoyl-2,2':5',2'':5'',2'''-quaterthiophene (1), 5,5'''-diperfluorohexylcarbonyl-2,2':5',2'':5'',2'''-quaterthiophene (2), and 2,7-[bis(5-perfluorohexylcarbonylthien-2-yl)]-4H-cyclopenta[2,1-b:3,4-b']-dithiophene-4-one (3). The analysis is performed by Raman and UV/Vis absorption/excitation/fluorescence spectroscopy in combination with density functional calculations. Theoretical calculations show that substitution with carbonyl groups and perfluorohexyl chains induces progressive quinoidization of the π-conjugated backbone in comparison to the carbonyl-free compound 5,5'''-dimethyl-2,2':5',2'':5'',2'''-quaterthiophene (DM-4T) used as reference. Raman spectra are dominated by a strong Raman line which mainly corresponds to a combination of C-C/C=C stretching vibrations spreading over the whole thiophene core. This band undergoes a remarkable downshift as a consequence of the structural changes induced by the electron-withdrawing groups on the π-conjugated backbone. The band splitting on incorporation of a central carbonyl bridge evidences the formation of two structural domains in the molecule. The excitation and fluorescence spectra recorded at low temperature show well-resolved vibronic structures associated with the most intense collective C-C/C=C stretching mode. Optical absorption and fluorescence bands exhibit remarkable bathochromic dispersion on carbonyl functionalization, indicative of extension of π conjugation. TDDFT calculations enable a detailed description of the trends observed in the absorption spectra. Resonance Raman spectra reflect the structural changes predicted for the S(0)→S(1) electronic transition and evidence the cross-conjugated character that the central carbonyl group confers on 3.

  3. Investigation of locally resonant absorption and factors affecting the absorption band of a phononic glass

    NASA Astrophysics Data System (ADS)

    Chen, Meng; Jiang, Heng; Feng, Yafei; Wang, Yuren

    2014-12-01

    We experimentally and theoretically investigated the mechanisms of acoustic absorption in phononic glass to optimize its properties. First, we experimentally studied its locally resonant absorption mechanism. From these results, we attributed its strong sound attenuation to its locally resonant units and its broadband absorption to its networked structure. These experiments also indicated that the porosity and thickness of the phononic glass must be tuned to achieve the best sound absorption at given frequencies. Then, using lumped-mass methods, we studied how the absorption bandgaps of the phononic glass were affected by various factors, including the porosity and the properties of the coating materials. These calculations gave optimal ranges for selecting the porosity, modulus of the coating material, and ratio of the compliant coating to the stiff matrix to achieve absorption bandgaps in the range of 6-30 kHz. This paper provides guidelines for designing phononic glasses with proper structures and component materials to work in specific frequency ranges.

  4. Deep-UV resonance Raman imaging of a cell (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Kumamoto, Yasuaki

    2016-09-01

    Raman microscopy enables a sensitive, label-free molecular imaging of cells. Employing deep-UV (DUV) light for Raman excitation allows selective measurement of nucleotide bases and aromatic amino acids in a cell, without spectral overlapping of components with a large quantity (i.e. lipid, peptide), because their Raman scattering are specifically enhanced due to the resonance effect. To implement DUV resonance Raman imaging of cells, I previously established a home-built Raman microscope equipped with a DUV laser (λ = 257.2 nm). Raman image representing the distribution of cellular nucleic acid can be reconstructed with the intensity of a Raman band selectively assigned to adenine and guanine. Unfortunately, DUV resonance Raman imaging of cells is severely hindered by molecular photodegradation that occurs after a molecule absorbs DUV light during Raman measurement, precluding a high signal-to-noise ratio and repetitive measurement. To address this issue, I developed a technique for molecular protection under DUV exposure; the trivalent ions of lanthanide group including terbium, europium, and thulium could significantly suppress the molecular photodegradation by relaxing the DUV-excited molecules. The buffer solution containing any of these lanthanide ions with the concentration of 100 µM or higher could provide less destruction of the cellular structures, including nucleotide bases, than the one without the ions, under DUV exposure. Utilizing such protective effects of the lanthanide ions, I successfully achieved a twice higher signal-to-noise ratio and repetitive DUV Raman imaging of cells.

  5. Applications of ultraviolet resonance raman spectroscopy to proteins

    NASA Astrophysics Data System (ADS)

    Spiro, Thomas G.; Grygon, Christine A.

    Recent developments in instrumentation for ultraviolet resonance Raman (UVRR) spectroscopy and its application to proteins are reviewed. With excitation near the ˜ 195 nm amide π-π* transition strong enhancement is seen of the amide vibrational modes, particularly amide II, whose intensity is sensitive to secondary structure. With measurements at 200 and 192 nm one can calculate the fractions of α-helix, β sheet and unordered segments from the known cross sections of these structures. The proline imide II band at ˜ 1460 cm -1 is strongly enhanced with 218 nm excitation and its frequency can be used to monitor cis-trans isomerization. Aromatic residues give rise to strong UVRR bands. Phenylalanine (Phe) and tyrosine (Tyr) show scattering patterns typical of substituted benzenes: enhancement of vibronic modes, especially ν 8a and ν 8b in resonance with the quasi-forbidden L a transition (˜ 205 and ˜ 223 nm for Phe and Tyr), and of breathing modes in resonance with the allowed B a,b transitions (˜ 188 and ˜ 193 nm for Phe and Tyr). Tyrosine, and especially tyrosinate, also show strong enhancement of ν 8a and ν 8b in the B a,b-resonant region, behavior attributed to electronic mixing of L a with B a via the OH (or O -) substituent. In proteins the Tyr ν 8a and ν 8b bands are most readily observed with 229 nm excitation, where the Phe contributions are minimal. The ν 8b frequency is sensitive to Tyr H-bonding and has been calibrated in terms of the H-bond strength. The Tyr 830/850 cm -1 Fermi doublet intensity ratio, which can be monitored at 200 nm is sensitive to H-bonding, but also to other environmental influences. With 218 nm excitation protein spectra are dominated by tryptophan (Trp) contributions. The 1340/1360 cm -1 Trp Fermi doublet is sensitive to solvent exposure, while the ˜ 880 cm -1 band frequency is sensitive to H-bonding. Histidine (His) excitation profiles show π-π* resonances at ˜ 218 and ˜ 204 nm. The UVRR bands are sensitive to

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

    PubMed Central

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

    2012-01-01

    An aluminum bow-tie nano-antenna is combined with the resonance Raman effect in the deep ultraviolet to dramatically increase the sensitivity of Raman spectra to a small volume of material, such as benzene used here. We further demonstrate gradient-field Raman peaks for several strong infrared modes. We achieve a gain of ∼105 in signal intensity from the near field enhancement due to the surface plasmon resonance in the aluminum nanostructure. The on-line resonance enhancement contributes another factor of several thousands, limited by the laser line width. Thus, an overall gain of hundreds of million is achieved. PMID:23066168

  7. 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.

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

    PubMed

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

    2013-09-01

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

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

    PubMed Central

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

    2013-01-01

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

  10. Vibrational resonance enhanced broadband multiphoton absorption in a triphenylamine derivative

    SciTech Connect

    Lu Changgui; Cui Yiping; Huang Wei; Yun Binfeng; Wang Zhuyuan; Hu Guohua; Cui Jing; Lu Zhifeng; Qian Ying

    2007-09-17

    Multiphoton absorption of 2,5-bis[4-(2-N,N-diphenylaminostyryl)phenyl]-1,3,4-oxadiazole was experimentally studied by using femtosecond laser pulses. This material demonstrates a very broad multiphoton absorption band of around 300 nm width with two peaks of 1250 and 1475 nm. The first peak results from the three-photon absorption process while the second is attributed to the vibrational resonance enhanced four-photon absorption process. Combination of these two processes provides a much broader multiphoton absorption band. In this letter, the analytical solution to nonlinear transmission of a three-photon absorption process is also given when the incident beam has a Gaussian transverse spatial profile.

  11. Visualization of Vibrational Modes in Real Space by Tip-Enhanced Non-Resonant Raman Spectroscopy.

    PubMed

    Duan, Sai; Tian, Guangjun; Luo, Yi

    2016-01-18

    We present a general theory to model the spatially resolved non-resonant Raman images of molecules. It is predicted that the vibrational motions of different Raman modes can be fully visualized in real space by tip-enhanced non-resonant Raman scattering. As an example, the non-resonant Raman images of water clusters were simulated by combining the new theory and first-principles calculations. Each individual normal mode gives rise its own distinct Raman image, which resembles the expected vibrational motions of the atoms very well. The characteristics of intermolecular vibrations in supermolecules could also be identified. The effects of the spatial distribution of the plasmon as well as nonlinear scattering processes were also addressed. Our study not only suggests a feasible approach to spatially visualize vibrational modes, but also provides new insights in the field of nonlinear plasmonic spectroscopy.

  12. Simultaneous UV-Visible Absorption and Raman Spectroelectrochemistry.

    PubMed

    Ibañez, David; Garoz-Ruiz, Jesus; Heras, Aranzazu; Colina, Alvaro

    2016-08-16

    The development of a new device based on the use of UV-vis bare optical fibers in a long optical path length configuration and the measurement of the Raman response in normal arrangement allows us to perform UV-vis and Raman spectroelectrochemistry simultaneously in a single experiment. To the best of our knowledge, this is the first time that a spectroelectrochemistry device is able to record both spectroscopic responses at the same time, which further expands the versatility of spectroelectrochemistry techniques and enables us to obtain much more high-quality information in a single experiment. Three different electrochemical systems, such as ferrocyanide, dopamine, and 3,4-ethylenedioxythiophene, have been studied to validate the cell and to demonstrate the performance of the device. Processes that take place in solution can be properly distinguished from processes that occur on the electrode surface during the electrochemical experiment, providing a whole picture of the reactions taking place at the electrode/solution interface. Therefore, this device allows us to study a larger number of complex electrochemical processes from different points of view taking into account not only the UV-vis spectral changes in the solution adjacent to the electrode but also the Raman signal at any location. Furthermore, complementary information, which could not be unambiguously extracted without considering together the two spectroscopic signals and the electrochemical response, is obtained in a novel way.

  13. State-by-state investigation of destructive interference in resonance Raman spectra of neutral tyrosine and the tyrosinate anion with the simplified sum-over-states approach.

    PubMed

    Cabalo, Jerry B; Saikin, Semion K; Emmons, Erik D; Rappoport, Dmitrij; Aspuru-Guzik, Alán

    2014-10-16

    UV resonance Raman scattering is uniquely sensitive to the molecular electronic structure as well as intermolecular interactions. To better understand the relationship between electronic structure and resonance Raman cross section, we carried out combined experimental and theoretical studies of neutral tyrosine and the tyrosinate anion. We studied the Raman cross sections of four vibrational modes as a function of excitation wavelength, and we analyzed them in terms of the contributions of the individual electronic states as well as of the Albrecht A and B terms. Our model, which is based on time-dependent density functional theory (TDDFT), reproduced the experimental resonance Raman spectra and Raman excitation profiles for both studied molecules with good agreement. We found that for the studied modes, the contributions of Albrecht's B terms in the Raman cross sections were important across the frequency range spanning the L(a,b) and B(a,b) electronic excitations in tyrosine and the tyrosinate anion. Furthermore, we demonstrated that interference with high-energy states had a significant impact and could not be neglected even when in resonance with a lower-energy state. The symmetry of the vibrational modes served as an indicator of the dominance of the A or B mechanisms. Excitation profiles calculated with a damping constant estimated from line widths of the electronic absorption bands had the best consistency with experimental results.

  14. Absorption of acoustic waves by sunspots. II - Resonance absorption in axisymmetric fibril models

    NASA Technical Reports Server (NTRS)

    Rosenthal, C. S.

    1992-01-01

    Analytical calculations of acoustic waves scattered by sunspots which concentrate on the absorption at the magnetohydrodynamic Alfven resonance are extended to the case of a flux-tube embedded in a uniform atmosphere. The model is based on a flux-tubes of varying radius that are highly structured, translationally invariant, and axisymmetric. The absorbed fractional energy is determined for different flux-densities and subphotospheric locations with attention given to the effects of twist. When the flux is highly concentrated into annuli efficient absorption is possible even when the mean magnetic flux density is low. The model demonstrates low absorption at low azimuthal orders even in the presence of twist which generally increases the range of wave numbers over which efficient absorption can occur. Resonance absorption is concluded to be an efficient mechanism in monolithic sunspots, fibril sunspots, and plage fields.

  15. Theoretical study of the resonance Raman spectra for meso-tetrakis(3,5-di-tertiarybutylphenyl)-porphyrin.

    PubMed

    Zheng, Ren-hui; Wei, Wen-mei; Zhu, Li-li; Shi, Qiang

    2014-12-10

    Applying time-dependent density functional theory (TDDFT), we study the resonance Raman spectra for the Q and B bands of the meso-tetrakis(3,5-di-tertiarybutylphenyl)-porphyrin (H2TBPP) molecule including both Raman A term (Franck-Condon term) and Raman B term (Herzberg-Teller term) contributions. It is found that Raman B term can be one order of magnitude larger than Raman A term and dominates resonance Raman for the Q band resonance. In comparison with the recent experimental Raman spectra of H2TBPP with incident light frequency 532nm, we predict the absence of 1580cm(-1) band in the resonance Raman spectra which agrees well with the experimental results, whereas the previous theoretical calculation using non-resonance strategy failed to do so.

  16. Resonance Raman spectra of the anion and cation radicals of bacterial photosynthetic pigments

    SciTech Connect

    Diers, J.R.; Bocian, D.F. )

    1994-12-08

    Resonance Raman (RR) spectra are reported for the radical ions of the bacterial photosynthetic pigments bacteriochlorophyll a (BCh) and its metal-free analog bacteriopheophytin a (BPh). The radical anions, BCh[sup [minus

  17. Vulnerable atherosclerotic plaque detection by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Cheng-hui; Boydston-White, Susie; Weisberg, Arel; Wang, Wubao; Sordillo, Laura A.; Perotte, Adler; Tomaselli, Vincent P.; Sordillo, Peter P.; Pei, Zhe; Shi, Lingyan; Alfano, Robert R.

    2016-12-01

    A clear correlation has been observed between the resonance Raman (RR) spectra of plaques in the aortic tunica intimal wall of a human corpse and three states of plaque evolution: fibrolipid plaques, calcified and ossified plaques, and vulnerable atherosclerotic plaques (VPs). These three states of atherosclerotic plaque lesions demonstrated unique RR molecular fingerprints from key molecules, rendering their spectra unique with respect to one another. The vibrational modes of lipids, cholesterol, carotenoids, tryptophan and heme proteins, the amide I, II, III bands, and methyl/methylene groups from the intrinsic atherosclerotic VPs in tissues were studied. The salient outcome of the investigation was demonstrating the correlation between RR measurements of VPs and the thickness measurements of fibrous caps on VPs using standard histopathology methods, an important metric in evaluating the stability of a VP. The RR results show that VPs undergo a structural change when their caps thin to 66 μm, very close to the 65-μm empirical medical definition of a thin cap fibroatheroma plaque, the most unstable type of VP.

  18. Infrared absorption and Raman scattering spectra of water under pressure via first principles molecular dynamics.

    PubMed

    Ikeda, Takashi

    2014-07-28

    From both the polarized and depolarized Raman scattering spectra of supercritical water a peak located at around 1600 cm(-1), attributed normally to bending mode of water molecules, was experimentally observed to vanish, whereas the corresponding peak remains clearly visible in the measured infrared (IR) absorption spectrum. In this computational study a theoretical formulation for analyzing the IR and Raman spectra is developed via first principles molecular dynamics combined with the modern polarization theory. We demonstrate that the experimentally observed peculiar behavior of the IR and Raman spectra for water are well reproduced in our computational scheme. We discuss the origins of a feature observed at 1600 cm(-1) in Raman spectra of ambient water.

  19. Coherent Raman scattering with incoherent light for a multiply resonant mixture: Theory

    NASA Astrophysics Data System (ADS)

    Kirkwood, Jason C.; Ulness, Darin J.; Stimson, Michael J.; Albrecht, A. C.

    1998-02-01

    The theory for coherent Raman scattering (CRS) with broadband incoherent light is presented for a multiply resonant, multicomponent mixture of molecules that exhibits simultaneous multiple resonances with the frequencies of the driving fields. All possible pairwise hyperpolarizability contributions to the signal intensity are included in the theoretical treatment-(resonant-resonant, resonant-nonresonant, and nonresonant-nonresonant correlations between chromophores) and it is shown how the different types of correlations manifest themselves as differently behaved components of the signal intensity. The Raman resonances are modeled as Lorentzians in the frequency domain, as is the spectral density of the incoherent light. The analytic results for this multiply resonant mixture are presented and applied to a specific binary mixture. These analytic results will be used to recover frequencies and dephasing times in a series of experiments on multiply resonant mixtures.

  20. 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

  1. 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.

  2. High-performance dispersive Raman and absorption spectroscopy as tools for drug identification

    NASA Astrophysics Data System (ADS)

    Pawluczyk, Olga; Andrey, Sam; Nogas, Paul; Roy, Andrew; Pawluczyk, Romuald

    2009-02-01

    Due to increasing availability of pharmaceuticals from many sources, a need is growing to quickly and efficiently analyze substances in terms of the consistency and accuracy of their chemical composition. Differences in chemical composition occur at very low concentrations, so that highly sensitive analytical methods become crucial. Recent progress in dispersive spectroscopy with the use of 2-dimensional detector arrays, permits for signal integration along a long (up to 12 mm long) entrance slit of a spectrometer, thereby increasing signal to noise ratio and improving the ability to detect small concentration changes. This is achieved with a non-scanning, non-destructive system. Two different methods using P&P Optica high performance spectrometers were used. High performance optical dispersion Raman and high performance optical absorption spectroscopy were employed to differentiate various acetaminophen-containing drugs, such as Tylenol and other generic brands, which differ in their ingredients. A 785 nm excitation wavelength was used in Raman measurements and strong Raman signals were observed in the spectral range 300-1800 cm-1. Measurements with the absorption spectrometer were performed in the wavelength range 620-1020 nm. Both Raman and absorption techniques used transmission light spectrometers with volume phase holographic gratings and provided sufficient spectral differences, often structural, allowing for drug differentiation.

  3. IR absorption and surface-enhanced Raman spectra of the isoquinoline alkaloid berberine

    NASA Astrophysics Data System (ADS)

    Strekal', N. D.; Motevich, I. G.; Nowicky, J. W.; Maskevich, S. A.

    2007-01-01

    We present the IR absorption and surface-enhanced Raman scattering (SERS) spectra of the isoquinoline alkaloid berberine adsorbed on a silver hydrosol and on the surface of a silver electrode for different potentials. Based on quantum chemical calculations, for the first time we have assigned the vibrations in the berberine molecule according to vibrational mode. The effect of the potential of the silver electrode on the geometry of sorption of the molecule on the surface is considered, assuming a short-range mechanism for enhancement of Raman scattering.

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

    SciTech Connect

    Rahn, L.A.

    1993-12-01

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

  5. A sound absorptive element comprising an acoustic resonance nanofibrous membrane.

    PubMed

    Kalinova, Klara

    2015-01-01

    As absorption of sound of lower frequencies is quite problematic with fibrous material made up of coarser fibers, development of highly efficient sound absorption material is called for. This is why this work deals with the development of new high sound absorption material. To absorb the low frequencies, especially the structures based on resonance principle of nanofibrous layers are used, when through resonance of some elements the acoustic energy is transferred into thermal energy. The goal of the invention is achieved by a sound absorbing means which contains resonance membrane formed by a layer of polymeric nanofibers, which is attached to a frame. For production of nanofibrous membranes, the cord electrospinning was used. The resonance membrane was then, upon impact of sound waves of low frequency, brought into forced vibrations, whereby the kinetic energy of the membrane was converted into thermal energy by friction of individual nanofibers, by the friction of the membrane with ambient air and possibly with other layers of material arranged in its proximity, and some of the energy was also transmitted to the frame, through which the vibrations of the resonance membrane were damped. The density and shape of the mesh of frame formations determine the resonance frequency of the acoustic means. The goal of the invention is therefore to eliminate or at least reduce the disadvantages of the present state of the art and to propose sound absorbing means that would be capable of absorbing, with good results sounds in as broadest frequency range as possible. Here, we also discussed some patents relevant to the topic.

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

    PubMed

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

    2013-10-04

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

  7. 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.

  8. 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.

  9. 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.

  10. Direct excitation of microwave-spin dressed states using a laser-excited resonance Raman interaction

    NASA Astrophysics Data System (ADS)

    Shahriar, M. S.; Hemmer, P. R.

    1990-10-01

    We have used a laser-induced resonance Raman transition between the ground-state hyperfine sublevels in a sodium atomic beam to excite individual dressed states of the microwave-spin hyperfine transition. In addition, we have used the microwave interaction to excite the Raman trapped state. Extension of this technique to mm waves or to the far infrared may lead to applications such as mm-wave-beam steering and holographic image conversion.

  11. Graphene Moiré patterns observed by umklapp double-resonance Raman scattering

    NASA Astrophysics Data System (ADS)

    Righi, A.; Costa, S. D.; Chacham, H.; Fantini, C.; Venezuela, P.; Magnuson, C.; Colombo, L.; Bacsa, W. S.; Ruoff, R. S.; Pimenta, M. A.

    2011-12-01

    This work reports a Raman study of graphene bilayer samples grown by chemical vapor deposition on a copper foil, using laser lines in the UV range. The Raman spectra show a number of extra peaks, classified in different families, which appear nonuniformly across the Cu surface, in regions with sizes of several μm. We interpret these new extra modes as due to Moiré patterns of twisted layers of graphene, each family of peaks being associated with different twist rotational angles. We theoretically analyze the results, introducing the concept of umklapp double-resonance Raman processes associated with reciprocal lattice vectors of the Moiré pattern supercells.

  12. Resonance Raman microspectroscopy of myeloperoxidase and cytochrome b558 in human neutrophilic granulocytes.

    PubMed Central

    Sijtsema, N M; Otto, C; Segers-Nolten, G M; Verhoeven, A J; Greve, J

    1998-01-01

    With (resonance) Raman microscospectroscopy, it is possible to investigate the chemical constitution of a very small volume (0.5 fl) in a living cell. We have measured resonance Raman spectra in the cytoplasm of living normal, myeloperoxidase (MPO)-deficient, and cytochrome b558-deficient neutrophils and in isolated specific and azurophilic granule fractions, using an excitation wavelength of 413.1 nm. Similar experiments were performed after reduction of the redox centers by the addition of sodium dithionite. The specific and azurophilic granules in both redox states appeared to have clearly distinguishable Raman spectra when exciting at a wavelength of 413.1 nm. The azurophilic granules and the cytochrome b558-deficient neutrophils showed Raman spectra similar to that of the isolated MPO. The spectra of the specific granules and the MPO-deficient neutrophils corresponded very well to published cytochrome b558 spectra. The resonance Raman spectrum of the cytoplasmic region of normal neutrophilic granulocytes could be fitted with a combination of the spectra of the specific and azurophilic granules, which shows that the Raman signal of neutrophilic granulocytes mainly originates from MPO and cytochrome b558, at an excitation wavelength of 413.1 nm. PMID:9635778

  13. Resonance Raman intensity analysis of chlorine dioxide dissolved in chloroform: The role of nonpolar solvation

    NASA Astrophysics Data System (ADS)

    Foster, Catherine E.; Barham, Bethany P.; Reid, Philip J.

    2001-05-01

    Absolute resonance Raman cross sections for chlorine dioxide (OClO) dissolved in chloroform are obtained at several excitation wavelengths spanning the photochemically relevant 2B1-2A2 optical transition. The absolute scattering cross sections of OClO are determined by reference to the 666 cm-1 transition of chloroform whose absolute scattering cross sections are reported here. The time-dependent theory for Raman and absorption are used to develop a mode-specific description of the 2A2 excited state surface. This description demonstrates that photoexcitation of OClO leads to significant structural evolution along the symmetric stretch and bend coordinates, with only limited evolution occurring along the asymmetric stretch. This description is similar to that determined for OClO dissolved in cyclohexane and water demonstrating that the excited-state structural evolution of OClO is similar in these solvents. Analysis of the OClO absolute scattering cross sections establishes that the homogeneous linewidth is 95±15 cm-1 in chloroform, essentially identical to the linewidths in cyclohexane and water. To establish the origin of this linewidth, the fluorescence cross section for OClO dissolved in cyclohexane is measured and found to be consistent with an excited-state lifetime of ˜200 fs. Comparison of this lifetime to the homogeneous linewidth establishes that the homogeneous broadening is dominated by solvent-induced pure dephasing. It is proposed that the apparent solvent independence of the homogeneous linewidth reflects the mechanical response of the solvent to the photoinitiated change in solute geometry. In support of this hypothesis, the homogeneous linewidth is reproduced using the viscoelastic continuum model of nonpolar solvation. Finally, it is argued that the restricted evolution along the asymmetric-stretch coordinate is due to dielectric solvent-solute interactions consistent with the increase in inhomogeneous linewidth with an increase in solvent

  14. Multi-wavelength resonance Raman spectroscopy of bacteria to study the effects of growth condition

    NASA Astrophysics Data System (ADS)

    Kunapareddy, Nagapratima; Grun, Jacob; Lunsford, Robert; Gillis, David; Nikitin, Sergei; Wang, Zheng

    2012-06-01

    We will examine the use of multi-wavelength UV resonance-Raman signatures to identify the effects of growth phase on different types of bacteria. Gram positive and gram-negative species, Escherichia coli, Bacillus cereus, Citrobacter koseri and Citrobacter braakii were grown to logarithmic and stationary phases in different culture media. Raman spectra of bacteria were obtained by sequential illumination of samples between 220 and 260 nm; a range which encompasses the resonance frequencies of cellular components. In addition to the information contained in the single spectrum, this two-dimensional signature contains information reflecting variations in resonance cross sections with illumination wavelength. Results of our algorithms in identifying the differences between these germs are discussed. Preliminary results indicate that growth affects the Raman signature, but not to an extent that would negate identification of the species.

  15. Resonance Raman Spectra of Hemoglobin and Cytochrome c: Inverse Polarization and Vibronic Scattering

    PubMed Central

    Spiro, Thomas G.; Strekas, Thomas C.

    1972-01-01

    Resonance Raman spectra of hemoglobin and cytochrome c in dilute solution contain prominent bands that exhibit inverse polarization, i.e., the polarization vector of the incident radiation is rotated through 90° for 90° scattering, giving infinite depolarization ratios. This phenomenon is shown to require an antisymmetric molecular-scattering tensor. The antisymmetry, which is characteristic of resonance scattering, is associated with the form of a particular class of vibrations, A20, of the tetragonal heme chromophores. The dependence of the resonance Raman spectra on the wavelength of the exciting radiation, as well as their polarization properties, demonstrates that the prominent bands correspond to vibronically active modes of the first electronic transition of the heme proteins, and provide confirmation of Albrecht's vibronic theory of Raman intensities. PMID:4506783

  16. NONLINEAR OPTICS: Stimulated resonant hyper-Raman scattering of light by polaritons in alkali metal vapors

    NASA Astrophysics Data System (ADS)

    Galaĭchuk, Yu A.; Yashkir, Yu N.

    1989-12-01

    A theory is developed for the calculation of the gain g due to stimulated resonant hyper-Raman scattering of light by polaritons in gaseous media. It is shown that throughout the tuning range of the pump frequency (including one- and two-photon resonances) a maximum of g corresponds to a dispersion curve of polaritons plotted ignoring attenuation. Theoretical results are used to analyze characteristics of hyper-Raman scattering in sodium vapor. It is shown that under normal experimental conditions the splitting of polariton branches is considerable (amounting to tens of reciprocal centimeters on the frequency scale and several angular degrees). The value of g is estimated for two-photon resonances in the case when the pump frequency is tunable in a wide range. The optimal conditions for stimulated hyper-Raman scattering are identified.

  17. Identifying or measuring selected substances or toxins in a subject using resonant raman signals

    NASA Technical Reports Server (NTRS)

    Lambert, James L. (Inventor); Borchert, Mark S. (Inventor)

    2005-01-01

    Methods and systems of the present invention identify the presence of and/or the concentration of a selected analyte in a subject by: (a) illuminating a selected region of the eye of a subject with an optical excitation beam, wherein the excitation beam wavelength is selected to generate a resonant Raman spectrum of the selected analyte with a signal strength that is at least 100 times greater than Raman spectrums generated by non-resonant wavelengths and/or relative to signals of normal constituents present in the selected region of the eye; (b) detecting a resonant Raman spectrum corresponding to the selected illuminated region of the eye; and (c) identifying the presence, absence and/or the concentration of the selected analyte in the subject based on said detecting step. The apparatus may also be configured to be able to obtain biometric data of the eye to identify (confirm the identity of) the subject.

  18. Multiwavelength Resonance Raman Characterization of the Effect of Growth Phase and Culture Medium on Bacteria.

    PubMed

    Kunapareddy, Nagapratima; Grun, Jacob; Lunsford, Robert; Nikitin, Sergei; Wang, Zheng; Gillis, David

    2015-08-01

    We examine the use of multiwavelength ultraviolet (UV) resonance-Raman signatures to identify the effects of growth phase and growth medium on gram-positive and gram-negative bacteria. Escherichia coli (E. coli), Citrobacter koseri (C. koseri), Citrobacter braakii (C. braakii), and Bacillus cereus (B. cereus) were grown to logarithmic and stationary phases in nutrient broth and brain heart infusion broth. Resonance Raman spectra of bacteria were obtained at multiple wavelengths between 220 and 260 nm; a range that encompasses the resonance frequencies of cellular constituents. We find that spectra of the same bacterial species exhibit differences due to both growth condition and growth phase, but the larger differences reflect changes due to growth phase. The differences in the Raman spectra correlate with genetic differences among the species. Using a Pearson correlation based algorithm, we achieve successful identification of these bacteria in 83% of the cases.

  19. Comparison between IR absorption and raman scattering spectra of liquid and supercritical 1-butanol.

    PubMed

    Sokolova, Maia; Barlow, Stephen J; Bondarenko, Galina V; Gorbaty, Yuri E; Poliakoff, Martyn

    2006-03-23

    Raman spectra of 1-butanol have been obtained at a constant pressure of 500 bar up to 350 degrees C and along isotherms 250, 300, and 350 degrees C up to 600 bar. The purpose of the experiment was to compare responses of Raman and IR absorption spectroscopy to the forming of O-H...O bonds in alcohols. As a result, some important inferences were drawn from the experiment. In particular, it has been estimated quantitatively how the intensity of Raman scattering in the region of the OH band depends on the extent of hydrogen bonding. As might be expected, the dependence is much weaker than in the case of the IR absorption. As was shown, the ratio of integrated intensities of bonded molecules in the absorption and scattering spectra is a constant and does not depend on temperature and density. The effect of cooperativity of hydrogen bonds is confirmed. It was also found that even at high pressures, a noticeable amount of nonbonded molecules exists at room temperature.

  20. Effects of inhomogeneous broadening on the resonance Raman excitation profile of lycopene

    NASA Astrophysics Data System (ADS)

    Cotting, J. E.; Hoskins, L. C.; Levan, M. E.

    1982-08-01

    The resonance Raman excitation profiles for the ν1, ν2, and ν3 vibrations of lycopene in ethyl alcohol, toluene, and carbon disulfide solvents have been measured. The results are interpreted in terms of a three-mode vibrational theory which includes both homogeneous and inhomogeneous broadening effects. Excellent agreement between calculated and observed excitation profiles and visible spectra was found, thus emphasizing the need to interpret resonance Raman data using a multimode vibrational model. The results indicate that the major broadening mechanism is homogeneous broadening, with about a 25% contribution from inhomogeneous broadening. The excitation profiles in carbon disulfide gave the largest inhomogeneous broadening.

  1. Resonance Raman investigation of the photoreduction of methylviologen with Ru(bpy) 2+3 and proflavine as sensitizers

    NASA Astrophysics Data System (ADS)

    Forster, Martin; Hester, Ronald E.

    1982-01-01

    Reduced methylviologen (MV +) is detected by conventional resonance Raman spectroscopy in photoreactions of Ru(bpy) 2+3 or proflavine (PFH +) with MV 2+ Using apparatus for modulated excitation resonance Raman (MERR) spectroscopy, the irreversible MV + production with PFH + as sensitizer is traced back to triplet-triplet annihilation with simultaneous destruction of PFH +.

  2. Sources of hot electrons in laser-plasma interaction with emphasis on Raman and turbulence absorption

    SciTech Connect

    Estabrook, K.; Kruer, W.L.; Phillion, D.W.; Turner, R.E.; Campbell, E.M.

    1982-04-06

    Heating targets with high power lasers results in a sizable fraction of the absorbed energy going into electrons of temperature much greater than thermal which can pre-heat the pellet core and accelerate fast ion blowoff which results in poor momentum transfer and hence poor compression efficiency. The present emphasis is to build lasers of higher frequency, ..omega../sub 0/, which at the same W/cm/sup 2/ results in more absorption into cooler electrons. Two physical reasons are that the laser can propagate to a higher electron density, n, infinity..omega../sub 0//sup 2/ resulting in more collisional inverse bremsstrahlung absorption proportional to n, and because the hot temperatures from some plasma absorption processes increase as the oscillatory velocity of an electron in the laser electric field v/sub 0//c = eE/(m/sub e/..omega../sub 0/). The heated electron temperatures from other plasma processes (Raman for example approx.(m/sub e//2)v/sup 2//sub phase/ and the higher laser frequency helps by increasing the competing collisional absorption and decreasing the Raman gain.

  3. Towards higher stability of resonant absorption measurements in pulsed plasmas

    SciTech Connect

    Britun, Nikolay; Michiels, Matthieu; Snyders, Rony

    2015-12-15

    Possible ways to increase the reliability of time-resolved particle density measurements in pulsed gaseous discharges using resonant absorption spectroscopy are proposed. A special synchronization, called “dynamic source triggering,” between a gated detector and two pulsed discharges, one representing the discharge of interest and another being used as a reference source, is developed. An internal digital delay generator in the intensified charge coupled device camera, used at the same time as a detector, is utilized for this purpose. According to the proposed scheme, the light pulses from the reference source follow the gates of detector, passing through the discharge of interest only when necessary. This allows for the utilization of short-pulse plasmas as reference sources, which is critical for time-resolved absorption analysis of strongly emitting pulsed discharges. In addition to dynamic source triggering, the reliability of absorption measurements can be further increased using simultaneous detection of spectra relevant for absorption method, which is also demonstrated in this work. The proposed methods are illustrated by the time-resolved measurements of the metal atom density in a high-power impulse magnetron sputtering (HiPIMS) discharge, using either a hollow cathode lamp or another HiPIMS discharge as a pulsed reference source.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  5. UV resonance Raman finds peptide bond-Arg side chain electronic interactions.

    PubMed

    Sharma, Bhavya; Asher, Sanford A

    2011-05-12

    We measured the UV resonance Raman excitation profiles and Raman depolarization ratios of the arginine (Arg) vibrations of the amino acid monomer as well as Arg in the 21-residue predominantly alanine peptide AAAAA(AAARA)(3)A (AP) between 194 and 218 nm. Excitation within the π → π* peptide bond electronic transitions result in UVRR spectra dominated by amide peptide bond vibrations. The Raman cross sections and excitation profiles indicate that the Arg side chain electronic transitions mix with the AP peptide bond electronic transitions. The Arg Raman bands in AP exhibit Raman excitation profiles similar to those of the amide bands in AP which are conformation specific. These Arg excitation profiles distinctly differ from the Arg monomer. The Raman depolarization ratios of Arg in monomeric solution are quite simple with ρ = 0.33 indicating enhancement by a single electronic transition. In contrast, we see very complex depolarization ratios of Arg in AP that indicate that the Arg residues are resonance enhanced by multiple electronic transitions.

  6. Resonance Raman Spectroscopy of Extreme Nanowires and Other 1D Systems

    PubMed Central

    Smith, David C.; Spencer, Joseph H.; Sloan, Jeremy; McDonnell, Liam P.; Trewhitt, Harrison; Kashtiban, Reza J.; Faulques, Eric

    2016-01-01

    This paper briefly describes how nanowires with diameters corresponding to 1 to 5 atoms can be produced by melting a range of inorganic solids in the presence of carbon nanotubes. These nanowires are extreme in the sense that they are the limit of miniaturization of nanowires and their behavior is not always a simple extrapolation of the behavior of larger nanowires as their diameter decreases. The paper then describes the methods required to obtain Raman spectra from extreme nanowires and the fact that due to the van Hove singularities that 1D systems exhibit in their optical density of states, that determining the correct choice of photon excitation energy is critical. It describes the techniques required to determine the photon energy dependence of the resonances observed in Raman spectroscopy of 1D systems and in particular how to obtain measurements of Raman cross-sections with better than 8% noise and measure the variation in the resonance as a function of sample temperature. The paper describes the importance of ensuring that the Raman scattering is linearly proportional to the intensity of the laser excitation intensity. It also describes how to use the polarization dependence of the Raman scattering to separate Raman scattering of the encapsulated 1D systems from those of other extraneous components in any sample. PMID:27168195

  7. Laser engines operating by resonance absorption. [thermodynamic feasibility study

    NASA Technical Reports Server (NTRS)

    Garbuny, M.; Pechersky, M. J.

    1976-01-01

    Basic tutorial article on the thermodynamic feasibility of laser engines at the present state of the art. Three main options are considered: (1) laser power applied externally to a heat reservoir (boiler approach); (2) internal heating of working fluid by resonance absorption; and (3) direct conversion of selective excitation into work. Only (2) is considered practically feasible at present. Basic concepts and variants, efficiency relations, upper temperature limits of laser engines, selection of absorbing gases, engine walls, bleaching, thermodynamic cycles of optimized laser engines, laser-powered turbines, laser heat pumps are discussed. Photon engines and laser dissociation engines are also considered.

  8. Resonance Raman Studies Of Lactoperoxidase And Sulflactoperoxidase: Drug-Induced Chlorin Formation

    NASA Astrophysics Data System (ADS)

    Andersson, Laura A.

    1989-07-01

    Thyroid peroxidase (TPO) is a membrane-bound heme enzyme that catalyzes iodination and coupling of thyroglobulin tyrosine residues in the biosynthesis of thyroid hormones. The soluble heme enzyme lactoperoxidase (LPO) also iodinates tyrosine efficiently and serves as a functional model for TPO. Whereas horseradish peroxidase oxidizes sulfur-containing compounds, e.g., cysteine and glutathione, these compounds interact with LPO and TPO without oxidation. Indeed, clinical treatment of thyroid disease involves the use of sulfur-containing drugs (goitrogens) to inactivate TPO. Reactions of TPO and LPO with goitrogens result in enzyme inhibition, in a process similar to the conversion of myoglobin to sulf-myoglobin (sulf-Mb). We have examined the electronic absorption and resonance Raman (RR) spectral properties of LPO treated with the potent antithyroid drug methylmercaptoimidazole (MMi). Interaction of LPO with MMi yields a stable, emerald green complex (SLPO (MNi]). The electronic absorption spectra of SLPO [MMi] are similar to those of sulf-Mb (which has a sulfur-modified iron chlorin macrocycle), and to those of the naturally occurring Escherichia coli and Neurospora crassa chlorin catalases. The Soret excitation RR spectrum of the SLPO [DIM] complex is distinct from that of native LPO, but is consistent with the spectral pattern for metallochlorins established by our laboratory. The SLPO [NW RR pattern is also analogous to that of chlorin-containing proteins such as the isomeric sulf-Mb's, myeloperoxidase, and the E. coli and N. crassa catalases. These data strongly suggest that MMi treatment of LPO results in conversion of the porphyrin prosthetic moiety to an iron chlorin. We infer that clinical treatment of thyroid disorders with the goitrogen drug MMi similarly converts the porphyrin prosthetic moiety of thyroid peroxidase to an iron chlorin. Spectral differences between sulf-Mb and SLPO [MMI] are particularly intriguing and suggest structural differences

  9. Photodetector with absorbing region having resonant periodic absorption between reflectors

    DOEpatents

    Bryan, Robert P.; Olbright, Gregory R.; Brennan, Thomas M.; Tsao, Jeffrey Y.

    1995-02-14

    A photodetector that is responsive to a wavelength or wavelengths of interest which have heretofore been unrealized. The photodetector includes a resonant cavity structure bounded by first and second reflectors, the resonant cavity structure being resonant at the wavelength or wavelengths of interest for containing a plurality of standing waves therein. The photodetector further includes a radiation absorbing region disposed within the resonant cavity structure, the radiation absorbing region including a plurality of radiation absorbing layers spaced apart from one another by a distance substantially equal to a distance between antinodes of adjacent ones of the standing waves. Each of radiation absorbing layers is spatially positioned at a location of one of the antinodes of one of the standing waves such that radiation absorption is enhanced. The radiation absorbing layers may be either bulk layers or quantum wells includes a plurality of layers, each of which is comprised of a strained layer of InGaAs. Individual ones of the InGaAs layers are spaced apart from one another by a GaAs barrier layer.

  10. Photodetector with absorbing region having resonant periodic absorption between reflectors

    DOEpatents

    Bryan, R.P.; Olbright, G.R.; Brennan, T.M.; Tsao, J.Y.

    1995-02-14

    A photodetector is disclosed that is responsive to a wavelength or wavelengths of interest which have heretofore been unrealized. The photodetector includes a resonant cavity structure bounded by first and second reflectors, the resonant cavity structure being resonant at the wavelength or wavelengths of interest for containing a plurality of standing waves therein. The photodetector further includes a radiation absorbing region disposed within the resonant cavity structure, the radiation absorbing region including a plurality of radiation absorbing layers spaced apart from one another by a distance substantially equal to a distance between antinodes of adjacent ones of the standing waves. Each of radiation absorbing layers is spatially positioned at a location of one of the antinodes of one of the standing waves such that radiation absorption is enhanced. The radiation absorbing layers may be either bulk layers or quantum wells includes a plurality of layers, each of which is comprised of a strained layer of InGaAs. Individual ones of the InGaAs layers are spaced apart from one another by a GaAs barrier layer. 11 figs.

  11. FTIR difference and resonance Raman spectroscopy of rhodopsins with applications to optogenetics

    NASA Astrophysics Data System (ADS)

    Saint Clair, Erica C.

    The major aim of this thesis is to investigate the molecular basis for the function of several types of rhodopsins with special emphasis on their application to the new field of optogenetics. Rhodopsins are transmembrane biophotonic proteins with 7 alpha-helices and a retinal chromophore. Studies included Archaerhodopsin 3 (AR3), a light driven proton pump similar to the extensively studied bacteriorhodopsin (BR); channelrhodopsins 1 and 2, light-activated ion channels; sensory rhodopsin II (SRII), a light-sensing protein that modulates phototaxis used in archaebacteria; and squid rhodopsins (sRho), the major photopigment in squid vision and a model for human melanopsin, which controls circadian rhythms. The primary techniques used in these studies were FTIR difference spectroscopy and resonance Raman spectroscopy. These techniques, in combination with site directed mutagenesis and other biochemical methodologies produced new knowledge regarding the structural changes of the retinal chromophore, the location and function of internal water molecules as well as specific amino acids and peptide backbone. Specialized techniques were developed that allowed rhodopsins to be studied in intact membrane environments and in some cases in vivo measurements were made on rhodopsin heterologously expressed in E. coli thus allowing the effects of interacting proteins and membrane potential to be investigated. Evidence was found that the local environment of one or more internal water molecules in SRII is altered by interaction with its cognate transducer, HtrII, and is also affected by the local lipid environment. In the case of AR3, many of the broad IR continuum absorption changes below 3000 cm -1, assigned to networks of water molecules involved in proton transport through cytoplasmic and extracellular portions in BR, were found to be very similar to BR. Bands assigned to water molecules near the Schiff base postulated to be involved in proton transport were, however, shifted

  12. Efficient Heterostructures for Combined Interference and Plasmon Resonance Raman Amplification.

    PubMed

    Alvarez-Fraga, Leo; Climent-Pascual, Esteban; Aguilar-Pujol, Montserrat; Ramírez-Jiménez, Rafael; Jiménez-Villacorta, Félix; Prieto, Carlos; de Andrés, Alicia

    2017-02-01

    The detection, identification, and quantification of different types of molecules and the optical imaging of, for example, cellular processes are important challenges. Here, we present how interference-enhanced Raman scattering (IERS) in adequately designed heterostructures can provide amplification factors relevant for both detection and imaging. Calculations demonstrate that the key factor is maximizing the absolute value of the refractive indices' difference between dielectric and metal layers. Accordingly, Si/Al/Al2O3/graphene heterostructures have been fabricated by optimizing the thickness and roughness and reaching enhancement values up to 700 for 488 nm excitation. The deviation from the calculated enhancement, 1200, is mainly due to reflectivity losses and roughness of the Al layer. The IERS platforms are also demonstrated to improve significantly the quality of white light images of graphene and are foreseen to be adequate to reveal the morphology of 2D and biological materials. A graphene top layer is adequate for most organic molecule deposition and often quenches possible fluorescence, permitting Raman signal detection, which, for a rhodamine 6G (R6G) monolayer, presents a gain of 400. Without graphene, the nonquenched R6G fluorescence is similarly amplified. The wavelength dependence of the involved refractive indices predicts much higher amplification (around 10(4)) for NIR excitation. These interference platforms can therefore be used to gain contrast and intensity in white light, Raman, and fluorescence imaging. We also demonstrate that surface-enhanced Raman scattering and IERS amplifications can be efficiently combined, leading to a gain of >10(5) (at 488 nm) by depositing a Ag nanostructured transparent film on the IERS platform. When the plasmonic structures deposited on the IERS platforms are optimized, single-molecule detection can be actively envisaged.

  13. Activated vibrational modes and Fermi resonance in tip-enhanced Raman spectroscopy.

    PubMed

    Sun, Mengtao; Fang, Yurui; Zhang, Zhenyu; Xu, Hongxing

    2013-02-01

    Using p-aminothiophenol (PATP) molecules on a gold substrate and high-vacuum tip-enhanced Raman spectroscopy (HV-TERS), we show that the vibrational spectra of these molecules are distinctly different from those in typical surface-enhanced Raman spectroscopy. Detailed first-principles calculations help to assign the Raman peaks in the TERS measurements as Raman-active and IR-active vibrational modes of dimercaptoazobenzene (DMAB), providing strong spectroscopic evidence for the dimerization of PATP molecules to DMAB under the TERS setup. The activation of the IR-active modes is due to enhanced electromagnetic field gradient effects within the gap region of the highly asymmetric tip-surface geometry. Fermi resonances are also observed in HV-TERS. These findings help to broaden the versatility of TERS as a promising technique for ultrasensitive molecular spectroscopy.

  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. 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. Chemical Binding Effects in Neutron Resonance Scattering and Absorption.

    NASA Astrophysics Data System (ADS)

    Shamaoun, Adib Iskandar

    The Doppler broadening of neutron absorption and scattering resonances is an effect of considerable importance in calculating reactor parameters. This broadening is known to depend upon the state of the atom from which the scattering of the neutron occurs. This dependence is called the chemical binding effect. A key assumption in the usual computations of Doppler broadening is to ignore the dependence of the total resonance width on the chemical binding state of the compound nucleus. This is an excellent approximation for the gamma line. We derive an expression for the neutron line width as a function of the energy of the compound nucleus for an ideal gas. The influence of energy on the width with energy is examined at two different temperatures 4K and 1000K. It is found that these effects are very small, of the order of 10^{4-} . The assumption of constancy of the resonance width is thus shown to be a good approximation for the neutron line width. Also we examine the influence of the crystalline binding on the 6.67 eV resonance energy of U-238 line shape in uranium carbide and uranium dioxide. This model treats the crystal as a gas with an effective temperature and an effective mass determined by harmonic crystal phonon spectrum developed by Koppel and Houston. Based on this model, the line shape of U-238 is Gaussian plus a recoilless part. We also compute the broadening using a harmonic crystal model. As the temperature of U-238 target is decreased, disagreement between the two models becomes pronounced. However the results agree in the limiting case of high temperature. As the nucleus becomes more tightly bound, shifts in the resonance peak to lower energies are also observed. A general formula for the differential scattering cross section is developed starting from the transition probability (T-matrix). The formalism is applied to the gas and harmonic crystal models to determine the chemical binding effect. Although the resonance broadening is determined in

  17. Resonance Raman spectroscopic evaluation of skin carotenoids as a biomarker of carotenoid status for human studies

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Resonance Raman Spectroscopy (RRS) is a non-invasive method that has been developed to assess carotenoid status in human tissues including human skin in vivo. Skin carotenoid status, as assessed by RRS, has been suggested as a promising biomarker for use in human studies. This manuscript describes...

  18. Resonance Raman Spectroscopy of Beta-Carotene and Lycopene: A Physical Chemistry Experiment.

    ERIC Educational Resources Information Center

    Hoskins, L. C.

    1984-01-01

    Discusses the theory of resonance Raman (RR) spectroscopy as it applies to beta-carotene and lycopene pigments (found in tomatoes and carrots, respectively). Also discusses an experiment which demonstrates the theoretical principles involved. The experiment has been tested over a three-year period and has received excellent acceptance by physical…

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

    SciTech Connect

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

    2006-07-14

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

  20. Simulation of the resonance Raman spectra for 5-halogenated (F, Cl, and Br) uracils.

    PubMed

    Sun, Shuai; Brown, Alex

    2015-04-30

    The resonance Raman spectra of the 5-halogenated (F, Cl, and Br) uracils are simulated via the Herzberg-Teller (HT) short-time dynamics formalism. The gradient of the S1 excited state is computed at the CAMB3LYP/aug-cc-pVTZ level of theory in the conductor-like polarizable continuum model for water (C-PCM, H2O), based on the equilibrium geometry determined using PBE0/aug-cc-pVTZ in H2O (C-PCM). The simulated resonance Raman spectra show good agreement with the experimental spectra in terms of both peak positions and intensities. The differences between the resonance Raman spectra of the three 5-halogenated uracils, caused by the effect of halogen substitution, are examined in terms of ground-state normal-mode eigenvectors and excited-state Cartesian gradients, according to the HT formalism. The differences in the normal-mode eigenvectors and excited-state Cartesian gradients between 5-fluorouracil and 5-chlorouracil are used to interpret the dissimilarity between their resonance Raman spectra. Meanwhile, the similarity between the spectra of 5-chlorouracil and 5-bromouracil is explained by the correspondence between their normal modes and excited-state gradients.

  1. Multidimensional resonance raman spectroscopy by six-wave mixing in the deep UV

    SciTech Connect

    Molesky, Brian P.; Giokas, Paul G.; Guo, Zhenkun; Moran, Andrew M.

    2014-09-21

    Two-dimensional (2D) resonance Raman spectroscopies hold great potential for uncovering photoinduced relaxation processes in molecules but are not yet widely applied because of technical challenges. Here, we describe a newly developed 2D resonance Raman experiment operational at the third-harmonic of a Titanium-Sapphire laser. High-sensitivity and rapid data acquisition are achieved by combining spectral interferometry with a background-free (six-pulse) laser beam geometry. The third-harmonic laser pulses are generated in a filament produced by the fundamental and second-harmonic pulses in neon gas at pressures up to 35 atm. The capabilities of the setup are demonstrated by probing ground-state wavepacket motions in triiodide. The information provided by the experiment is explored with two different representations of the signal. In one representation, Fourier transforms are carried out with respect to the two experimentally controlled delay times to obtain a 2D Raman spectrum. Further insights are derived in a second representation by dispersing the signal pulse in a spectrometer. It is shown that, as in traditional pump-probe experiments, the six-wave mixing signal spectrum encodes the wavepacket's position by way of the (time-evolving) emission frequency. Anharmonicity additionally induces dynamics in the vibrational resonance frequency. In all cases, the experimental signals are compared to model calculations based on a cumulant expansion approach. This study suggests that multi-dimensional resonance Raman spectroscopies conducted on systems with Franck-Condon active modes are fairly immune to many of the technical issues that challenge off-resonant 2D Raman spectroscopies (e.g., third-order cascades) and photon-echo experiments in the deep UV (e.g., coherence spikes). The development of higher-order nonlinear spectroscopies operational in the deep UV is motivated by studies of biological systems and elementary organic photochemistries.

  2. Signal enhancement of surface enhanced Raman scattering and surface enhanced resonance Raman scattering using in situ colloidal synthesis in microfluidics.

    PubMed

    Wilson, Rab; Bowden, Stephen A; Parnell, John; Cooper, Jonathan M

    2010-03-01

    We demonstrate the enhanced analytical sensitivity of both surface enhanced Raman scattering (SERS) and surface enhanced resonance Raman scattering (SERRS) responses, resulting from the in situ synthesis of silver colloid in a microfluidic flow structure, where both mixing and optical interrogation were integrated on-chip. The chip-based sensor was characterized with a model Raman active label, rhodamine-6G (R6G), and had a limit of detection (LOD) of ca. 50 fM (equivalent to single molecule detection). The device was also used for the determination of the natural pigment, scytonemin, from cyanobacteria (as an analogue for extraterrestrial life existing in extreme environments). The observed LOD of approximately 10 pM (ca. <400 molecules) demonstrated the analytical advantages of working with freshly synthesized colloid in such a flow system. In both cases, sensitivities were between 1 and 2 orders of magnitude greater in the microfluidic system than those measured using the same experimental parameters, with colloid synthesized off-chip, under quiescent conditions.

  3. Differential absorption and Raman lidar for water vapor profile measurements - A review

    NASA Technical Reports Server (NTRS)

    Grant, William B.

    1991-01-01

    Differential absorption lidar and Raman lidar have been applied to the range-resolved measurements of water vapor density for more than 20 years. Results have been obtained using both lidar techniques that have led to improved understanding of water vapor distributions in the atmosphere. This paper reviews the theory of the measurements, including the sources of systematic and random error; the progress in lidar technology and techniques during that period, including a brief look at some of the lidar systems in development or proposed; and the steps being taken to improve such lidar systems.

  4. Raman and absorption spectrophotometric studies of selected lanthanide, californium-doped lanthanide, and actinide trihalides in the solid state

    SciTech Connect

    Wilmarth, W.R.

    1988-03-01

    The solid-state absorption spectra of Cf(III) ions as a dopant in lanthanide trihalide hosts (LnCl/sub 3/: Ln = Ce, Sm, and Y; LnBr/sub 3/: Ln = Ce, Sm, Tb, and Y; LnI/sub 3/: Ln = Ce and Y) have been recorded. The spectra of Cf(III) have been correlated with the various crystal structures. The phonon Raman spectra and solid-state absorption spectra of PmF/sub 3/, PmCl/sub 3/, PmBr/sub 3/, and two crystal modifications of PmI/sub 3/ have been recorded. Symmetry assignments have been made for the Raman-active bands for these trihalides and also the sesquioxide. The room-temperature absorption spectra have been correlated to crystal field effects. The symmetry assignments of the Raman-active phonon modes have been made based on polarized Raman spectra from single crystals of YF/sub 3/-type orthorhombic TbF/sub 3/ and PuBr/sub 3/-type orthorhombic NdBr/sub 3/. Raman spectra of other isostructural lanthanide compounds have been recorded and compared. Symmetry assignments for these compounds have been made by analogy to the single-crystal assignments. Raman spectra have been obtained and catalogued for a number of actinide compounds. Symmetry assignments have been made for the observed Raman-active phonon bands in this work based on the assignments made for isostructural lanthanide compounds. 29 figs., 22 tabs.

  5. Time-gated pre-resonant femtosecond stimulated Raman spectroscopy of diethylthiatricarbocyanine iodide.

    PubMed

    Kim, Hyung Min; Kim, Hyunmin; Yang, Ilseung; Jin, Seung Min; Suh, Yung Doug

    2014-03-21

    We present time-gated femtosecond stimulated Raman spectroscopy (fSRS) under the pre-resonance Raman conditions of diethylthiatricarbocyanine (DTTC) iodide. A 'pseudo emission-free' condition is achieved by delivering the probe beam ahead of the pump beam. Regeneratively amplified pulse trains are employed to create an angle-geometry (non-collimated) mixing between the pump and probe beams, leading to highly sensitive measurement of the stimulated Raman gain. Time-integrated spectroscopy allows for a more quantitative distinction between the contributions of stimulated Raman scattering and stimulated emission. We successfully obtain a highly sensitive (signal-to-noise ratio >100) stimulated Raman spectrum under the optimized conditions, which compares favourably to results obtained using two-dimensional correlation spectroscopy (2DCOS). Given the optical pre-resonance of ∼0.1 eV, the background signals mostly originate from the stimulated emission of excited electrons and are significantly reduced by partial overlapping of the pump and probe beams; a genuine fSRS spectral profile is obtained for a temporal delay of ∼0.2 ps between the two beams.

  6. Resonance Raman spectroscopic and density functional theory study of p-nitroacetophenone (PNAP)

    NASA Astrophysics Data System (ADS)

    Pei, Kemei; Ma, Yufang; Zheng, Xuming; Li, Haiyang

    2007-03-01

    Resonance Raman spectra of p-nitroacetophenone(PNAP) have been obtained in resonance with the charge-transfer (CT) band using 252.7, 266 and 273.9 nm in methanol solvent. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mainly along the C dbnd O stretching ν8(1691 cm -1) and the benzene ring stretch ν10(1593 cm -1). A preliminary resonance Raman intensity analysis was done and the results for PNAP were compared with nitrobenzene and aceptophenone. Our results indicate that -NO 2 is more photoactive than -COCH 3. The isomerization process of PNAP takes place somewhere after the wave packet leaves the Franck-Condon region.

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

    NASA Astrophysics Data System (ADS)

    Ye, ChuanXiang; Zhao, Yi; Liang, WanZhen

    2015-10-01

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

  8. Interpretation of the resonance Raman spectra of linear tetrapyrroles based on DFT calculations

    NASA Astrophysics Data System (ADS)

    Kneip, Christa; Hildebrandt, Peter; Németh, Károly; Mark, Franz; Schaffner, Kurt

    1999-10-01

    Raman spectra of linear methine-bridged tetrapyrroles in different conformational and protonation states were calculated on the basis of scaled force fields obtained by density functional theory. Results are reported for protonated phycocyanobilin in the extended ZZZasa configuration, as it is found in C-phycocyanin of cyanobacteria. The calculated spectra are in good agreement with experimental spectra of the protein-bound chromophore in the α-subunit of C-phycocyanin and allow a plausible and consistent assignment of most of the observed resonance Raman bands in the region between 1000 and 1700 cm -1.

  9. Distance dependence of surface-enhanced resonance raman enhancement in Langmuir-Blodgett dye multilayers

    SciTech Connect

    Cotton, T.M.; Uphaus, R.A.; Moebius, D.

    1986-11-06

    Monolayers of a surface-active dye incorporated into inert matrix material were transferred onto structurally defined silver island films by the Langmuir-Blodgett technique. The dye-containing monolayers were spaced from the surface by accurately known increments by deposition of inert spacer monolayers. Surface-enhanced resonance Raman spectra were observed from dye molecules spaced as distant as six spacer increments (ca. 16 nm) from the silver surface. These results indicate an electromagnetic mechanism is operative in this system in contradiction to a chemical mechanism which would require direct contact between the Raman-active species and the metal surface.

  10. Data acquisition system developed for the resonance absorption project

    SciTech Connect

    Arnone, G.J.; Hollas, C.L.

    1993-12-01

    Minimizing signal errors and losses in high-rate gamma-ray imaging systems places demands on the signal-processing and data acquisition electronics. We will describe the data acquisition system developed for the resonance absorption project and techniques used to minimize dead-time and data losses. The data acquisition system acquires pulse-height spectra from an array of gamma-ray detectors and is made available to multiple processors by using the VMEbus standard to provide concurrent data analysis. A SUN workstation is used to develop the application software and also provides the user interface. We have developed a pulse-height-analysis board that has been optimized for low dead time. By incorporating an independent, high-speed signal channel for each detector, we are able to improve performance over multiplexed techniques.

  11. Simultaneous surface plasmon resonance and x-ray absorption spectroscopy

    SciTech Connect

    Serrano, A.; Rodriguez de la Fuente, O.; Collado, V.; Rubio-Zuazo, J.; Castro, G. R.; Monton, C.; Garcia, M. A.

    2012-08-15

    We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10{sup -3} to 10{sup -5}, depending on the particular experiment.

  12. Total absorption in ultra-thin lossy layer on transparent substrate using dielectric resonance structure

    NASA Astrophysics Data System (ADS)

    Matsui, T.; Iizuka, H.

    2017-03-01

    A resonant sub-wavelength structure made of a high-refractive-index dielectric material exhibits a resonator-like response and provides unity reflection. We show that near-unity absorption is obtained by using a sub-wavelength resonant structure, which consists of periodic high-refractive-index nano-blocks, when an ultra-thin absorption layer is attached to a transparent dielectric substrate. The resonant structure does not necessarily touch the absorption layer and, therefore, a coating film can be inserted between the absorption layer and the periodic structure. Our results significantly extend application scenarios of detectors and optoelectronic devices that can be implemented on transparent dielectric substrates.

  13. Effects of locally resonant modes on underwater sound absorption in viscoelastic materials.

    PubMed

    Wen, Jihong; Zhao, Honggang; Lv, Linmei; Yuan, Bo; Wang, Gang; Wen, Xisen

    2011-09-01

    Recently, by introducing locally resonant scatterers with spherical shape proposed in phononic crystals into design of underwater sound absorption materials, the low-frequency underwater sound absorption phenomenon induced by the localized resonances is observed. To reveal this absorption mechanism, the effect of the locally resonant mode on underwater sound absorption should be studied. In this paper, the finite element method, which is testified efficiently by comparing the calculation results with those of the layer multiple scattering method, is introduced to investigate the dynamic modes and the corresponding sound absorption of localized resonance. The relationship between the resonance modes described with the displacement contours of one unit cell and the corresponding absorption spectra is discussed in detail, which shows that the localized resonance leads to the absorption peak, and the mode conversion from longitudinal to transverse waves at the second absorption peak is more efficient than that at the first one. Finally, to show the modeling capability of FEM and investigate shape effects of locally resonant scatterers on underwater sound absorption, the absorption properties of viscoelastic materials containing locally resonant scatterers with ellipsoidal shape are discussed.

  14. Raman resonance in the strained Ge quantum dot array.

    PubMed

    Talochkin, A B; Markov, V A

    2008-07-09

    We study the Raman resonance of a Ge quantum dot (QD) array grown pseudomorphically to a Si matrix using low-temperature molecular-beam epitaxy. A change of the resonance energy and the shape of the resonance curve in comparison with bulk Ge are observed. These features are shown to be explained by taking into account QD strain and the quasistationary character of the electronic states responsible for the observed resonance. Application of a model of the two-dimensional critical point of the interband density of states allows us to estimate the damping parameter and localization size of these states. It is shown that the observed enhancement of the resonance amplitude in a QD array as compared to the bulk case is related to transformation of the interband density of states into the δ-function due to quantization of the electron-hole spectrum.

  15. Solute-solvent intermolecular vibronic coupling as manifested by the molecular near-field effect in resonance hyper-Raman scattering.

    PubMed

    Shimada, Rintaro; Hamaguchi, Hiro-o

    2011-01-21

    Vibronic coupling within the excited electronic manifold of the solute all-trans-β-carotene through the vibrational motions of the solvent cyclohexane is shown to manifest as the "molecular near-field effect," in which the solvent hyper-Raman bands are subject to marked intensity enhancements under the presence of all-trans-β-carotene. The resonance hyper-Raman excitation profiles of the enhanced solvent bands exhibit similar peaks to those of the solute bands in the wavenumber region of 21,700-25,000 cm(-1) (10,850-12,500 cm(-1) in the hyper-Raman exciting wavenumber), where the solute all-trans-β-carotene shows a strong absorption assigned to the 1A(g) → 1B(u) transition. This fact indicates that the solvent hyper-Raman bands gain their intensities through resonances with the electronic states of the solute. The observed excitation profiles are quantitatively analyzed and are successfully accounted for by an extended vibronic theory of resonance hyper-Raman scattering that incorporates the vibronic coupling within the excited electronic manifold of all-trans-β-carotene through the vibrational motions of cyclohexane. It is shown that the major resonance arises from the B-term (vibronic) coupling between the first excited vibrational level (v = 1) of the 1B(u) state and the ground vibrational level (v = 0) of a nearby A(g) state through ungerade vibrational modes of both the solute and the solvent molecules. The inversion symmetry of the solute all-trans-β-carotene is preserved, suggesting the weak perturbative nature of the solute-solvent interaction in the molecular near-field effect. The present study introduces a new concept, "intermolecular vibronic coupling," which may provide an experimentally accessible∕theoretically tractable model for understanding weak solute-solvent interactions in liquid.

  16. Tropospheric ozone differential-absorption lidar using stimulated Raman scattering in carbon dioxide.

    PubMed

    Nakazato, Masahisa; Nagai, Tomohiro; Sakai, Tetsu; Hirose, Yasuo

    2007-04-20

    A UV ozone differential-absorption lidar (DIAL) utilizing a Nd:YAG laser and a single Raman cell filled with carbon dioxide (CO(2)) is designed, developed, and evaluated. The generated wavelengths are 276, 287, and 299 nm, comprising the first to third Stokes lines of the stimulated Raman scattering technique. The correction terms originated from the aerosol extinction, the backscatter, and the absorption by other gases are estimated using a model atmosphere. The experimental results demonstrate that the emitted output energies were 13 mJ/pulse at 276 nm and 287 nm and 5 mJ/pulse at 299 nm, with pump energy of 91 mJ/pulse and a CO(2) pressure of 0.7 MPa. The three Stokes lines account for 44.0% of the available energy. The use of argon or helium as a buffer gas in the Raman cell was also investigated, but this leads to a dramatic decrease in the third Stokes line, which makes this wavelength practically unusable. Our observations confirmed that 30 min of integration were sufficient to observe ozone concentration profiles up to 10 km. Aerosol extinction and backscatter correction are estimated and applied. The aerosol backscatter correction profile using 287 and 299 nm as reference wavelengths is compared with that using 355 nm. The estimated statistical error is less than 5% at 1.5 km and 10% at 2.6 km. Comparisons with the operational carbon-iodine type chemical ozonesondes demonstrate 20% overestimation of the ozone profiles by the DIAL technique.

  17. G-band resonant Raman study of 62 isolated single-wall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Jorio, A.; Souza Filho, A. G.; Dresselhaus, G.; Dresselhaus, M. S.; Swan, A. K.; Ünlü, M. S.; Goldberg, B. B.; Pimenta, M. A.; Hafner, J. H.; Lieber, C. M.; Saito, R.

    2002-04-01

    We report G-band resonance Raman spectra of single-wall carbon nanotubes (SWNTs) at the single-nanotube level. By measuring 62 different isolated SWNTs resonant with the incident laser, and having diameters dt ranging between 0.95 nm and 2.62 nm, we have conclusively determined the dependence of the two most intense G-band features on the nanotube structure. The higher-frequency peak is not diameter dependent (ω+G=1591 cm-1), while the lower-frequency peak is given by ω-G=ω+G-C/d2t, with C being different for metallic and semiconducting SWNTs (CM>CS). The peak frequencies do not depend on nanotube chiral angle. The intensity ratio between the two most intense features is in the range 0.1resonance conditions, i.e., SWNTs for which the incident photons are in resonance with the ES44 interband transition and scattered photons are in resonance with ES33. Since the Eii values depend sensitively on both nanotube diameter and chirality, the (n,m) SWNTs that should exhibit such a special G-band spectra can be predicted by resonance Raman theory. The agreement between theoretical predictions and experimental observations about these special G-band phenomena gives additional support for the (n,m) assignment from resonance Raman spectroscopy.

  18. Detection of electron paramagnetic resonance absorption using frequency modulation.

    PubMed

    Hirata, Hiroshi; Kuyama, Toshifumi; Ono, Mitsuhiro; Shimoyama, Yuhei

    2003-10-01

    A frequency modulation (FM) method was developed to measure electron paramagnetic resonance (EPR) absorption. The first-derivative spectrum of 1,1-diphenyl-2-picrylhydrazyl (DPPH) powder was measured with this FM method. Frequency modulation of up to 1.6 MHz (peak-to-peak) was achieved at a microwave carrier frequency of 1.1 GHz. This corresponds to a magnetic field modulation of 57microT (peak-to-peak) at 40.3 mT. By using a tunable microwave resonator and automatic control systems, we achieved a practical continuous-wave (CW) EPR spectrometer that incorporates the FM method. In the present experiments, the EPR signal intensity was proportional to the magnitude of frequency modulation. The background signal at the modulation frequency (1 kHz) for EPR detection was also proportional to the magnitude of frequency modulation. An automatic matching control (AMC) system reduced the amplitude of noise in microwave detection and improved the baseline stability. Distortion of the spectral lineshape was seen when the spectrometer settings were not appropriate, e.g., with a lack of the open-loop gain in automatic tuning control (ATC). FM is an alternative to field modulation when the side-effect of field modulation is detrimental for EPR detection. The present spectroscopic technique based on the FM scheme is useful for measuring the first derivative with respect to the microwave frequency in investigations of electron-spin-related phenomena.

  19. Surface-enhanced Raman spectroscopy on a surface plasmon resonance biosensor platform for gene diagnostics

    NASA Astrophysics Data System (ADS)

    Yuan, W.; Ho, H. P.; Suen, Y. K.; Kong, S. K.; Lin, Chinlon; Prasad, Paras N.; Li, J.; Ong, Daniel H. C.

    2008-02-01

    We propose to integrate the surface-enhanced Raman spectroscopy (SERS) detection capability with a surface plasmon resonance (SPR) biosensor platform. As a demonstration setup, the experimental scheme is built from a Total Internal Reflection Fluorescence (TIRF) microscope. The sample surface is a gold-coated plasmonic crystal substrate. Two oligonucleotide (ODN) probes that have been labeled with two different Raman active dyes are used to achieve a sandwich assay of target ODNs or polynucleotide. Upon complementary hybridizations between the target and probe ODNs, the target can be identified by detecting the narrow-band spectroscopic fingerprints of the Raman tags. This concept has high potential for achieving multiplexed detection of ODN targets because a very large number of probes can be incorporated to the plasmonic crystal substrate, which may find applications in gene based diseases diagnostics. We also explored the detection of single molecules and achieved some preliminary results.

  20. The impact of the neck material on the sound absorption performance of Helmholtz resonators

    NASA Astrophysics Data System (ADS)

    Yang, Dong; Wang, Xiaolin; Zhu, Min

    2014-12-01

    Helmholtz resonators with sound absorption materials filling the neck may have an improved sound absorption capacity. In this work, parallel perforated ceramics with different perforation diameters were installed into the neck of a Helmholtz resonator to improve its acoustic impedance to simultaneously achieve a better acoustic absorption coefficient and a wider absorption bandwidth. An experimental system was built to investigate the effect of the perforation diameters on the sound absorption performance of the resonator. It is found that nonlinear effects near the resonance frequency affect the resonator's neck mouth impedance and further its sound absorption performance significantly. For frequency range 50-500 Hz, a model of the neck mouth impedance is developed based on a revised Forchheimer relationship. The experimental results are in good agreement with the theoretical model.

  1. Polarization rotation under two-photon Raman resonance for magnetometry

    SciTech Connect

    Pradhan, S.; Behera, R.; Das, A. K.

    2012-04-23

    The polarization rotation and coherent population trapping signal arising due to two photon process using linearly polarized light are found to be significantly enhanced for a Zeeman degenerate system. The zero crossing of the dispersive profile is found to be shifting proportional to the applied magnetic field, albeit the absorptive profile position remains invariant for a slightly imbalanced orthogonal circular polarization component. It provides an alternative method for precise measurement of vector magnetic field without requirement of a bias field. The use of polarization rotation signal for magnetic field measurement offers added advantage due to improved signal to noise ratio.

  2. Shifted excitation resonance Raman difference spectroscopy using a microsystem light source at 488 nm

    NASA Astrophysics Data System (ADS)

    Maiwald, M.; Sowoidnich, K.; Schmidt, H.; Sumpf, B.; Erbert, G.; Kronfeldt, H.-D.

    2010-04-01

    Experimental results in shifted excitation resonance Raman difference spectroscopy (SERRDS) at 488 nm will be presented. A novel compact diode laser system was used as excitation light source. The device is based on a distributed feedback (DFB) diode laser as a pump light source and a nonlinear frequency doubling using a periodically poled lithium niobate (PPLN) waveguide crystal. All elements including micro-optics are fixed on a micro-optical bench with a footprint of 25 mm × 5 mm. An easy temperature management of the DFB laser and the crystal was used for wavelength tuning. The second harmonic generation (SHG) provides an additional suppression of the spontaneous emission. Raman spectra of polystyrene demonstrate that no laser bandpass filter is needed for the Raman experiments. Resonance-Raman spectra of the restricted food colorant Tartrazine (FD&C Yellow 5, E 102) in distilled water excited at 488 nm demonstrate the suitability of this light source for SERRDS. A limit of detection (LOD) of 0.4 μmol.l-1 of E102 enables SERRDS at 488 nm for trace detection in e.g. food safety control as an appropriate contactless spectroscopic technique.

  3. Surface-enhanced resonance Raman spectroscopic characterization of the protein native structure.

    PubMed

    Feng, Manliang; Tachikawa, Hiroyasu

    2008-06-11

    Surface-enhanced resonance Raman scattering (SERRS) spectra of biological species are often different from their resonance Raman (RR) spectra. A home-designed Raman flow system is used to determine the factors that contribute to the difference between the SERRS and RR of met-myoglobin (metMb). The results indicate that both the degree of protein-nanoparticles interaction and the laser irradiation contribute to the structural changes and are responsible for the observed differences between the SERRS and RR spectra of metMb. The prolonged adsorption of the protein molecules on the nanoparticle surface, which is the condition normally used for the conventional SERRS experiments, disturbs the heme pocket structure and facilitates the charge transfer process and the photoinduced transformation of proteins. The disruption of the heme pocket results in the loss of the distal water molecule, and the resulting SERRS spectrum of metMb shows a 5-coordinated high-spin heme. The flow system, when operated at a moderately high flow rate, can basically eliminate the factors that disturb the protein structure while maintaining a high enhancement factor. The SERRS spectrum obtained from a 1 x 10 (-7) M metMb solution using this flow system is basically identical to the RR spectrum of a 5 x 10 (-4) M metMb solution. Therefore, the Raman flow system reported here should be useful for characterizing the protein-nanoparticles interaction and the native structure of proteins using SERRS spectroscopy.

  4. Resonant Raman scattering theory for Kitaev models and their Majorana fermion boundary modes

    NASA Astrophysics Data System (ADS)

    Perreault, Brent; Knolle, Johannes; Perkins, Natalia B.; Burnell, F. J.

    2016-09-01

    We study the inelastic light scattering response in two- (2D) and three-dimensional (3D) Kitaev spin-liquid models with Majorana spinon band structures in the symmetry classes BDI and D leading to protected gapless surface modes. We present a detailed calculation of the resonant Raman/Brillouin scattering vertex relevant to iridate and ruthenate compounds whose low-energy physics is believed to be proximate to these spin-liquid phases. In the symmetry class BDI, we find that while the resonant scattering on thin films can detect the gapless boundary modes of spin liquids, the nonresonant processes do not couple to them. For the symmetry class D, however, we find that the coupling between both types of light-scattering processes and the low-energy surface states is strongly suppressed. Additionally, we describe the effect of weak time-reversal symmetry breaking perturbations on the bulk Raman response of these systems.

  5. Fully reflective deep ultraviolet to near infrared spectrometer and entrance optics for resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Schulz, B.; Bäckström, J.; Budelmann, D.; Maeser, R.; Rübhausen, M.; Klein, M. V.; Schoeffel, E.; Mihill, A.; Yoon, S.

    2005-07-01

    We present the design and performance of a new triple-grating deep ultraviolet to near-infrared spectrometer. The system is fully achromatic due to the use of reflective optics. The minimization of image aberrations by using on- and off- axis parabolic mirrors as well as elliptical mirrors yields a strong stray light rejection with high resolution over a wavelength range between 165 and 1000nm. The Raman signal is collected with a reflective entrance objective with a numerical aperture of 0.5, featuring a Cassegrain-type design. Resonance Raman studies on semiconductors and on correlated compounds, such as LaMnO3, highlight the performance of this instrument, and show diverse resonance effects between 1.96 and 5.4eV.

  6. Continuous cell sorting in a flow based on single cell resonance Raman spectra.

    PubMed

    McIlvenna, David; Huang, Wei E; Davison, Paul; Glidle, Andrew; Cooper, Jon; Yin, Huabing

    2016-04-21

    Single cell Raman spectroscopy measures a spectral fingerprint of the biochemistry of cells, and provides a powerful method for label-free detection of living cells without the involvement of a chemical labelling strategy. However, as the intrinsic Raman signals of cells are inherently weak, there is a significant challenge in discriminating and isolating cells in a flowing stream. Here we report an integrated Raman-microfluidic system for continuous sorting of a stream of cyanobacteria, Synechocystis sp. PCC6803. These carotenoid-containing microorganisms provide an elegant model system enabling us to determine the sorting accuracy using the subtly different resonance Raman spectra of microorganism cultured in a (12)C or (13)C carbon source. Central to the implementation of continuous flow sorting is the use of "pressure dividers" that eliminate fluctuations in flow in the detection region. This has enabled us to stabilise the flow profile sufficiently to allow automated operation with synchronisation of Raman acquisition, real-time classification and sorting at flow rates of ca. <100 μm s(-1), without the need to "trap" the cells. We demonstrate the flexibility of this approach in sorting mixed cell populations with the ability to achieve 96.3% purity of the selected cells at a speed of 0.5 Hz.

  7. Anisotropy of electron-phonon interaction in nanoscale CdSe platelets as seen via off-resonant and resonant Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Cherevkov, S. A.; Fedorov, A. V.; Artemyev, M. V.; Prudnikau, A. V.; Baranov, A. V.

    2013-07-01

    The off-resonant and resonant Raman spectra of optical phonons in colloidal CdSe nanoplatelets (NPLs) with the thickness of 4, 5, and 6 CdSe monolayers are analyzed. These spectra are dominated by SO and LO phonon bands of CdSe whose frequencies are thickness independent in the off-resonant Raman but demonstrate evident thickness dependence similar to that observed for confined optical phonons in CdSe quantum dots in the resonant Raman. The results show that conventional optical phonons propagating along the NPL lateral planes contribute mainly to the off-resonant Raman while confined optical phonons propagating in the perpendicular direction dominate the Raman spectra excited in the resonance with confined exciton transitions of CdSe NPLs. An anisotropic electron-phonon interaction is proposed to be responsible for this effect in the CdSe NPLs. A formation of Cd-S monolayer on the surface of CdSe NPLs treated by thiol-containing ligands is also detected in Raman spectra.

  8. η collective mode as A1 g Raman resonance in cuprate superconductors

    NASA Astrophysics Data System (ADS)

    Montiel, X.; Kloss, T.; Pépin, C.; Benhabib, S.; Gallais, Y.; Sacuto, A.

    2016-01-01

    We discuss the possible existence of a spin singlet excitation with charge ±2 (η mode) originating the A1 g Raman resonance in cuprate superconductors. This η mode relates the d -wave superconducting singlet pairing channel to a d -wave charge channel. We show that the η boson forms a particle-particle bound state below the 2 Δ threshold of the particle-hole continuum where Δ is the maximum d -wave gap. Within a generalized random phase approximation and Bethe-Salpeter approximation study, we find that this mode has energies similar to the resonance observed with inelastic neutron scattering below the superconducting (SC) coherent peak at 2 Δ in various SC cuprate compounds. We show that it is a very good candidate for the resonance observed in Raman scattering below the 2 Δ peak in the A1 g symmetry. Since the η mode sits in the S =0 channel, it may be observable via Raman, x-ray, or electron energy loss spectroscopy probes.

  9. Solitons and frequency combs in silica microring resonators: Interplay of the Raman and higher-order dispersion effects

    NASA Astrophysics Data System (ADS)

    Milián, C.; Gorbach, A. V.; Taki, M.; Yulin, A. V.; Skryabin, D. V.

    2015-09-01

    The influence of Raman scattering and higher order dispersions on solitons and frequency comb generation in silica microring resonators is investigated. The Raman effect introduces a threshold value in the resonator quality factor above which the frequency-locked solitons cannot exist, and instead, a rich dynamics characterized by generation of self-frequency-shifting solitons and dispersive waves is observed. A mechanism for broadening the Cherenkov radiation through Hopf instability of the frequency-locked solitons is also reported.

  10. Heating of the solar corona by the resonant absorption of Alfven waves

    NASA Technical Reports Server (NTRS)

    Davila, Joseph M.

    1986-01-01

    An improved method for calculating the resonance absorption heating rate is discussed and the results are compared with observations in the solar corona. The primary conclusion to be drawn from these calculations is that to the level of the approximation adopted, the observations of the heating rate and nonthermal line broadening in the solar corona are consistent with heating by the resonance absorption mechanism.

  11. 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 CO2 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 CO2, large photoelectrocatalytic effect for the reduction of CO2 was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO2 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.

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

    SciTech Connect

    Mance, J. G.; Felver, J. J.; Dexheimer, S. L.

    2015-02-28

    We detect the change in vibrational frequency associated with the transition from a delocalized to a localized electronic state using femtosecond vibrational wavepacket techniques. The experiments are carried out in the mixed-valence linear chain material [Pt(en){sub 2}][Pt(en){sub 2}Cl{sub 2}]⋅(ClO{sub 4}){sub 4} (en = ethylenediamine, C{sub 2}H{sub 8}N{sub 2}), a quasi-one-dimensional system with strong electron-phonon coupling. Vibrational spectroscopy of the equilibrated self-trapped exciton is carried out using a multiple pulse excitation technique: an initial pump pulse creates a population of delocalized excitons that self-trap and equilibrate, and a time-delayed second pump pulse tuned to the red-shifted absorption band of the self-trapped exciton impulsively excites vibrational wavepacket oscillations at the characteristic vibrational frequencies of the equilibrated self-trapped exciton state by the resonant impulsive stimulated Raman mechanism, acting on the excited state. The measurements yield oscillations at a frequency of 160 cm{sup −1} corresponding to a Raman-active mode of the equilibrated self-trapped exciton with Pt-Cl stretching character. The 160 cm{sup −1} frequency is shifted from the previously observed wavepacket frequency of 185 cm{sup −1} associated with the initially generated exciton and from the 312 cm{sup −1} Raman-active symmetric stretching mode of the ground electronic state. We relate the frequency shifts to the changes in charge distribution and local structure that create the potential that stabilizes the self-trapped state.

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

    SciTech Connect

    Whitehead, C.A.; Cannon, B.D.; Wacker, J.F.

    1994-12-01

    A method for measuring low relative abundances of {sup 85}Kr in one liter or less samples of air has been under development here at Pacific Northwest Laboratory. The goal of the Krypton Isotope Laser Analysis (KILA) method is to measure ratios of 10{sup {minus}10} or less of {sup 85}Kr to more abundant stable krypton. Mass spectrometry and beta counting are the main competing technologies used in rare-gas trace analysis and are limited in application by such factors as sample size, counting times, and selectivity. The use of high-resolution lasers to probe hyperfine levels to determine isotopic abundance has received much attention recently. In this study, we report our progress on identifying and implementing techniques for trace {sup 85}Kr analysis on small gas samples in a static cell as well as limitations on sensitivity and selectivity for the technique. High-resolution pulsed and cw lasers are employed in a laser-induced fluorescence technique that preserves the original sample. This technique, is based on resonant isotopic depletion spectroscopy (RIDS) in which one isotope is optically depleted while preserving the population of a less abundant isotope. The KILA method consists of three steps. In the first step, the 1s{sub 5} metastable level of krypton is populated via radiative cascade following two-photon excitation of the 2p{sub 6} energy level. Next, using RBDS, the stable krypton isotopes are optically depleted to the ground state through the 1s{sub 4} level with the bulk of the {sup 85}Kr population being preserved. Finally, the remaining metastable population is probed to determine {sup 85}Kr concentration. The experimental requirements for each of these steps are outlined below.

  14. 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).

  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. Low-energy neutron flux measurement using a resonance absorption filter surrounding a lithium glass scintillator

    NASA Astrophysics Data System (ADS)

    Ghal-Eh, N.; Koohi-Fayegh, R.; Hamidi, S.

    2007-06-01

    The resonance absorption filter technique has been used to determine the thermal/epithermal neutron flux. The main idea in this technique is to use an element with a high and essentially singular resonance in the neutron absorption cross section as a filter surrounding a miniature-type lithium glass scintillator. The count with and without the filter surrounding the detector gives the number of resonance-energy neutrons. Some preliminary results and a comparison with the MCNP code are shown.

  17. Intervalley scattering by acoustic phonons in two-dimensional MoS2 revealed by double-resonance Raman spectroscopy.

    PubMed

    Carvalho, Bruno R; Wang, Yuanxi; Mignuzzi, Sandro; Roy, Debdulal; Terrones, Mauricio; Fantini, Cristiano; Crespi, Vincent H; Malard, Leandro M; Pimenta, Marcos A

    2017-03-09

    Double-resonance Raman scattering is a sensitive probe to study the electron-phonon scattering pathways in crystals. For semiconducting two-dimensional transition-metal dichalcogenides, the double-resonance Raman process involves different valleys and phonons in the Brillouin zone, and it has not yet been fully understood. Here we present a multiple energy excitation Raman study in conjunction with density functional theory calculations that unveil the double-resonance Raman scattering process in monolayer and bulk MoS2. Results show that the frequency of some Raman features shifts when changing the excitation energy, and first-principle simulations confirm that such bands arise from distinct acoustic phonons, connecting different valley states. The double-resonance Raman process is affected by the indirect-to-direct bandgap transition, and a comparison of results in monolayer and bulk allows the assignment of each Raman feature near the M or K points of the Brillouin zone. Our work highlights the underlying physics of intervalley scattering of electrons by acoustic phonons, which is essential for valley depolarization in MoS2.

  18. Intervalley scattering by acoustic phonons in two-dimensional MoS2 revealed by double-resonance Raman spectroscopy

    PubMed Central

    Carvalho, Bruno R.; Wang, Yuanxi; Mignuzzi, Sandro; Roy, Debdulal; Terrones, Mauricio; Fantini, Cristiano; Crespi, Vincent H.; Malard, Leandro M.; Pimenta, Marcos A.

    2017-01-01

    Double-resonance Raman scattering is a sensitive probe to study the electron-phonon scattering pathways in crystals. For semiconducting two-dimensional transition-metal dichalcogenides, the double-resonance Raman process involves different valleys and phonons in the Brillouin zone, and it has not yet been fully understood. Here we present a multiple energy excitation Raman study in conjunction with density functional theory calculations that unveil the double-resonance Raman scattering process in monolayer and bulk MoS2. Results show that the frequency of some Raman features shifts when changing the excitation energy, and first-principle simulations confirm that such bands arise from distinct acoustic phonons, connecting different valley states. The double-resonance Raman process is affected by the indirect-to-direct bandgap transition, and a comparison of results in monolayer and bulk allows the assignment of each Raman feature near the M or K points of the Brillouin zone. Our work highlights the underlying physics of intervalley scattering of electrons by acoustic phonons, which is essential for valley depolarization in MoS2. PMID:28276472

  19. Intervalley scattering by acoustic phonons in two-dimensional MoS2 revealed by double-resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Carvalho, Bruno R.; Wang, Yuanxi; Mignuzzi, Sandro; Roy, Debdulal; Terrones, Mauricio; Fantini, Cristiano; Crespi, Vincent H.; Malard, Leandro M.; Pimenta, Marcos A.

    2017-03-01

    Double-resonance Raman scattering is a sensitive probe to study the electron-phonon scattering pathways in crystals. For semiconducting two-dimensional transition-metal dichalcogenides, the double-resonance Raman process involves different valleys and phonons in the Brillouin zone, and it has not yet been fully understood. Here we present a multiple energy excitation Raman study in conjunction with density functional theory calculations that unveil the double-resonance Raman scattering process in monolayer and bulk MoS2. Results show that the frequency of some Raman features shifts when changing the excitation energy, and first-principle simulations confirm that such bands arise from distinct acoustic phonons, connecting different valley states. The double-resonance Raman process is affected by the indirect-to-direct bandgap transition, and a comparison of results in monolayer and bulk allows the assignment of each Raman feature near the M or K points of the Brillouin zone. Our work highlights the underlying physics of intervalley scattering of electrons by acoustic phonons, which is essential for valley depolarization in MoS2.

  20. Applicability of surface-enhanced resonance Raman scattering for the direct discrimination of ballpoint pen inks.

    PubMed

    Seifar, R M; Verheul, J M; Ariese, F; Brinkman, U A; Gooijer, C

    2001-08-01

    In situ surface-enhanced resonance Raman spectroscopy (SERRS) with excitation at 685 nm is suitable for the direct discrimination of blue and black ballpoint pen inks on paper. For black inks, shorter excitation wavelengths can also be used. For blue inks, SERRS at 514.5 and 457.9 nm does not provide adequate discriminative power. At these excitation wavelengths, the SERRS signals of the Methyl Violet derivatives present in inks easily dominate the overall spectrum because of resonance enhancement and preferential interaction with silver sol particles. At 685 nm, this problem is not encountered as the Methyl Violet derivatives do not show resonance enhancement, while other components may still exhibit resonance. Thirteen blue and thirteen black ink lines were examined. For the blue and black inks, on the basis of the 685 nm SERR spectra, eight and six groups of spectra, respectively, could be distinguished. This discrimination largely agrees with information from thin layer chromatography (TLC) experiments, although some differences in group compositions are found. The in situ SERR spectra show good repeatability with regard to the Raman frequencies, band shapes and relative intensities of the spectral bands. However, absolute intensities cannot be used for discrimination purposes.

  1. UV resonance Raman investigation of the aqueous solvation dependence of primary amide vibrations.

    PubMed

    Punihaole, David; Jakubek, Ryan S; Dahlburg, Elizabeth M; Hong, Zhenmin; Myshakina, Nataliya S; Geib, Steven; Asher, Sanford A

    2015-03-12

    We investigated the normal mode composition and the aqueous solvation dependence of the primary amide vibrations of propanamide. Infrared, normal Raman, and UV resonance Raman (UVRR) spectroscopy were applied in conjunction with density functional theory (DFT) to assign the vibrations of crystalline propanamide. We examined the aqueous solvation dependence of the primary amide UVRR bands by measuring spectra in different acetonitrile/water mixtures. As previously observed in the UVRR spectra of N-methylacetamide, all of the resonance enhanced primary amide bands, except for the Amide I (AmI), show increased UVRR cross sections as the solvent becomes water-rich. These spectral trends are rationalized by a model wherein the hydrogen bonding and the high dielectric constant of water stabilizes the ground state dipolar (-)O-C═NH2(+) resonance structure over the neutral O═C-NH2 resonance structure. Thus, vibrations with large C-N stretching show increased UVRR cross sections because the C-N displacement between the electronic ground and excited state increases along the C-N bond. In contrast, vibrations dominated by C═O stretching, such as the AmI, show a decreased displacement between the electronic ground and excited state, which result in a decreased UVRR cross section upon aqueous solvation. The UVRR primary amide vibrations can be used as sensitive spectroscopic markers to study the local dielectric constant and hydrogen bonding environments of the primary amide side chains of glutamine (Gln) and asparagine (Asn).

  2. Analysis of structure-function relationships in cytochrome c oxidase and its biomimetic analogs via resonance Raman and surface enhanced resonance Raman spectroscopies.

    PubMed

    Weidinger, Inez M

    2015-01-01

    Cytochrome c oxidase (CcO) catalyzes the four electron reduction of molecular oxygen to water while avoiding the formation of toxic peroxide; a quality that is of high relevance for the development of oxygen-reducing catalysts. Resonance Raman spectroscopy has been used since many years as a technique to identify electron transfer pathways in cytochrome c oxidase and to identify the key intermediates in the catalytic cycle. This information can be compared to artificial systems such as modified heme-copper enzymes, molecular heme-copper catalysts or CcO/electrode complexes in order to shed light into the reaction mechanism of these non-natural systems. Understanding the structural commonalities and differences of CcO with its non-natural analogs is of great value for designing efficient oxygen-reducing catalysts. In this review therefore Raman spectroscopic measurements on artificial heme-copper enzymes and model complexes are summarized and compared to the natural enzyme cytochrome c oxidase. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems.

  3. Surface-Enhanced Resonance Raman Scattering Nanostars for High Precision Cancer Imaging

    PubMed Central

    Harmsen, Stefan; Huang, Ruimin; Wall, Matthew A.; Karabeber, Hazem; Samii, Jason M.; Spaliviero, Massimiliano; White, Julie R.; Monette, Sébastien; O’Connor, Rachael; Pitter, Kenneth L.; Sastra, Stephen A.; Saborowski, Michael; Holland, Eric C.; Singer, Samuel; Olive, Kenneth P.; Lowe, Scott W.; Blasberg, Ronald G.; Kircher, Moritz F.

    2015-01-01

    The inability to visualize the true extent of cancers represents a significant challenge in many areas of oncology. The margins of most cancer types are not well demarcated because the cancer diffusely infiltrates the surrounding tissues. Furthermore, cancers may be multifocal and characterized by the presence of microscopic satellite lesions. Such microscopic foci represent a major reason for persistence of cancer, local recurrences, and metastatic spread and are usually impossible to visualize with currently available imaging technologies. An imaging method to reveal the tumor extent is desired clinically and surgically. Here we show the precise visualization of tumor margins, microscopic tumor invasion, and multifocal loco-regional tumor spread using a new generation of surface-enhanced resonance Raman scattering (SERRS) nanoparticles, which are termed here SERRS-nanostars. The SERRS-nanostars feature a star-shaped gold core, a Raman reporter resonant in the near-infrared spectrum, and a primer-free silication method. In mouse models of pancreatic cancer, breast cancer, prostate cancer, and sarcoma, SERRS-nanostars enabled accurate detection of macroscopic malignant lesions as well as microscopic disease, without the need for a targeting moiety. Moreover, the sensitivity (1.5 femtomolar limit of detection under in vivo Raman imaging conditions) of SERRS-nanostars allowed imaging of premalignant lesions of pancreatic and prostatic neoplasias. High sensitivity and broad applicability, in conjunction with their inert gold-silica composition, render SERRS-nanostars a promising imaging agent for more precise cancer imaging and resection. PMID:25609167

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

    NASA Astrophysics Data System (ADS)

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

    2003-07-01

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

  5. Cavity enhanced ultra-thin aluminum plasmonic resonator for surface enhanced infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Wei, Wei; Jiang, Xiao; Nong, Jinpeng; Chen, Na; Lan, Guilian; Tang, Linlong

    2016-11-01

    Owing to the advantages of natural abundance, low cost, and amenability to manufacturing processes, aluminum has recently been recognized as a highly promising plasmonic material that attracts extensive research interest. Here, we propose a cavity-enhanced ultra-thin plasmonic resonator for surface enhanced infrared absorption spectroscopy. The considered resonator consists of a patterned ultra-thin aluminum grating strips, a dielectric spacer layer and a reflective layer. In such structure, the resonance absorption is enhanced by the cavity formed between the patterned aluminum strips and the reflective layer. It is demonstrated that the spectral features of the resonator can be tuned by adjusting the structural parameters. Furthermore, in order to achieve a deep and broad spectral line shape, the spacer layer thickness should be properly designed to realize the simultaneous resonances for the electric and the magnetic excitations. The enhanced infrared absorption characteristics can be used for infrared sensing of the environment. When the resonator is covered with a molecular layer, the resonator can be used as a surface enhanced infrared absorption substrate to enhance the absorption signal of the molecules. A high enhanced factor of 1.15×105 can be achieved when the resonance wavelength of resonator is adjusted to match the desired vibrational mode of the molecules. Such a cavity-enhanced plasmonic resonator, which is easy for practical fabrication, is expected to have potential applications for infrared sensing with high-performance.

  6. Interaction of proflavine with DNA studied by colloid surface enhanced resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Koglin, E.; Séquaris, J.-M.

    1986-03-01

    The interaction of the mutagenic highly fluourescing proflavine (3,6-diaminoacridine: PF) dye with calf thymus DNA has been studied by Surface Enhanced Resonance Raman Scattering (SERRS). Since the Ag-colloids almost completely quenche the strong fluorescence it is possible to obtain excellent vibrational spectra in a wide frequency range providing valuable information about the intercalation. The intercalation does not affect the vibrational frequencies of the proflavine dye. On the other hand, intensity changes are observed in some of the ring- and NH 2-modes of proflavine upon intercalation. This Raman hypochromism is characteristic for ring stacking interactions and in the SERRS spetroscopy for an additional effects of the dye orientation to the surface.

  7. Quasiperfect absorption by subwavelength acoustic panels in transmission using accumulation of resonances due to slow sound

    NASA Astrophysics Data System (ADS)

    Jiménez, Noé; Romero-García, Vicent; Pagneux, Vincent; Groby, Jean-Philippe

    2017-01-01

    We theoretically and experimentally report subwavelength resonant panels for low-frequency quasiperfect sound absorption including transmission by using the accumulation of cavity resonances due to the slow sound phenomenon. The subwavelength panel is composed of periodic horizontal slits loaded by identical Helmholtz resonators (HRs). Due to the presence of the HRs, the propagation inside each slit is strongly dispersive, with near-zero phase velocity close to the resonance of the HRs. In this slow sound regime, the frequencies of the cavity modes inside the slit are down-shifted and the slit behaves as a subwavelength resonator. Moreover, due to strong dispersion, the cavity resonances accumulate at the limit of the band gap below the resonance frequency of the HRs. Near this accumulation frequency, simultaneously symmetric and antisymmetric quasicritical coupling can be achieved. In this way, using only monopolar resonators quasiperfect absorption can be obtained in a material including transmission.

  8. Resonant Raman Scattering from Bound Magnetorotons in the Fractional Quantum Hall Regime

    NASA Astrophysics Data System (ADS)

    He, Song

    1996-03-01

    We investigate excitation spectra of a fractional quantum Hall system at ν=1/3 using both theoretical and experimental techniques. Using finite-size numerical diagonalizations, we have studied systematically the excitation spectra, the nature of the low-lying excited states, and the density response function of a ν=1/3 system. Our numerical results indicate that two rotons at the roton minimum can form a weakly bound composite object, giving rise to excited states below the collective mode at long wavelengths. We argue that only these two roton composite objects contribute to the resonant Raman scattering at low momentum transfers. Using the experimental technique of resonant Raman scattering, we have identified the contributions to the Raman intensity from the internal excitations of the fractional quantum Hall system by studying their dependence on the incoming light energy, the filling factor, and the temperature. As a function of the energy shift, the Raman intensity shows a sharp peak at an energy shift of about twice of the energy gap at the roton minimum. We propose that this sharp peak is related to a two roton bound state. The sharp peak is followed by a broader peak, which we think is related to the two-roton continuum. When a grating pattern is put on the sample so that small but finite momentum transfer can be achieved, we observed another peak at about twice of the energy gap Δ_q=∞. We suspect this peak is related to the collective mode at long wavelength. Finally, we propose an excitation spectra consistent with our numerical and experimental results. * This work is a collaboration with P. M. Platzman, A. Pinczuk, B. S. Dennis, L. L. Sohn, L. N. Pfeiffer, and K. W. West.

  9. Evidence for proximal control of ligand specificity in hemeproteins: Absorption and Raman studies of cryogenically trapped photoproducts of ligand bound myoglobins

    NASA Astrophysics Data System (ADS)

    Ahmed, A. M.; Campbell, B. F.; Caruso, D.; Chance, M. R.; Chavez, M. D.; Courtney, S. H.; Friedman, J. M.; Iben, I. E. T.; Ondrias, M. R.; Yang, M.

    1991-12-01

    The absorption and resonance Raman spectra of cryogenically trapped photoproducts of oxy and carboxy derivatives of myoglobin (Mb) are compared and analyzed in an attempt to understand the structural basis for ligand specificity in hemeproteins. Pulsed and cw excitations over a wide temperature range are used in order to differentiate between kinetic hole burning (KHB), optical pumping of structural relaxation, and spontaneous relaxation effects. Using these techniques, we are able to correlate changes in the absorption spectrum (band III at ≈ 760 nm) with low-frequency Raman bands. Based on these correlations we are able to determine which proximal heme pocket parameters are participating in KHB and optical pumping phenomena. Differences in the spectra of the ligand specific photoproducts have revealed differences in the populations of conformational substates (CS) that participate in the geminate recombination (process I) at cryogenic temperatures. A model is presented that relates the ligand specific spectral differences to structural and functional differences in the bound protein. What emerges is evidence that Mb and hemoglobin (Hb) can differentiate between O 2 and CO based on proximal control of the bond forming step between the ligand and the iron.

  10. Resonance Raman and theoretical investigation of the photodissociation dynamics of benzamide in S3 state.

    PubMed

    Pei, Ke-Mei; Ma, Yufang; Zheng, Xuming

    2008-06-14

    Resonance Raman spectra were obtained for benzamide in methanol and acetonitrile solutions with excitation wavelengths in resonance with the S(3) state. These spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with the motions mainly along the benzene ring C[Double Bond]C stretch nu(9), the Ph-CO-NH(2) and ring benzene stretch nu(14), the CCH in plane bend nu(17), the Ph-CO-NH(2) stretch and NH(2) rock nu(19), the ring trigonal bend nu(23), and the ring deformation and Ph-CO-NH(2) stretch nu(29). A preliminary resonance Raman intensity analysis was done, and the results were compared to those previously reported for acetophenone to examine the substituent effect. Solvent effect on the short-time photodissociation dynamics of benzamide was also examined. A conical intersection point S(2)S(3) between S(3) and S(2) potential energy surfaces of benzamide was determined by using a complete active space self-consistent field theory computations. The structural differences and similarities between S(3)S(2) point and S(0) were examined, and the results were used to correlate to the Franck-Condon photodissociation dynamics of benzamide in S(3) state.

  11. Resonance Effects in the Ultraviolet Raman Spectroscopy of Collagen in Mineralized Tissues

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

    Ultraviolet resonance Raman spectroscopy (UVRRS) was used to investigate type I collagen in solid tissues including tendon, dentin, and bone. With 244 nm excitation, spectral features from both the amide backbone (amide I, II, and III) and resonance-enhanced side-chain vibrations (Y8a, tyrosine) were observed. This contrasts with reported Raman spectra of proteins in solution excited with similar UV wavelengths, where side chain vibrations, but not strong amide features, are observed. The height of the dominant amide I feature in teeth and bone can be reversibly increased/decreased in dentin by dehydration/rehydration cycles. Also, the amide I peak is relatively stronger in both human bone and dentin from older donors. The strong intensity of the amide I UVRRS feature in these mineralized tissues is attributed to an increase in the width of the π-> π^* amide resonance in collagen compared to the solution phase. These findings suggest that UVRRS can be used as a specific probe of the collagen environment in bone and dentin.

  12. 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.

  13. Amantadine DNA interaction as studied by classical and resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Staničová, J.; Fabriciová, G.; Chinsky, L.; Šutiak, V.; Miškovský, P.

    1999-03-01

    The interaction of the antiviral agent amantadine with calf thymus DNA was studied by classical and UV-resonance Raman spectroscopy. It was found that: (i) the drug interacts with purine bases adenine and guanine via hydrogen bonds formation between N7 positions of purines and amino group of amantadine and (ii) the interaction leads to partial DNA structure change, which is demonstrated by a deformation of the hydrogen bonds of the A-T base pairs and by a partial deformation of the sugar-phosphate backbone of DNA, which does not lead to the DNA conformation transition.

  14. Measurements of vitamin B12 in human blood serum using resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Tsiminis, G.; Schartner, E. P.; Brooks, J. L.; Hutchinson, M. R.

    2016-12-01

    Vitamin B12 (cobalamin and its derivatives) deficiency has been identified as a potential modifiable risk factor for dementia and Alzheimer's disease. Chronic deficiency of vitamin B12 has been significantly associated with an increased risk of cognitive decline. An effective and efficient method for measuring vitamin B12 concentration in human blood would enable ongoing tracking and assessment of this potential modifiable risk factor. In this work we present an optical sensor based on resonance Raman spectroscopy for rapid measurements of vitamin B12 in human blood serum. The measurement takes less than a minute and requires minimum preparation (centrifuging) of the collected blood samples.

  15. Resonant raman scattering in complexes of nc-Si/SiO2 quantum dots and oligonucleotides

    NASA Astrophysics Data System (ADS)

    Bairamov, F. B.; Poloskin, E. D.; Kornev, A. A.; Chernev, A. L.; Toporov, V. V.; Dubina, M. V.; Röder, C.; Sprung, C.; Lipsanen, H.; Bairamov, B. Kh.

    2014-11-01

    We report on the functionalization of nanocrystalline nc-Si/SiO2 semiconductor quantum dots (QDs) by short d(20G, 20T) oligonucleotides. The obtained complexes have been studied by Raman spectroscopy techniques with high spectral and spatial resolution. A new phenomenon of multiband resonant light scattering on single oligonucleotide molecules has been discovered, and peculiarities of this effect related to the nonradiative transfer of photoexcitation from nc-Si/SiO2 quantum dots to d(20G, 20T) oligonucleotide molecules have been revealed.

  16. Resonant femtosecond stimulated Raman spectroscopy with an intense actinic pump pulse: Application to conical intersections

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    We theoretically investigate the feasibility of characterizing conical intersections with time-resolved resonant femtosecond stimulated Raman spectroscopy (FSRS) using an intense actinic pump pulse. We perform nonperturbative numerical simulations of FSRS signals for a three-electronic-state two-vibrational-mode model, which is inspired by the S 2 ( π π * )- S 1 ( n π * ) conical intersection in pyrazine. Our results show that moderately strong actinic pulses increase the intensity of vibrational fingerprint lines in FSRS transients. They facilitate the extraction of useful spectroscopic information by enhancing peaks revealing the coupling and tuning modes of the conical intersection.

  17. Surface-enhanced resonance Raman scattering in optical tweezers using co-axial second harmonic generation.

    PubMed

    Jordan, Pamela; Cooper, Jon; McNay, Graeme; Docherty, Frances; Graham, Duncan; Smith, W; Sinclair, Gavin; Padgett, Miles

    2005-05-30

    Silica particles were partially coated with silver, and a suitable chromophore, such that they could be simultaneously trapped within an optical tweezers system, and emit a surface-enhanced resonance Raman scattering (SERRS) response. A standard 1064 nm TEM00 mode laser was used to trap the bead whilst a frequency doubling crystal inserted into the beam gave several microwatts of 532 nm co-linear light to excite the SERRS emission. The con fi guration has clear applications in providing apparatus that can simultaneously manipulate a particle whilst obtaining surface sensitive sensory information.

  18. Resonant femtosecond stimulated Raman spectroscopy with an intense actinic pump pulse: Application to conical intersections.

    PubMed

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

    2017-02-28

    We theoretically investigate the feasibility of characterizing conical intersections with time-resolved resonant femtosecond stimulated Raman spectroscopy (FSRS) using an intense actinic pump pulse. We perform nonperturbative numerical simulations of FSRS signals for a three-electronic-state two-vibrational-mode model, which is inspired by the S2(ππ(*))-S1(nπ(*)) conical intersection in pyrazine. Our results show that moderately strong actinic pulses increase the intensity of vibrational fingerprint lines in FSRS transients. They facilitate the extraction of useful spectroscopic information by enhancing peaks revealing the coupling and tuning modes of the conical intersection.

  19. 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.

  20. In vivo resonant Raman measurement of macular carotenoid pigments in the young and the aging human retina

    NASA Astrophysics Data System (ADS)

    Gellermann, Werner; Ermakov, Igor V.; Ermakova, Maia R.; McClane, Robert W.; Zhao, Da-You; Bernstein, Paul S.

    2002-06-01

    We have used resonant Raman scattering spectroscopy as a novel, noninvasive, in vivo optical technique to measure the concentration of the macular carotenoid pigments lutein and zeaxanthin in the living human retina of young and elderly adults. Using a backscattering geometry and resonant molecular excitation in the visible wavelength range, we measure the Raman signals originating from the single- and double-bond stretch vibrations of the π-conjugated molecule's carbon backbone. The Raman signals scale linearly with carotenoid content, and the required laser excitation is well below safety limits for macular exposure. Furthermore, the signals decline significantly with increasing age in normal eyes. The Raman technique is objective and quantitative and may lead to a new method for rapid screening of carotenoid pigment levels in large populations at risk for vision loss from age-related macular degeneration, the leading cause of blindness in the elderly in the United States.

  1. Localized surface plasmon resonance and surface enhanced Raman scattering responses of Au@Ag core-shell nanorods with different thickness of Ag shell.

    PubMed

    Ma, Yanan; Zhou, Jun; Zou, Weibo; Jia, Zhenhong; Petti, Lucia; Mormile, Pasquale

    2014-06-01

    The properties of the localized surface plasmon resonance (LSPR) and the surface enhanced Raman scattering (SERS) of the core-shell bimetallic nanostructures, that is the monodisperse Au@Ag core-shell nanorods with different thickness of Ag shell, are theoretically and experimental researched. The UV-vis-NIR absorption spectra of the Au@Ag core-shell nanorods are measured and displayed their blue-shifts of the longitudinal plasmon resonance peaks with increasing of Ag concentrations in the colloidal solution. And the absorption spectra of the Au@Ag core-shell nanorods are simulated by the Finite Element Method (FEM), which are in agreement with the experimental measurements and reveal their LSPR mechanism as the varying structures. In addition, Rhodamine 6G, as a Raman reporter molecule, is used to investigate SERS of gold nanorods and Au@Ag core-shell nanorods. It is found that Au@Ag core-shell nanorods have better SERS responses, comparing with those of Au nanorods, and their SERS intensities are increased with the increases of the Ag shell thickness, which demonstrate that the chemisorptive bond effect and the morphology of the nanoparticle play key roles to the SERS signals. It is significant to design the biosensor based on the properties of Au@Ag core-shell nanorods.

  2. Visibility Estimation for Neutron Resonance Absorption Radiography using a Pulsed Neutron Source

    NASA Astrophysics Data System (ADS)

    Kai, Tetsuya; Maekawa, Fujio; Oshita, Hidetoshi; Sato, Hirotaka; Shinohara, Takenao; Ooi, Motoki; Harada, Masahide; Uno, Shoji; Otomo, Toshiya; Kamiyama, Takashi; Kiyanagi, Yoshiaki

    Neutron resonance absorption radiography is a technique to enhance neutron transmission images of specific nucleus at neutron resonance energies. Demonstration measurements by using a lithium-glass pixel type scintillator and a gas electron multiplication (GEM) neutron detector were carried out at NOBORU beam line in MLF/J-PARC for sodium, manganese, cobalt, copper, zinc, molybdenum, cadmium, indium, tantalum and gold. To discuss advantages of the resonance absorption radiography the mass attenuation coefficient at resonance energy of each element was compared to that at 25 meV. In addition a visibility index derived by a resonance peak cross section and a relative width (full width at half maximum divided by its resonance energy) was proposed to summarize visibility of the neutron resonance absorption radiography for natural elements. The values of visibility index and the resonance energy indicated that large advantages of the resonance absorption radiography were obtainable for the following elements: sodium (Na), manganese (Mn), cobalt (Co), rhodium (Rh), silver (Ag), cadmium (Cd), indium (In), xenon (Xe), cesium (Cs), samarium (Sm), europium (Eu), dysprosium (Dy), erbium (Er), thulium (Tm), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), iridium (Ir) and gold (Au).

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  4. Visualizing resonances in the complex plane with vibrational phase contrast coherent anti-Stokes Raman scattering.

    PubMed

    Jurna, Martin; Garbacik, Erik T; Korterik, Jeroen P; Herek, Jennifer L; Otto, Cees; Offerhaus, Herman L

    2010-09-15

    In coherent anti-Stokes Raman scattering (CARS), the emitted signal carries both amplitude and phase information of the molecules in the focal volume. Most CARS experiments ignore the phase component, but its detection allows for two advantages over intensity-only CARS. First, the pure resonant response can be determined, and the nonresonant background rejected, by extracting the imaginary component of the complex response, enhancing the sensitivity of CARS measurements. Second, selectivity is increased via determination of the phase and amplitude, allowing separation of individual molecular components of a sample even when their vibrational bands overlap. Here, using vibrational phase contrast CARS (VPC-CARS), we demonstrate enhanced sensitivity in quantitative measurements of ethanol/methanol mixtures and increased selectivity in a heterogeneous mixture of plastics and water. This powerful technique opens a wide range of possibilities for studies of complicated systems where overlapping resonances limit standard methodologies.

  5. Enhancing the absorption properties of acoustic porous plates by periodically embedding Helmholtz resonators.

    PubMed

    Groby, J-P; Lagarrigue, C; Brouard, B; Dazel, O; Tournat, V; Nennig, B

    2015-01-01

    This paper studies the acoustical properties of hard-backed porous layers with periodically embedded air filled Helmholtz resonators. It is demonstrated that some enhancements in the acoustic absorption coefficient can be achieved in the viscous and inertial regimes at wavelengths much larger than the layer thickness. This enhancement is attributed to the excitation of two specific modes: Helmholtz resonance in the viscous regime and a trapped mode in the inertial regime. The enhancement in the absorption that is attributed to the Helmholtz resonance can be further improved when a small amount of porous material is removed from the resonator necks. In this way the frequency range in which these porous materials exhibit high values of the absorption coefficient can be extended by using Helmholtz resonators with a range of carefully tuned neck lengths.

  6. Experimental demonstration of coherent perfect absorption in a silicon photonic racetrack resonator.

    PubMed

    Rothenberg, Jacob M; Chen, Christine P; Ackert, Jason J; Dadap, Jerry I; Knights, Andrew P; Bergman, Keren; Osgood, Richard M; Grote, Richard R

    2016-06-01

    We present the first experimental demonstration of coherent perfect absorption (CPA) in an integrated device using a silicon racetrack resonator at telecommunication wavelengths. Absorption in the racetrack is achieved by Si+-ion-implantation, allowing for phase controllable amplitude modulation at the resonant wavelength. The device is measured to have an extinction of 24.5 dB and a quality-factor exceeding 3000. Our results will enable integrated CPA devices for data modulation and detection.

  7. Mechanism enabling the observation of the formally optically-forbidden 2Ag- and 1Bu- states in resonance-Raman excitation profiles of spheroidene in KBr disc

    NASA Astrophysics Data System (ADS)

    Nagae, Hiroyoshi; Koyama, Yasushi

    2010-07-01

    An expression for the Albrecht A-term resonance-Raman excitation profiles (RREP) of a pigment dispersed in a KBr disc, in such a way that the pigment molecules aggregate in a microcrystal and the microcrystals are dispersed in the KBr disc, is formulated by taking into account the self-absorption of incident and scattered light and the distribution of microcrystals properly. Based on the resultant formula, simulations for the RREPs of spheroidene dispersed in KBr disc were carried out in the spectral region from 12,000 to 24,000 cm -1. Fairly good agreement between the simulations and the observed RREPs was obtained for different concentrations of spheroidene. Mechanisms have been investigated which enable the observation of the formally optically-forbidden (very weakly allowed) 2Ag- and 1Bu- states of spheroidne in RREPs free from the contribution of the optically-allowed 1Bu+ state, and a two-step self-absorption mechanism is proposed.

  8. 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).

  9. Resonance Absorption of Laser Light by Warm and Cold Plasmas.

    DTIC Science & Technology

    1981-03-01

    34 Ponderomotive Force................38 Hot Electron Energy ................40 Validity bf Assumptions..............41 V. Conclusions...Indicated by Arrows) for the Warm and Cold Plasma Models ..... ................ 31 7 Cold Plasma: Fraction of Laser Energy Resonantly Absorbed as a...Function of Incident Angle .. ............ 35 8 Warm Plasma: Fraction of Laser Energy Resonantly Absorbed as a Function of Incident Angle (T = 637 ev and

  10. Error analysis of Raman differential absorption lidar ozone measurements in ice clouds.

    PubMed

    Reichardt, J

    2000-11-20

    A formalism for the error treatment of lidar ozone measurements with the Raman differential absorption lidar technique is presented. In the presence of clouds wavelength-dependent multiple scattering and cloud-particle extinction are the main sources of systematic errors in ozone measurements and necessitate a correction of the measured ozone profiles. Model calculations are performed to describe the influence of cirrus and polar stratospheric clouds on the ozone. It is found that it is sufficient to account for cloud-particle scattering and Rayleigh scattering in and above the cloud; boundary-layer aerosols and the atmospheric column below the cloud can be neglected for the ozone correction. Furthermore, if the extinction coefficient of the cloud is ?0.1 km(-1), the effect in the cloud is proportional to the effective particle extinction and to a particle correction function determined in the limit of negligible molecular scattering. The particle correction function depends on the scattering behavior of the cloud particles, the cloud geometric structure, and the lidar system parameters. Because of the differential extinction of light that has undergone one or more small-angle scattering processes within the cloud, the cloud effect on ozone extends to altitudes above the cloud. The various influencing parameters imply that the particle-related ozone correction has to be calculated for each individual measurement. Examples of ozone measurements in cirrus clouds are discussed.

  11. Lipid-cell interactions in human monocytes investigated by doubly-resonant coherent anti-Stokes Raman scattering microscopy

    PubMed Central

    Weeks, Tyler; Schie, Iwan; den Hartigh, Laura J.; Rutledge, John C.; Huser, Thomas

    2011-01-01

    We demonstrate that doubly-resonant coherent anti-Stokes Raman scattering can provide enhanced and highly specific contrast for molecules containing unique Raman-active small molecular groups. This combination provides contrast for molecules that can otherwise be difficult to discriminate by Raman spectroscopy. Here, human monocytes were incubated with either deuterated oleic acid or 17-octadecynoic acid (a fatty acid with an end terminal acetylene group). The carbon-deuterium stretching vibration of the deuterated fatty acid, as well as the unique alkyne stretching vibration of the alkyne-containing fatty acid, were used to provide contrast for these exogenous free fatty acids. The combination of these unique modes with the common aliphatic carbon-hydrogen stretching vibration inherent to all fatty acid allowed for doubly-resonant detection of these unique molecules and enabled us to detect the presence of these lipids in areas within a cell where each molecular resonance by itself did not generate sufficient signal. PMID:21361680

  12. Ultranarrow resonance peaks in the transmission and reflection spectra of a photonic crystal cavity with Raman gain

    SciTech Connect

    Arkhipkin, V. G.; Myslivets, S. A.

    2009-12-15

    The Raman gain of a probe light in a three-state LAMBDA scheme placed into a defect of a one-dimensional photonic crystal is studied theoretically. We show that there exists a pump intensity range, where the transmission and reflection spectra of the probe field exhibit simultaneously occurring narrow peaks (resonances) whose position is determined by the Raman resonance. Transmission and reflection coefficients can be larger than unity at pump intensities on the order of tens of muW/cm{sup 2}. When the pump intensity is outside this region, the peak in the transmission spectrum turns into a narrow dip. The nature of narrow resonances is attributed to a drastic dispersion of the nonlinear refractive index in the vicinity of the Raman transition, which leads to a significant reduction in the group velocity of the probe wave.

  13. Investigating the phase-dependent photochemical reaction dynamics of chlorine dioxide using resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Hayes, Sophia C.; Wallace, Paul M.; Bolinger, Josh C.; Reid, Philip J.

    Recent progress in understanding the phase-dependent reactivity demonstrated by halooxides is outlined. Specifically, resonance Raman intensity analysis (RRIA) and time-resolved resonance Raman (TRRR) studies of chlorine dioxide (OClO) photochemistry in solution are presented. Using RRIA, it has been determined that the excited-state structural evolution that occurs along the asymmetric-stretch coordinate in the gas phase is restricted in solution. The absence of evolution along this coordinate results in the preservation of groundstate symmetry in the excited state. The role of symmetry in defining the reaction coordinate and the solvent-solute interactions responsible for modification of the excited-state potential energy surface are discussed. TRRR studies are presented which demonstrate that geminate recombination of the primary photoproducts resulting in the reformation of ground-state OClO is a central feature of OClO photochemistry in solution. These studies also demonstrate that a fraction of photoexcited OClO undergoes photoisomerization to form ClOO, with the ground-state thermal decomposition of this species resulting in Cl production on the subnanosecond timescale. Finally, time-resolved anti-Stokes experiments are presented which demonstrate that the OClO vibrational-relaxation dynamics are solvent dependent. The current picture of OClO photochemistry derived from these studies is discussed, and future directions for study are outlined.

  14. Resonance Raman spectrum of the solvated electron in methanol: simulation within a cluster model.

    PubMed

    Neumann, Stefanie; Eisfeld, Wolfgang; Sobolewski, Andrzej L; Domcke, Wolfgang

    2006-05-04

    The microsolvation of the CH(3)OH(2) hypervalent radical in methanol clusters has been investigated by density functional theory. It is shown that the CH(3)OH(2) radical spontaneously decomposes within methanol clusters into protonated methanol and a localized solvated electron cloud. The geometric and electronic structures of these clusters as well as their vibrational frequencies have been characterized. Resonance Raman intensities, associated with the s --> p transition of the unpaired electron, have been estimated for CH(3)OH(2)M(n) (M = CH(3)OH, n = 1-3) clusters. It is shown that with increasing cluster size the simulated spectra converge toward the resonance Raman spectrum of the solvated electron in methanol measured recently by Tauber and Mathies (J. Am. Chem. Soc. 2004, 126, 3414). The results suggest that CH(3)OH(2)M(n) clusters are useful finite-size model systems for the computational investigation of the spectroscopic properties of the solvated electron in liquid methanol.

  15. Resonant behaviour of MHD waves on magnetic flux tubes. I - Connection formulae at the resonant surfaces. II - Absorption of sound waves by sunspots

    NASA Technical Reports Server (NTRS)

    Sakurai, Takashi; Goossens, Marcel; Hollweg, Joseph V.

    1991-01-01

    The present method of addressing the resonance problems that emerge in such MHD phenomena as the resonant absorption of waves at the Alfven resonance point avoids solving the fourth-order differential equation of dissipative MHD by recourse to connection formulae across the dissipation layer. In the second part of this investigation, the absorption of solar 5-min oscillations by sunspots is interpreted as the resonant absorption of sounds by a magnetic cylinder. The absorption coefficient is interpreted (1) analytically, under certain simplifying assumptions, and numerically, under more general conditions. The observed absorption coefficient magnitude is explained over suitable parameter ranges.

  16. Role of ribose in the initial excited state structural dynamics of thymidine in water solution: a resonance Raman and density functional theory investigation.

    PubMed

    Zhu, Xin-Ming; Wang, Hui-gang; Zheng, Xuming; Phillips, David Lee

    2008-12-11

    Resonance Raman spectra were obtained for thymidine and thymine with excitation wavelengths in resonance with the approximately 260 nm band absorption spectrum. The spectra indicate that the Franck-Condon (FC) region photodissociation dynamics of thymidine have multidimensional character with motion predominantly along the nominal C5=C6 stretch + C6-H bend nu17 (delta = 0.75, lambda = 468 cm(-1)), the nominal thymine ring stretch + C6-H bend + N1-C1, stretch nu29 (delta = 0.73, lambda = 363 cm(-1)), the nominal thymine ring stretch + C5-CH3/ N1-C1, stretch nu37 (delta = 0.69, lambda = 292 cm(-1)), and accompanied by the moderate and minor changes in the nu40, nu20 and nu23, nu55, nu60, nu61, nu63 modes. A preliminary resonance Raman intensity analysis was done, and these results for thymidine and thymine were compared to each other. The roles of ribose in the FC structure dynamics of thymidine were explored and the results were used to correlate to its lifetime constants tau1 and tau2 for two nonradiative decay channels. Spi/Sn conical intersection versus a distorted structure of Spi,min in the FC region was briefly discussed.

  17. Resonances in reflection, transmission and absorption of 1-D triangular-relief metallic gratings

    NASA Astrophysics Data System (ADS)

    Sassi, Imed; Dhibi, Abdelhak; Oumezzine, Mohamed

    2017-02-01

    We present numerical simulations in order to investigate the resonances in reflection, transmission, and absorption of surface plasmons for triangular gratings. The results reveal a number of resonances depending of grating geometrical parameters, surface materials, and characteristics of incident light. For metals Cu, Ag, Au, Ni, Pd, and Pt, the intensive weakly flat grating-resonance at TM-polarized incident light under normal direction is at wavelength λ = 0.83 ± 0.01 μ{m}, and a weaker grating resonance is at wavelength around 0.46 &mu{m}. For strongly flat grating weak resonances appear for some metals, and disappear for others.

  18. Three-photon-absorption resonance for all-optical atomic clocks

    SciTech Connect

    Zibrov, Sergei; Novikova, Irina; Phillips, David F.; Taichenachev, Aleksei V.; Yudin, Valeriy I.; Walsworth, Ronald L.; Zibrov, Alexander S.

    2005-07-15

    We report an experimental study of an all-optical three-photon-absorption resonance (known as an 'N resonance') and discuss its potential application as an alternative to atomic clocks based on coherent population trapping. We present measurements of the N-resonance contrast, width and light shift for the D{sub 1} line of {sup 87}Rb with varying buffer gases, and find good agreement with an analytical model of this resonance. The results suggest that N resonances are promising for atomic clock applications.

  19. Estimation of neutron energy for first resonance from absorption cross section for thermal neutrons

    NASA Technical Reports Server (NTRS)

    Bogart, Donald

    1951-01-01

    Examination of published data for some 52 isotopes indicates that the neutron energy for which the first resonance occurs is related to the magnitude of the thermal absorption cross section. The empirical relation obtained is in qualitative agreement with the results of a simplified version of the resonance theory of the nucleus of Breit-Wigner.

  20. Infrared Pulse-laser Long-path Absorption Measurement of Carbon Dioxide Using a Raman-shifted Dye Laser

    NASA Technical Reports Server (NTRS)

    Minato, Atsushi; Sugimoto, Nobuo; Sasano, Yasuhiro

    1992-01-01

    A pulsed laser source is effective in infrared laser long-path absorption measurements when the optical path length is very long or the reflection from a hard target is utilized, because higher signal-to-noise ratio is obtained in the detection of weak return signals. We have investigated the performance of a pulse-laser long-path absorption system using a hydrogen Raman shifter and a tunable dye laser pumped by a Nd:YAG laser, which generates second Stokes radiation in the 2-micron region.

  1. Resonance Raman spectroscopy and density functional theory study of the photodissociation dynamics of acetophenone in cyclohexane solution

    NASA Astrophysics Data System (ADS)

    Ma, Yufang; Pei, Kemei; Zheng, Xuming; Li, Haiyang

    2007-11-01

    Resonance Raman spectra were acquired for acetophenone using 228.7, 239.5, and 245.9 nm excitations in cyclohexane solution. The spectra display overtones of the benzene ring C-C stretch (1578 cm -1) and the carbonyl C dbnd O stretch (1671 cm -1) modes and their combination bands with other five vibrational modes. A preliminary resonance Raman intensity analysis was done and these results for acetophenone were compared to the those previously reported for 2-hydroxyacetophenone. The differences between the vibrational reorganizational energies for acetophenone relative to those of 2-hydroxyacetophenone were briefly discussed.

  2. A simple mechanical model for resonance absorption: The Alfvén resonance

    NASA Astrophysics Data System (ADS)

    Hollweg, Joseph V.

    1997-10-01

    We consider resonance absorption of magnetohydrodynamic waves, and the Alfvén resonance layer in particular. We show that the dissipative layer can be modeled as a simple mechanical system consisting of a few harmonic oscillators which are coupled by friction. The mechanical model reproduces known results for the externally driven system in steady state, such as the structure of the dissipative layer, the ``waves'' of heating which propagate across the layer, and the fact that the total heating is independent of time. The total work done on the oscillators by the driver is always positive; the external driver sees the total system as a single damped oscillator driven exactly at resonance. Nonetheless, some of the oscillators return energy back to the driver. The total kinetic energy of all the oscillators and the total potential energy are nearly independent of time, because the integrals, across the dissipative layer, of the square of the velocity and the square of the displacement, are truly constants in time. Waves of kinetic and potential energy propagate across the system in the same sense as the waves of heating. We also investigate an initial value problem in which the driver is turned on at t=0. There is no single number representing the time required for the dissipative layer to reach a steady state. The waves of heating which are found in the steady state are also present in the buildup phase. However, if the driver is turned off after the system has reached a steady state, then the waves of heating are less obvious. We consider the effects of a nonlinear frictional coupling between the oscillators, designed to mimic the effects of Kelvin-Helmholtz instabilities. The nonlinear coupling has surprisingly little effect on the system. The total steady state heating rate is the same as in the linear system; even with nonlinear dissipation, the dissipative layer adjusts itself to absorb a predetermined amount of energy being pumped in by the external driver

  3. Coherent perfect absorption induced by the nonlinearity of a Helmholtz resonator.

    PubMed

    Achilleos, V; Richoux, O; Theocharis, G

    2016-07-01

    In this work, coherent perfect absorption of sound waves induced by the nonlinear response of a Helmholtz Resonator side loaded to a waveguide, is reported. It is shown that this two-port system can perfectly absorb two high amplitude symmetric incident waves under a certain condition. For the one-sided incidence configuration, this condition leads to an absorption equal to 0.5. Experiments verify these results and are in agreement with an analytical nonlinear impedance model for the resonator. The nonlinear control of perfect absorption opens new possibilities in the design of high amplitude sound attenuators for aero-engine applications.

  4. Perfect and broadband acoustic absorption by critically coupled sub-wavelength resonators

    NASA Astrophysics Data System (ADS)

    Romero-García, V.; Theocharis, G.; Richoux, O.; Merkel, A.; Tournat, V.; Pagneux, V.

    2016-01-01

    Perfect absorption is an interdisciplinary topic with a large number of applications, the challenge of which consists of broadening its inherently narrow frequency-band performance. We experimentally and analytically report perfect and broadband absorption for audible sound, by the mechanism of critical coupling, with a sub-wavelength multi-resonant scatterer (SMRS) made of a plate-resonator/closed waveguide structure. In order to introduce the role of the key parameters, we first present the case of a single resonant scatterer (SRS) made of a Helmholtz resonator/closed waveguide structure. In both cases the controlled balance between the energy leakage of the several resonances and the inherent losses of the system leads to perfect absorption peaks. In the case of the SMRS we show that systems with large inherent losses can be critically coupled using resonances with large leakage. In particular, we show that in the SMRS system, with a thickness of λ/12 and diameter of λ/7, several perfect absorption peaks overlap to produce absorption bigger than 93% for frequencies that extend over a factor of 2 in audible frequencies. The reported concepts and methodology provide guidelines for the design of broadband perfect absorbers which could contribute to solve the major issue of noise reduction.

  5. Perfect and broadband acoustic absorption by critically coupled sub-wavelength resonators

    PubMed Central

    Romero-García, V.; Theocharis, G.; Richoux, O.; Merkel, A.; Tournat, V.; Pagneux, V.

    2016-01-01

    Perfect absorption is an interdisciplinary topic with a large number of applications, the challenge of which consists of broadening its inherently narrow frequency-band performance. We experimentally and analytically report perfect and broadband absorption for audible sound, by the mechanism of critical coupling, with a sub-wavelength multi-resonant scatterer (SMRS) made of a plate-resonator/closed waveguide structure. In order to introduce the role of the key parameters, we first present the case of a single resonant scatterer (SRS) made of a Helmholtz resonator/closed waveguide structure. In both cases the controlled balance between the energy leakage of the several resonances and the inherent losses of the system leads to perfect absorption peaks. In the case of the SMRS we show that systems with large inherent losses can be critically coupled using resonances with large leakage. In particular, we show that in the SMRS system, with a thickness of λ/12 and diameter of λ/7, several perfect absorption peaks overlap to produce absorption bigger than 93% for frequencies that extend over a factor of 2 in audible frequencies. The reported concepts and methodology provide guidelines for the design of broadband perfect absorbers which could contribute to solve the major issue of noise reduction. PMID:26781863

  6. Perfect and broadband acoustic absorption by critically coupled sub-wavelength resonators.

    PubMed

    Romero-García, V; Theocharis, G; Richoux, O; Merkel, A; Tournat, V; Pagneux, V

    2016-01-19

    Perfect absorption is an interdisciplinary topic with a large number of applications, the challenge of which consists of broadening its inherently narrow frequency-band performance. We experimentally and analytically report perfect and broadband absorption for audible sound, by the mechanism of critical coupling, with a sub-wavelength multi-resonant scatterer (SMRS) made of a plate-resonator/closed waveguide structure. In order to introduce the role of the key parameters, we first present the case of a single resonant scatterer (SRS) made of a Helmholtz resonator/closed waveguide structure. In both cases the controlled balance between the energy leakage of the several resonances and the inherent losses of the system leads to perfect absorption peaks. In the case of the SMRS we show that systems with large inherent losses can be critically coupled using resonances with large leakage. In particular, we show that in the SMRS system, with a thickness of λ/12 and diameter of λ/7, several perfect absorption peaks overlap to produce absorption bigger than 93% for frequencies that extend over a factor of 2 in audible frequencies. The reported concepts and methodology provide guidelines for the design of broadband perfect absorbers which could contribute to solve the major issue of noise reduction.

  7. Combined surface plasmon resonance and X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Garcia, Miguel Angel; Serrano, Aida; Rodriguez de La Fuente, Oscar; Castro, German R.

    2012-02-01

    We present a system for the excitation and measurement of surface plasmons in metallic films based on the Kretschmann-Raether configuration that can be installed in a synchrotron beamline. The device was mounted an tested in a hard X-ray Absorption beamline, BM25 Spline at ESRF. Whit this device it is possible to carry on experiments combining surface plasmon and X-ray absorption spectroscopies. The surface plasmons can be use to monitor in situ changes induced by the X-rays in the metallic films or the dielectric overlayer. Similarly, the changes in the electronic configuration of the material when surface plasmons are excited can be measured by X-ray absorption spectroscopy. The resolution of the system allows to observe changes in the signals of the order of 10-3 to 10-5 depending on the particular experiment and used configuration. The system is available for experiments at the beamline.

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

    SciTech Connect

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

    1981-12-16

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

  9. Probing the pigment binding sites in LHCII with resonance Raman spectroscopy: The effect of mutations at S123.

    PubMed

    Kish, Elizabeth; Wang, Ke; Llansola-Portoles, Manuel J; Ilioaia, Cristian; Pascal, Andrew A; Robert, Bruno; Yang, Chunhong

    2016-09-01

    Resonance Raman spectroscopy was used to evaluate the structure of light-harvesting chlorophyll (Chl) a/b complexes of photosystem II (LHCII), reconstituted from wild-type (WT) and mutant apoproteins over-expressed in Escherichia coli. The point mutations involved residue S123, exchanged for either P (S123P) or G (S123G). In all reconstituted proteins, lutein 2 displayed a distorted conformation, as it does in purified LHCII trimers. Reconstituted WT and S123G also exhibited a conformation of bound neoxanthin (Nx) molecules identical to the native protein, while the S123P mutation was found to induce a change in Nx conformation. This structural change of neoxanthin is accompanied by a blue shift of the absorption of this carotenoid molecule. The interactions assumed by (and thus the structure of the binding sites of) the bound Chls b were found identical in all the reconstituted proteins, and only marginally perturbed as compared to purified LHCII. The interactions assumed by bound Chls a were also identical in purified LHCII and the reconstituted WT. However, the keto carbonyl group of one Chl a, originally free-from-interactions in WT LHCII, becomes involved in a strong H-bond with its environment in LHCII reconstituted from the S123P apoprotein. As the absorption in the Qy region of this protein is identical to that of the LHCII reconstituted from the WT apoprotein, we conclude that the interaction state of the keto carbonyl of Chl a does not play a significant role in tuning the binding site energy of these molecules.

  10. A resonance Raman spectroscopic and CASSCF investigation of the Franck-Condon region structural dynamics and conical intersections of thiophene.

    PubMed

    Wu, Xian-Fang; Zheng, Xuming; Wang, Hui-Gang; Zhao, Yan-Yin; Guan, Xiangguo; Phillips, David Lee; Chen, Xuebo; Fang, Weihai

    2010-10-07

    Resonance Raman spectra were acquired for thiophene in cyclohexane solution with 239.5 and 266 nm excitation wavelengths that were in resonance with ∼240 nm first intense absorption band. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mostly along the reaction coordinates of six totally symmetry modes and three nontotally symmetry modes. The appearance of the nontotally symmetry modes, the C-S antisymmetry stretch +C-C=C bend mode ν(21)(B(2)) at 754 cm(-1) and the H(7)C(3)-C(4)H(8) twist ν(9)(A(2)) at 906 cm(-1), suggests the existence of two different types of vibronic-couplings or curve-crossings among the excited states in the Franck-Condon region. The electronic transition energies, the excited state structures, and the conical intersection points (1)B(1)/(1)A(1) and (1)B(2)/(1)A(1) between 2 (1)A(1) and 1 (1)B(2) or 1 (1)B(1) potential energy surfaces of thiophene were determined by using complete active space self-consistent field theory computations. These computational results were correlated with the Franck-Condon region structural dynamics of thiophene. The ring opening photodissociation reaction pathway through cleavage of one of the C-S bonds and via the conical intersection point (1)B(1)/(1)A(1) was revealed to be the predominant ultrafast reaction channel for thiophene in the lowest singlet excited state potential energy hypersurface, while the internal conversion pathway via the conical intersection point (1)B(2)/(1)A(1) was found to be the minor decay channel in the lowest singlet excited state potential energy hypersurface.

  11. Key hydride vibrational modes in [NiFe] hydrogenase model compounds studied by resonance Raman spectroscopy and density functional calculations.

    PubMed

    Shafaat, Hannah S; Weber, Katharina; Petrenko, Taras; Neese, Frank; Lubitz, Wolfgang

    2012-11-05

    Hydrogenase proteins catalyze the reversible conversion of molecular hydrogen to protons and electrons. While many enzymatic states of the [NiFe] hydrogenase have been studied extensively, there are multiple catalytically relevant EPR-silent states that remain poorly characterized. Analysis of model compounds using new spectroscopic techniques can provide a framework for the study of these elusive states within the protein. We obtained optical absorption and resonance Raman (RR) spectra of (dppe)Ni(μ-pdt)Fe(CO)(3) and [(dppe)Ni(μ-pdt)(μ-H)Fe(CO)(3)][BF(4)], which are structural and functional model compounds for the EPR-silent Ni-SI and Ni-R states of the [NiFe] hydrogenase active site. The studies presented here use RR spectroscopy to probe vibrational modes of the active site, including metal-hydride stretching vibrations along with bridging ligand-metal and Fe-CO bending vibrations, with isotopic substitution used to identify key metal-hydride modes. The metal-hydride vibrations are essentially uncoupled and represent isolated, localized stretching modes; the iron-hydride vibration occurs at 1530 cm(-1), while the nickel-hydride vibration is observed at 945 cm(-1). The significant discrepancy between the metal-hydride vibrational frequencies reflects the slight asymmetry in the metal-hydride bond lengths. Additionally, time-dependent density functional theory (TD-DFT) calculations were carried out to obtain theoretical RR spectra of these compounds. On the basis of the detailed comparison of theory and experiment, the dominant electronic transitions and significant normal modes probed in the RR experiments were assigned; the primary transitions in the visible wavelengths represent metal-to-metal and metal-to-ligand charge transfer bands. Inherent properties of metal-hydride vibrational modes in resonance Raman spectra and DFT calculations are discussed together with the prospects of observing such vibrational modes in metal-hydride-containing proteins. Such a

  12. Enhanced optical absorption and electric field resonance in diabolo metal bar optical antennas.

    PubMed

    Pan, Zeyu; Guo, Junpeng

    2013-12-30

    Resonance behaviors of the fundamental resonance mode of diabolo metal bar optical antennas are investigated by using finite-difference time-domain (FDTD) numerical simulations and a dipole oscillator model. It is found that as the waist of the diabolo metal bar optical antenna is reduced, optical energy absorption cross section and near field enhancement at resonance increase significantly. Also reduction of the diabolo waist width causes red-shift of the resonant wavelengths in the spectra of absorption cross-section, scattering cross-section, and the near electric field. A dipole oscillator model including the self-inductance force is used to fit the FDTD numerical simulation results. The dipole oscillator model characterizes well the resonance behaviors of narrow waist diabolo metal bar optical antennas.

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

    SciTech Connect

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

    2015-09-28

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

  14. Amplification of ultra-short laser pulses via resonant backward Raman amplification in plasma

    NASA Astrophysics Data System (ADS)

    Mishra, S. K.; Andreev, A.

    2016-08-01

    In this paper, we have examined the possibility of using resonant backward Raman amplification (BRA) as an efficient mechanism in amplifying the low intensity ultra-short ( ≤ fs ) pulses using plasma as intermediate amplifying medium; such pulses are anticipated to get produced in the form of the secondary sources at ALPS (Attosecond Light Pulse Source) center of ELI (Extreme Light Infrastructure). In preliminary assessment of the scheme, the analytical expressions for the pump/seed laser pulses and plasma characteristic features are obtained which concisely describe the parameter regime of resonant BRA applicability in achieving significant amplification. The consistency of the scheme in the context of ELI-ALPS sources has been validated through particle in cell (PIC) simulations. The peak intensity of the amplified seed pulse predicted via simulation results is found in reasonable agreement with the analytical estimates. Utilizing these analytical expressions as a basis in perspective of ELI-ALPS parameter access, a specific example displaying the key plasma and laser parameters for amplifying weak seed pulse has been configured; the limitations and conceivable remedies in resonant BRA implementation have also been highlighted.

  15. Identification of metalloporphyrins with high sensitivity using graphene-enhanced resonance Raman scattering.

    PubMed

    Kim, Bo-Hyun; Kim, Daechul; Song, Sungho; Park, DongHyuk; Kang, Il-Suk; Jeong, Dae Hong; Jeon, Seokwoo

    2014-03-18

    Graphene-enhanced resonance Raman scattering (GERRS) was performed for the detection of three different metallo-octaethylporphyrins (M-OEPs; M = 2H, FeCl, and Pt) homogeneously thermal vapor deposited on a graphene surface. GERRS of M-OEPs were measured using three different excitation wavelengths, λ(ex) = 405, 532, and 633 nm, and characterized detail vibrational bands for the identification of M-OEPs. The GERRS spectra of Pt-OEP at λ(ex) = 532 nm showed ~29 and ~162 times signal enhancement ratio on graphene and on graphene with Ag nanoclusters, respectively, compared to the spectra from bare SiO2 substrate. This enhancement ratio, however, was varied with M-OEPs and excitation wavelengths. The characteristic peaks and band shapes of GERRS for each M-OEP were measured with high sensitivity (100 pmol of thermal vapor deposited Pt-OEP), and these facilitate the selectively recognition of molecules. Also, the peaks shift and broadening provide the evidence of the interaction between graphene and M-OEPs through the charge transfer and π-orbital interaction. The increase of graphene layer induced the decrease of signal intensity and GERRS effect was almost not observed on the thick graphite flakes. Further experiments with various substrates demonstrated that the interaction of single layer of graphene with molecule is the origin of the Raman signal enhancement of M-OEPs. In this experiment, we proved the graphene is a good alternative substrate of Raman spectroscopy for the selective detection of various metalloporphyrins with high sensitivity.

  16. 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.

  17. Surface-enhanced resonance Raman scattering spectroscopy applied to phytochrome and its model compounds. 1. Biliverdin photoisomers

    SciTech Connect

    Holt, R.E.; Farrens, D.L.; Song, Pillsoon; Cotton, T.M. )

    1989-12-20

    The application of surface-enhanced resonance Raman scattering (SERRS) spectroscopy to the analysis of the configuration of biliverdin dimethyl ester (BVDE) is reported. SERRS spectra obtained by adsorption of the compounds onto an electrochemically roughened silver electrode and recorded at 7 K were intense and free of significant photodegradation. The similarity of the SERRS and resonance Raman (RR) spectra obtained under identical conditions suggests that no perturbation of the electronic structure of the BVDE occurs upon interaction with the silver surface, and that the distribution of conformers comprising the BVDE solution is not changed. SERRS spectra of the deuterated and monoprotonated Z,Z,Z isomer are also presented. To investigate the influence of configuration upon the Raman spectrum we have synthesized and purified the E,Z,A, and Z,Z,E isomers of BVDE. Excellent SERRS spectra were obtained from the solutions of the compounds eluted directly from the TLC plates.

  18. Multi-resonant absorption in ultra-thin silicon solar cells with metallic nanowires.

    PubMed

    Massiot, Inès; Colin, Clément; Sauvan, Christophe; Lalanne, Philippe; Cabarrocas, Pere Roca I; Pelouard, Jean-Luc; Collin, Stéphane

    2013-05-06

    We propose a design to confine light absorption in flat and ultra-thin amorphous silicon solar cells with a one-dimensional silver grating embedded in the front window of the cell. We show numerically that multi-resonant light trapping is achieved in both TE and TM polarizations. Each resonance is analyzed in detail and modeled by Fabry-Perot resonances or guided modes via grating coupling. This approach is generalized to a complete amorphous silicon solar cell, with the additional degrees of freedom provided by the buffer layers. These results could guide the design of resonant structures for optimized ultra-thin solar cells.

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

    PubMed Central

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

    2016-01-01

    Measurements of spin excitations are essential for an understanding of spin-mediated pairing for superconductivity; and resonant inelastic X-ray scattering (RIXS) provides a considerable opportunity to probe high-energy spin excitations. However, whether RIXS correctly measures the collective spin excitations of doped superconducting cuprates remains under debate. Here we demonstrate distinct Raman- and fluorescence-like RIXS excitations of Bi1.5Pb0.6Sr1.54CaCu2O8+δ. Combining photon-energy and momentum dependent RIXS measurements with theoretical calculations using exact diagonalization provides conclusive evidence that the Raman-like RIXS excitations correspond to collective spin excitations, which are magnons in the undoped Mott insulators and evolve into paramagnons in doped superconducting compounds. In contrast, the fluorescence-like shifts are due primarily to the continuum of particle-hole excitations in the charge channel. Our results show that under the proper experimental conditions RIXS indeed can be used to probe paramagnons in doped high-Tc cuprate superconductors. PMID:26794437

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    SciTech Connect

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

    2016-01-22

    Measurements of spin excitations are essential for an understanding of spin-mediated pairing for superconductivity; and resonant inelastic X-ray scattering (RIXS) provides a considerable opportunity to probe high-energy spin excitations. However, whether RIXS correctly measures the collective spin excitations of doped superconducting cuprates remains under debate. Here we demonstrate distinct Raman- and fluorescence-like RIXS excitations of Bi1.5Pb0.6Sr1.54CaCu2O8+δ. Combining photon-energy and momentum dependent RIXS measurements with theoretical calculations using exact diagonalization provides conclusive evidence that the Raman-like RIXS excitations correspond to collective spin excitations, which are magnons in the undoped Mott insulators and evolve into paramagnons in doped superconducting compounds. In contrast, the fluorescence-like shifts are due primarily to the continuum of particle-hole excitations in the charge channel. Our results show that under the proper experimental conditions RIXS indeed can be used to probe paramagnons in doped high-Tc cuprate superconductors.

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

    DOE PAGES

    Huang, H. Y.; Jia, C. J.; Chen, Z. Y.; ...

    2016-01-22

    Measurements of spin excitations are essential for an understanding of spin-mediated pairing for superconductivity; and resonant inelastic X-ray scattering (RIXS) provides a considerable opportunity to probe high-energy spin excitations. However, whether RIXS correctly measures the collective spin excitations of doped superconducting cuprates remains under debate. Here we demonstrate distinct Raman- and fluorescence-like RIXS excitations of Bi1.5Pb0.6Sr1.54CaCu2O8+δ. Combining photon-energy and momentum dependent RIXS measurements with theoretical calculations using exact diagonalization provides conclusive evidence that the Raman-like RIXS excitations correspond to collective spin excitations, which are magnons in the undoped Mott insulators and evolve into paramagnons in doped superconducting compounds. In contrast,more » the fluorescence-like shifts are due primarily to the continuum of particle-hole excitations in the charge channel. Our results show that under the proper experimental conditions RIXS indeed can be used to probe paramagnons in doped high-Tc cuprate superconductors.« less

  3. Optical pathology study of human abdominal aorta tissues using confocal micro resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Cheng-hui; Boydston-White, Susie; Wang, Wubao; Sordillo, Laura A.; Shi, Lingyan; Weisberg, Arel; Tomaselli, Vincent P.; Sordillo, Peter P.; Alfano, Robert R.

    2016-03-01

    Resonance Raman (RR) spectroscopic technique has a high potential for label-free and in-situ detection of biomedical lesions in vivo. This study evaluates the ability of RR spectroscopy method as an optical histopathology tool to detect the atherosclerotic plaque states of abdominal aorta in vitro. This part demonstrates the RR spectral molecular fingerprint features from different sites of the atherosclerotic abdominal aortic wall tissues. Total 57 sites of five pieces aortic samples in intimal and adventitial wall from an autopsy specimen were examined using confocal micro Raman system of WITec 300R with excitation wavelength of 532nm. The preliminary RR spectral biomarkers of molecular fingerprints indicated that typical calcified atherosclerotic plaque (RR peak at 964cm-1) tissue; fibrolipid plaque (RR peaks at 1007, 1161, 1517 and 2888cm-1) tissue, lipid pool with the fatty precipitation cholesterol) with collagen type I (RR peaks at 864, 1452, 1658, 2888 and 2948cm-1) in the soft tissue were observed and investigated.

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

    SciTech Connect

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

    2014-06-14

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

  5. Characterization of carotenoids in soil bacteria and investigation of their photodegradation by UVA radiation via resonance Raman spectroscopy.

    PubMed

    Kumar B N, Vinay; Kampe, Bernd; Rösch, Petra; Popp, Jürgen

    2015-07-07

    A soil habitat consists of an enormous number of pigmented bacteria with the pigments mainly composed of diverse carotenoids. Most of the pigmented bacteria in the top layer of the soil are photoprotected from exposure to huge amounts of UVA radiation on a daily basis by these carotenoids. The photostability of these carotenoids depends heavily on the presence of specific features like a carbonyl group or an ionone ring system on its overall structure. Resonance Raman spectroscopy is one of the most sensitive and powerful techniques to detect and characterize these carotenoids and also monitor processes associated with them in their native system at a single cell resolution. However, most of the resonance Raman profiles of carotenoids have very minute differences, thereby making it extremely difficult to confirm if these differences are attributed to the presence of different carotenoids or if it is a consequence of their interaction with other cellular components. In this study, we devised a method to overcome this problem by monitoring also the photodegradation of the carotenoids in question by UVA radiation wherein a differential photodegradation response will confirm the presence of different carotenoids irrespective of the proximities in their resonance Raman profiles. Using this method, the detection and characterization of carotenoids in pure cultures of five species of pigmented coccoid soil bacteria is achieved. We also shed light on the influence of the structure of the carotenoid on its photodegradation which can be exploited for use in the characterization of carotenoids via resonance Raman spectroscopy.

  6. Dermal carotenoids as measured by resonance Raman spectroscopy as a biomarker of response to a fruit/vegetable intervention study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dermal carotenoid status may have utility as a biomarker for vegetable and fruit consumption. Resonance Raman spectroscopy (RRS) is a valid, non-invasive method to assess dermal carotenoids as a biomarker of usual vegetable and fruit intake, but has not been evaluated in response to a whole-diet in...

  7. Raman-like resonant secondary emission causes valley coherence in CVD-grown monolayer Mo S2

    NASA Astrophysics Data System (ADS)

    Yoshikawa, Naotaka; Tani, Shuntaro; Tanaka, Koichiro

    2017-03-01

    Monolayer transition metal dichalcogenides are promising materials for "valleytronics." They have band gaps at energy-degenerate K and K' valleys with opposite spins. Due to the lack of inversion symmetry, electron-hole pairs can be selectively created at K or K' valleys by circularly polarized photons. In addition, linearly polarized light excitation creates the coherent superposition of exciton valley states, referred to as the generation of valley coherence. In this study we performed polarization resolved photoluminescence and resonant Raman spectroscopy of CVD-grown monolayer Mo S2 . We found that the lowest exciton photoluminescence becomes polarized, indicating the effective generation of valley polarization and valley coherence due to the resonant effect, accompanied by a drastic change of the polarization selection rule of Raman scattering. These results were theoretically explained from the viewpoint of the selection rules of resonant Raman scattering. We conclude that the Raman-like resonant second-order optical process should be the main mechanism of valley coherence.

  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. Dispersion of the resonant nonlinear optical susceptibility obtained with femtosecond time-domain coherent anti-Stokes Raman scattering.

    PubMed

    Yang, Shan; Ganikhanov, Feruz

    2013-11-15

    We propose and experimentally demonstrate a method that is capable of resolving both real and imaginary parts of third-order nonlinearity (χ(3)) in the vicinity of Raman resonances. Dispersion of χ(3) can be obtained from a medium probed within microscopic volumes with a spectral resolution of better than 0.10 cm(-1).

  10. A Study on the Excitation and Resonant Absorption of Coronal Loop Kink Oscillations

    NASA Astrophysics Data System (ADS)

    Yu, Dae Jung; Van Doorsselaere, Tom

    2016-11-01

    We study theoretically the issue of externally driven excitations of standing kink waves and their resonant absorption into torsionally polarized m = 1 waves in the coronal loops in pressureless plasmas. We use the ideal MHD equations, for which we develop an invariant imbedding method available in cylindrical geometry. We assume a sinusoidal density profile at the loop boundary where the density inside the loop is lower than the outside and vice versa. We present field distributions for these two cases and find that they have similar behaviors. We compare the results for the overdense loops, which describe the usual coronal loops, with the analytical solutions of Soler et al. obtained using the Frobenius method. Our results show some similarity for thin nonuniform layers but deviate a lot for thick nonuniform layers. For the first case, which describes the wave train propagation in funnels, we find that resonant absorption depends crucially on the thickness of the nonuniform boundary, loop length, and density contrast. The resonant absorption of the kink mode is dominant when the loop length is sufficiently larger compared with its radius (thin loop). The behavior of the far-field pattern of the scattered wave by the coronal loop is closely related to that of the resonant absorption. For the mode conversion phenomena in inhomogeneous plasmas, a certain universal behavior of the resonant absorption is found for the first time. We expect that the main feature may also apply to the overdense loops and discuss its relation to the damping rate.

  11. Characterizing millisecond intermediates in hemoproteins using rapid-freeze-quenched resonance Raman spectroscopy

    PubMed Central

    Matsumura, Hirotoshi; Moënne-Loccoz, Pierre

    2014-01-01

    Summary The combination of rapid-freeze-quenching (RFQ) technique and resonance Raman (RR) spectroscopy represents a unique tool to investigate the nature of short-lived intermediates formed during the enzymatic reaction of metalloproteins. Commercially available equipment allows trapping of intermediates within the millisecond to second timescale for low-temperature RR analysis and direct detection of metal-ligand vibrations and porphyrin skeletal vibrations in hemoproteins. This chapter briefly discusses previous RFQ-RR studies carried-out in our laboratory, and presents as a practical example protocols for the preparation of RFQ samples of the reaction of metmyoglobin with nitric oxide (NO) which requires anaerobic conditions. We also describe important controls and practical procedure for the analysis of these samples by low-temperature RR spectroscopy. PMID:24639256

  12. Freely designable optical frequency conversion in Raman-resonant four-wave-mixing process

    PubMed Central

    Zheng, Jian; Katsuragawa, Masayuki

    2015-01-01

    Nonlinear optical processes are governed by the relative-phase relationships among the relevant electromagnetic fields in these processes. In this Report, we describe the physics of arbitrary manipulation of Raman-resonant four-wave-mixing process by artificial control of relative phases. As a typical example, we show freely designable optical-frequency conversions to extreme spectral regions, mid-infrared and vacuum-ultraviolet, with near-unity quantum efficiencies. Furthermore, we show that such optical-frequency conversions can be realized by using a surprisingly simple technology where transparent plates are placed in a nonlinear optical medium and their positions and thicknesses are adjusted precisely. In a numerical simulation assuming practically applicable parameters in detail, we demonstrate a single-frequency tunable laser that covers the whole vacuum-ultraviolet spectral range of 120 to 200 nm. PMID:25748023

  13. Theoretical analysis of resonant raman scattering: Simulations of lineshapes and excitation profiles

    NASA Astrophysics Data System (ADS)

    Angeloni, Leonardo; Fracassi, Pier Francesco; Della Valle, Raffaele Guido

    1985-04-01

    The steady-state response of a three-level system in the presence of a strong laser field is described with the density operator formalism, in order to derive an analytical expression for the intensity of resonance Raman scattering. The Liouville equation for the density operator is written in quantum form for both the molecular system and the radiation field, making use of the dipole and rotating-wave approximations for the matter-radiation interaction, and of the Markov approximation for the molecular decays. The equation is solved exactly for the laser field, and in perturbative way for the generated field. The results account for power broadening of the generated line. Rabi intensity-dip of the generated signal, and for the excitation profiles in the Franck-Condom approximation.

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

    NASA Astrophysics Data System (ADS)

    Bairamov, B. Kh.

    2016-04-01

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

  15. Raman spectroscopy of magneto-phonon resonances in graphene and graphite

    NASA Astrophysics Data System (ADS)

    Goler, Sarah; Yan, Jun; Pellegrini, Vittorio; Pinczuk, Aron

    2012-08-01

    The magneto-phonon resonance or MPR occurs in semiconductor materials when the energy spacing between Landau levels is continuously tuned to cross the energy of an optical phonon mode. MPRs have been largely explored in bulk semiconductors, in two-dimensional systems and in quantum dots. Recently there has been significant interest in the MPR interactions of the Dirac fermion magneto-excitons in graphene, and a rich splitting and anti-crossing phenomena of the even parity E2g long wavelength optical phonon mode have been theoretically proposed and experimentally observed. The MPR has been found to crucially depend on disorder in the graphene layer. This is a feature that creates new venues for the study of interplays between disorder and interactions in the atomic layers. We review here the fundamentals of MRP in graphene and the experimental Raman scattering works that have led to the observation of these phenomena in graphene and graphite.

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

    SciTech Connect

    Wade, Jessica; Wood, Sebastian; Kim, Ji-Seon; Beatrup, Daniel; Hurhangee, Michael; McCulloch, Iain; Durrant, James R.; Bronstein, Hugo

    2015-06-28

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

  17. Solvent effects on the resonance Raman spectra of bacteriochlorophyll a cation radical

    NASA Astrophysics Data System (ADS)

    Misono, Yasuhito; Nishizawa, Ei-ichi; Limantara, Leenawaty; Koyama, Yasushi; Itoh, Koichi

    1995-04-01

    Resonance Raman (RR) spectra were measured for the cation radical of bacteriochlorophyll a in acetone, methanol, dichloromethane and mixed solvents of acetone and methanol. The ring-breathing (C a-C m stretching) frequency of the radical (abbreviated as vr+) was observed at 1601 cm -1 in acetone (forming a penta-coordinated monomer), at 1587 cm -1 in a methanol (forming a hexa-coordinated monomer) and at 1600 cm -1 in dichloromethane (forming a penta-coordinated aggregate). The RR spectrum of the radical in dichloromethane is almost identical to the transient RR spectrum ascribed to 'the aggregated T 1 species of Bchl a' formed in the particular solvent by Nishizawa, Limantara, Nanjou, Nagae, Kakuno and Koyama, indicating that their interpretation needs to be revised.

  18. Study of the orientational ordering of carotenoids in lipid bilayers by resonance-Raman spectroscopy.

    PubMed Central

    van de Ven, M; Kattenberg, M; van Ginkel, G; Levine, Y K

    1984-01-01

    The orientational ordering of beta-carotene and crocetin embedded in lamellar model membranes has been investigated by angle-resolved resonance Raman scattering at a temperature well above the phase transition of the lipid chains. It is shown that the ordering of the carotenoids is dependent on the chemical composition of the lipid bilayers. The orientational distribution functions found clearly show that beta-carotene is oriented parallel to the bilayer plane (dioleoyl lecithin) or perpendicular to it (soybean lecithin). For dimyristoyl lecithin at 40 degrees C, egg-lecithin, and digalactosyl diacylglycerol two maxima were found in the orientational distribution: one parallel and one perpendicular to the bilayer surface. Crocetin embedded in soybean lecithin bilayers yields a similar bimodal distribution function. Because of rapid photodegradation no results could be obtained for spirilloxanthin. PMID:6743750

  19. Tunable THz wave absorption by graphene-assisted plasmonic metasurfaces based on metallic split ring resonators

    NASA Astrophysics Data System (ADS)

    Ahmadivand, Arash; Sinha, Raju; Karabiyik, Mustafa; Vabbina, Phani Kiran; Gerislioglu, Burak; Kaya, Serkan; Pala, Nezih

    2017-01-01

    Graphene plasmonics has been introduced as a novel platform to design various nano- and microstructures to function in a wide range of spectrum from optical to THz frequencies. Herein, we propose a tunable plasmonic metamaterial in the THz regime by using metallic (silver) concentric microscale split ring resonator arrays on a multilayer metasurface composed of silica and silicon layers. We obtained an absorption percentage of 47.9% including two strong Fano resonant dips in THz regime for the purely plasmonic metamaterial without graphene layer. Considering the data of an atomic graphene sheet (with the thickness of 0.35 nm) in both analytical and experimental regimes obtained by prior works, we employed a graphene layer under concentric split ring resonator arrays and above the multilayer metasurface to enhance the absorption ratio in THz bandwidth. Our numerical and analytical results proved that the presence of a thin graphene layer enhances the absorption coefficient of MM to 64.35%, at the highest peak in absorption profile that corresponds to the Fano dip position. We also have shown that changing the intrinsic characteristics of graphene sheet leads to shifts in the position of Fano dips and variations in the absorption efficiency. The maximum percentage of absorption ( 67%) was obtained for graphene-based MM with graphene layer with dissipative loss factor of 1477 Ω. Employing the antisymmetric feature of the split ring resonators, the proposed graphene-based metamaterial with strong polarization dependency is highly sensitive to the polarization angle of the incident THz beam.

  20. Impact of MIE-Resonances on the Atmospheric Absorption of Water Clouds

    NASA Technical Reports Server (NTRS)

    Wiscombe, W.; Kinne, S.; Nussenzveig, H.; Lau, William K. M. (Technical Monitor)

    2002-01-01

    Clouds strongly modulate radiative transfer processes in the Earth's atmosphere. Studies, which simulate bulk properties of clouds, such as absorption, require methods that accurately account for multiple scattering among individual cloud particles. Multiple scattering processes are well described by MIE-theory, if interacting particles have a spherical shape. This is a good assumption for water droplets. Thus, simulations for water clouds (especially for interactions with solar radiation) usually apply readily available MIE-codes. The presence of different drop-sizes, however, necessitates repetitive calculations for many sizes. The usual representation by a few sizes is likely to miss contributions from densely distributed, sharp resonances. Despite their usually narrow width, integrated over the entire size-spectrum of a cloud droplet distribution, the impact of missed resonances could add up. The consideration of these resonances tends to increase cloud extinction and cloud absorption. This mechanism for a larger (than by MIE-methods predicted) solar absorption has the potential to explain observational evidence of larger than predicted cloud absorption at solar wavelengths. The presentation will address the absorption impact of added resonances for typical properties of water clouds (e.g. drop size distributions, drop concentrations and cloud geometry). Special attention will be given to scenarios with observational evidence of law than simulated solar absorption; particularly if simultaneous measurements of cloud micro- and macrophysical properties are available.

  1. "Parallel factor analysis of multi-excitation ultraviolet resonance Raman spectra for protein secondary structure determination".

    PubMed

    Oshokoya, Olayinka O; JiJi, Renee D

    2015-09-10

    Protein secondary structural analysis is important for understanding the relationship between protein structure and function, or more importantly how changes in structure relate to loss of function. The structurally sensitive protein vibrational modes (amide I, II, III and S) in deep-ultraviolet resonance Raman (DUVRR) spectra resulting from the backbone C-O and N-H vibrations make DUVRR a potentially powerful tool for studying secondary structure changes. Experimental studies reveal that the position and intensity of the four amide modes in DUVRR spectra of proteins are largely correlated with the varying fractions of α-helix, β-sheet and disordered structural content of proteins. Employing multivariate calibration methods and DUVRR spectra of globular proteins with varying structural compositions, the secondary structure of a protein with unknown structure can be predicted. A disadvantage of multivariate calibration methods is the requirement of known concentration or spectral profiles. Second-order curve resolution methods, such as parallel factor analysis (PARAFAC), do not have such a requirement due to the "second-order advantage." An exceptional feature of DUVRR spectroscopy is that DUVRR spectra are linearly dependent on both excitation wavelength and secondary structure composition. Thus, higher order data can be created by combining protein DUVRR spectra of several proteins collected at multiple excitation wavelengths to give multi-excitation ultraviolet resonance Raman data (ME-UVRR). PARAFAC has been used to analyze ME-UVRR data of nine proteins to resolve the pure spectral, excitation and compositional profiles. A three factor model with non-negativity constraints produced three unique factors that were correlated with the relative abundance of helical, β-sheet and poly-proline II dihedral angles. This is the first empirical evidence that the typically resolved "disordered" spectrum represents the better defined poly-proline II type structure.

  2. Ionization and transient absorption control with a resonant attosecond clock

    NASA Astrophysics Data System (ADS)

    Argenti, Luca

    2014-04-01

    Metastable states are important actors in the ionisation of atoms and molecules. Sub-femtosecond extreme ultraviolet pulses can coherently populate several transiently bound states at once, thus starting the attosecond clocks which are required to monitor and control ultrafast electronic evolution above the ionisation threshold. Here we illustrate, from a theoretical point of view, the effects coherent superpositions of 1Po doubly excited states in the helium atom have on channel-resolved photoelectron spectra as well as on the transient absorption spectrum of the atom in the extreme ultraviolet region, when they are created by a single-attosecond pulse in the presence of a strong few-cycle near-infrared/visible pulse which acts as a probe. Interference fringes varying rapidly with the pump-probe time delay are visible in both photoelectron and transient absorption spectra. From such fringes, the wave packet itself can conceivably be reconstructed. Conversely, all observables are modulated by the characteristic beating periods of the wave packet, so that control of partial ionisation yields, branching ratios, and light absorption or amplification can be achieved.

  3. Scanning near-field optical coherent anti-Stokes Raman microscopy (SNOM-CARS) with femtosecond laser pulses in vibrational and electronic resonance.

    PubMed

    Namboodiri, Mahesh; Khan, Tahir Zeb; Bom, Sidhant; Flachenecker, Günter; Materny, Arnulf

    2013-01-14

    Accessing ultrafast photoinduced molecular dynamics on a femtosecond time-scale with vibrational selectivity and at the same time sub-diffraction limited spatial resolution would help to gain important information about ultrafast processes in nanostructures. While nonlinear Raman techniques have been used to obtain highly resolved images in combination with near-field microscopy, the use of femtosecond laser pulses in electronic resonance still constitutes a big challenge. Here, we present our first results on coherent anti-Stokes Raman scattering (fs-CARS) with femtosecond laser pulses detected in the near-field using scanning near-field optical microscopy (SNOM). We demonstrate that highly spatially resolved images can be obtained from poly(3-hexylthiophene) (P3HT) nano-structures where the fs-CARS process was in resonance with the P3HT absorption and with characteristic P3HT vibrational modes without destruction of the samples. Sub-diffraction limited lateral resolution is achieved. Especially the height resolution clearly surpasses that obtained with standard microCARS. These results will be the basis for future investigations of mode-selective dynamics in the near field.

  4. Microwave Resonator Measurements of Atmospheric Absorption Coefficients: A Preliminary Design Study

    NASA Technical Reports Server (NTRS)

    Walter, Steven J.; Spilker, Thomas R.

    1995-01-01

    A preliminary design study examined the feasibility of using microwave resonator measurements to improve the accuracy of atmospheric absorption coefficients and refractivity between 18 and 35 GHz. Increased accuracies would improve the capability of water vapor radiometers to correct for radio signal delays caused by Earth's atmosphere. Calibration of delays incurred by radio signals traversing the atmosphere has applications to both deep space tracking and planetary radio science experiments. Currently, the Cassini gravity wave search requires 0.8-1.0% absorption coefficient accuracy. This study examined current atmospheric absorption models and estimated that current model accuracy ranges from 5% to 7%. The refractivity of water vapor is known to 1% accuracy, while the refractivity of many dry gases (oxygen, nitrogen, etc.) are known to better than 0.1%. Improvements to the current generation of models will require that both the functional form and absolute absorption of the water vapor spectrum be calibrated and validated. Several laboratory techniques for measuring atmospheric absorption and refractivity were investigated, including absorption cells, single and multimode rectangular cavity resonators, and Fabry-Perot resonators. Semi-confocal Fabry-Perot resonators were shown to provide the most cost-effective and accurate method of measuring atmospheric gas refractivity. The need for accurate environmental measurement and control was also addressed. A preliminary design for the environmental control and measurement system was developed to aid in identifying significant design issues. The analysis indicated that overall measurement accuracy will be limited by measurement errors and imprecise control of the gas sample's thermodynamic state, thermal expansion and vibration- induced deformation of the resonator structure, and electronic measurement error. The central problem is to identify systematic errors because random errors can be reduced by averaging

  5. Deformations of the Heme Group of Different Ferrocytochrome c Proteins Probed by Resonance Raman Spectroscopy

    SciTech Connect

    Hagarman, Andrew; Schweitzer-Stenner, Reinhard; Wallace, Carmichael; Laberge, Monique

    2008-11-14

    We measured the low-frequency polarized resonance Raman spectra of horse heart, chicken, and yeast(C102T) ferrocytochromes c with Soret excitation. We examined the out-of-plane deformations of the heme groups by determining the relative intensities and depolarization ratios of a variety of out-of-plane and in-plane Raman active bands. Analysis of relative Raman intensities shows differences in non-planarity of the heme groups of yeast(C102T), horse heart and chicken cytochrome c. Cytochrome c has been shown to have a dominant ruffling (B{sub 1u}) deformation by means of normal coordinate structural decomposition (NSD) analysis of the heme group in crystal structures. The presence and intensity of B{sub 1u} modes, {gamma}{sub 10}-{gamma}{sub 12}, support the indication of ruffling being the major contribution to the non-planar deformations in cytochrome c. Other types of non-planar deformations like doming (A{sub 2U}) and waving (E{sub g}) can be deduced from the Raman activity of {gamma}{sub 5} (A{sub 2u}), {gamma}{sub 21} and {gamma}{sub 22} (E{sub g}). The depolarization ratios of {gamma}{sub 5}, {gamma}{sub 10}, {gamma}{sub 11} and {gamma}{sub 12} are larger than 0.125, indicating the presence of other deformations such as saddling (B{sub 2u}) and propellering (A{sub 1u}), which is again in agreement with the crystal structures of horse heart and yeast ferrocytochrome c. An analysis of the intensities and depolarization ratios of out-of-plane modes revealed that ruffling is comparable in yeast and horse heart cytochrome c, saddling is larger and doming as well as propellering are lower in yeast cytochrome c. With respect to doming and ruffling our results contradict values obtained from the NSD analysis of the corresponding crystal structures. With respect to saddling, our data are in agreement with the crystal structure. The NSD analysis of heme structures resulting from MD simulations did not correlate very well with the spectroscopically obtained results

  6. Interaction between indium tin oxide nanoparticles and cytochrome c: A surface-enhanced Raman scattering and absorption spectroscopic study

    SciTech Connect

    Yang, Yimin E-mail: tqiu@seu.edu.cn; Du, Deyang; Fan, Jiyang; Qiu, Teng E-mail: tqiu@seu.edu.cn; Kong, Fan

    2015-06-28

    Indium-tin-oxide (ITO) nanoparticles were annealed in vacuum or reducing atmosphere to obtain different surface structures and investigate their influence on the adsorptive character and conformation of cytochrome c (Cyt c) molecule. Annealing-induced morphometric or structural changes of ITO nanoparticles were characterized by instruments of transmission electron microscopy, x-ray diffraction, and Raman scattering. Semiconductor ITO nanoparticle-enhanced Raman scattering of Cyt c was observed and the enhanced efficiency was found to closely depend on the surface structures which control the adsorbance of buffer anions needed for Cyt c loading. Direct electron transfer between Cyt c and ITO surface at the moment of molecular elastic collision was found and a reverse electron transfer process for O-terminated surface and metal-terminated surface was observed, according to absorption spectroscopic measurement on the residual solution.

  7. The effects of Kelvin-Helmholtz instability on resonance absorption layers in coronal loops

    NASA Technical Reports Server (NTRS)

    Karpen, Judith T.; Dahlburg, Russell B.; Davila, Joseph M.

    1994-01-01

    One of the long-standing uncertainties in the wave-resonance theory of coronal heating is the stability of the resonance layer. The wave motions in the resonance layer produce highly localized shear flows which vary sinusoidally in time with the resonance period. This configuration is potentially susceptible to the Kelvin-Helmholtz instability (KHI), which can enhance small-scale structure and turbulent broadening of shear layers on relatively rapid ideal timescales. We have investigated numerically the response of a characteristic velocity profile, derived from resonance absorption models, to finite fluid perturbations comparable to photospheric fluctuations. We find that the KHI primarily should affect long (approximately greater than 6 x 10(exp 4) km) loops where higher velocity flows (M approximately greater than 0.2) exist in resonance layers of order 100 km wide. There, the Kelvin-Helmholtz growth time is comparable to or less than the resonance quarter-period, and the potentially stabilizing magnetic effects are not felt until the instability is well past the linear growth stage. Not only is the resonance layer broadened by the KHI, but also the convective energy transport out of the resonance layer is increased, thus adding to the efficiency of the wave-resonance heating process. In shorter loops, e.g., those in bright points and compact flares, the stabilization due to the magnetic field and the high resonance frequency inhibit the growth of the Kelvin-Helmholtz instability beyond a minimal level.

  8. 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.

  9. Dispersion of electron-phonon resonances in one-layer graphene and its demonstration in micro-Raman scattering.

    PubMed

    Strelchuk, V V; Nikolenko, A S; Gubanov, V O; Biliy, M M; Bulavin, L A

    2012-11-01

    In the present work, we used Raman spectroscopy as sensitive tool for characterization of dispersion of electron-phonon resonances in one-layer graphene. We analyzed Stokes and anti-Stokes components of the Raman spectra to investigate the temperature dependence of the graphene G-band on the power of exciting radiation. Appearance and drastic intensity increase of zone-edge D-like modes caused by introduction of structural defects and/or deformations in the graphene layer were observed in the Raman spectra at high powers of excitation. We investigated phonon dispersion of one-layer graphene for iTO phonon branch at K point along K-M direction, which is involved in double-resonance Raman scattering. Raman dispersion slope of D-band is in good agreement with results of theoretical calculations based on the Green's functions approach based on the screened electron-electron interaction. Deviation of the experimental iTO phonon frequency from the linear dependence on excitation energy was observed at excitation E(exc) = 3.81 eV. Self-consistent classification of phonon states according to the symmetry for all dispersion branches of one-layer graphene was carried out.

  10. Omnidirectional and broadband absorption enhancement from trapezoidal Mie resonators in semiconductor metasurfaces

    PubMed Central

    Pala, Ragip A.; Butun, Serkan; Aydin, Koray; Atwater, Harry A.

    2016-01-01

    Light trapping in planar ultrathin-film solar cells is limited due to a small number of optical modes available in the thin-film slab. A nanostructured thin-film design could surpass this limit by providing broadband increase in the local density of states in a subwavelength volume and maintaining efficient coupling of light. Here we report a broadband metasurface design, enabling efficient and broadband absorption enhancement by direct coupling of incoming light to resonant modes of subwavelengthscale Mie nanoresonators defined in the thin-film active layer. Absorption was investigated both theoretically and experimentally in prototypes consisting of lithographically patterned, two-dimensional periodic arrays of silicon nanoresonators on silica substrates. A crossed trapezoid resonator shape of rectangular cross section is used to excite broadband Mie resonances across visible and near-IR spectra. Our numerical simulations, optical absorption measurements and photocurrent spectral response measurements demonstrate that crossed trapezoidal Mie resonant structures enable angle-insensitive, broadband absorption. A short circuit current density of 12.0 mA/cm2 is achieved in 210 nm thick patterned Si films, yielding a 4-fold increase compared to planar films of the same thickness. It is suggested that silicon metasurfaces with Mie resonator arrays can provide useful insights to guide future ultrathin-film solar cell designs incorporating nanostructured thin active layers. PMID:27641965

  11. Porogranular materials composed of elastic Helmholtz resonators for acoustic wave absorption.

    PubMed

    Griffiths, Stéphane; Nennig, Benoit; Job, Stéphane

    2017-01-01

    A theoretical and experimental study of the acoustic absorption of granular porous media made of non-cohesive piles of spherical shells is presented. These shells are either rigid or elastic, possibly drilled with a neck (Helmholtz resonators), and either porous or impervious. A description is given of acoustic propagation through these media using the effective medium models proposed by Johnson (rigid particles) and Boutin (rigid Helmholtz resonators), which are extended to the configurations studied in this work. A solution is given for the local equation of elasticity of a shell coupled to the viscous flow of air through the neck and the micropores. The models and the simulations are compared to absorption spectra measured in reflection in an impedance tube. The effective medium models and the measurements show excellent agreement for configurations made of rigid particles and rigid Helmholtz resonators that induce an additional peak of absorption at low frequency. A shift of the Helmholtz resonance toward low frequencies, due to the softness of the shells is revealed by the experiments for elastic shells made of soft elastomer and is well reproduced by the simulations. It is shown that microporous shells enhance and broaden acoustic absorption compared to stiff or elastic resonators.

  12. Hanle electromagnetically induced transparency and absorption resonances with a Laguerre Gaussian beam

    SciTech Connect

    Anupriya, J.; Ram, Nibedita; Pattabiraman, M.

    2010-04-15

    We describe a computational and experimental study on Hanle electromagnetically induced transparency and absorption resonance line shapes with a Laguerre Gaussian (LG) beam. It is seen that the LG beam profile brings about a significant narrowing in the line shape of the Hanle resonance and ground-state Zeeman coherence in comparison to a Gaussian beam. This narrowing is attributed to the azimuthal mode index of the LG field.

  13. Evidence for the 2B1-2A1 electronic transition in chlorine dioxide from resonance Raman depolarization ratios

    NASA Astrophysics Data System (ADS)

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

    1997-11-01

    The resonance Raman depolarization ratios of chlorine dioxide (OClO) dissolved in cyclohexane are measured and analyzed to establish the existence of a 2A1 excited state that is nearly degenerate with the optically stronger, 2A2 excited state. The depolarization ratio of the symmetric stretch fundamental transition is measured at several excitation wavelengths spanning the lowest-energy electronic transition centered at ˜360 nm. The depolarization ratio of this transition reaches a maximum value of 0.25±0.04 directly on resonance suggesting that scattered intensity is not derived from a single excited state. The depolarization ratios are modeled utilizing the time-dependent formalism for Raman scattering. This analysis demonstrates that the observed Raman depolarization ratios are derived from contributions of two excited states of 2A1 and 2A2 symmetry to the observed scattering. The results presented here support the emerging picture of OClO excited-state reaction dynamics in which photoexcitation to the 2A2 excited state is followed by internal conversion from this state to the 2A1 surface. Both the role of the 2A1 state in the photochemistry of OClO and the importance of this state in modeling resonance Raman intensities are discussed.

  14. Structural dynamics of phenylisothiocyanate in the light-absorbing excited states: Resonance Raman and complete active space self-consistent field calculation study

    SciTech Connect

    Ouyang, Bing Xue, Jia-Dan Zheng, Xuming E-mail: zxm@zstu.edu.cn; Fang, Wei-Hai E-mail: fangwh@dnu.edu.cn

    2014-05-21

    The excited state structural dynamics of phenyl isothiocyanate (PITC) after excitation to the light absorbing S{sub 2}(A′), S{sub 6}(A′), and S{sub 7}(A′) excited states were studied by using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The UV absorption bands of PITC were assigned. The vibrational assignments were done on the basis of the Fourier transform (FT)-Raman and FT-infrared measurements, the density-functional theory computations, and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohexane, acetonitrile, and methanol solvents were, respectively, obtained at 299.1, 282.4, 266.0, 252.7, 228.7, 217.8, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PITC. The results indicated that the structural dynamics in the S{sub 2}(A′), S{sub 6}(A′), and S{sub 7}(A′) excited states were very different. The conical intersection point CI(S{sub 2}/S{sub 1}) were predicted to play important role in the low-lying excited state decay dynamics. Two major decay channels were predicted for PITC upon excitation to the S{sub 2}(A′) state: the radiative S{sub 2,min} → S{sub 0} transition and the nonradiative S{sub 2} → S{sub 1} internal conversion via CI(S{sub 2}/S{sub 1}). The differences in the decay dynamics between methyl isothiocyanate and PITC in the first light absorbing excited state were discussed. The role of the intersystem crossing point ISC(S{sub 1}/T{sub 1}) in the excited state decay dynamics of PITC is evaluated.

  15. Structural dynamics of phenylisothiocyanate in the light-absorbing excited states: resonance Raman and complete active space self-consistent field calculation study.

    PubMed

    Ouyang, Bing; Xue, Jia-Dan; Zheng, Xuming; Fang, Wei-Hai

    2014-05-21

    The excited state structural dynamics of phenyl isothiocyanate (PITC) after excitation to the light absorbing S2(A'), S6(A'), and S7(A') excited states were studied by using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The UV absorption bands of PITC were assigned. The vibrational assignments were done on the basis of the Fourier transform (FT)-Raman and FT-infrared measurements, the density-functional theory computations, and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohexane, acetonitrile, and methanol solvents were, respectively, obtained at 299.1, 282.4, 266.0, 252.7, 228.7, 217.8, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PITC. The results indicated that the structural dynamics in the S2(A'), S6(A'), and S7(A') excited states were very different. The conical intersection point CI(S2/S1) were predicted to play important role in the low-lying excited state decay dynamics. Two major decay channels were predicted for PITC upon excitation to the S2(A') state: the radiative S(2,min) → S0 transition and the nonradiative S2 → S1 internal conversion via CI(S2/S1). The differences in the decay dynamics between methyl isothiocyanate and PITC in the first light absorbing excited state were discussed. The role of the intersystem crossing point ISC(S1/T1) in the excited state decay dynamics of PITC is evaluated.

  16. Strong forward-backward asymmetry of stimulated Raman scattering in lithium-niobate-based whispering gallery resonators.

    PubMed

    Leidinger, M; Sturman, B; Buse, K; Breunig, I

    2016-06-15

    We show experimentally and prove theoretically that the pump-power thresholds of stimulated Raman scattering (SRS) in lithium-niobate-based whispering gallery resonators (WGRs) are strongly different for the signal waves propagating in the backward and forward directions with respect to the pump wave. This feature is due to a strong polaritonic effect. It leads to a cascade of alternating forward-backward Raman lines with increasing pump power. The measured polarization and spectral properties of SRS are in good agreement with theory. Similar properties have to be inherent in other WGRs made of polar crystals.

  17. Vibrationally resonant imaging of a single living cell by supercontinuum-based multiplex coherent anti-Stokes Raman scattering microspectroscopy

    NASA Astrophysics Data System (ADS)

    Kano, Hideaki; Hamaguchi, Hiro-O.

    2005-02-01

    Supercontinuum-based multiplex coherent anti-Stokes Raman scattering (CARS) microspectroscopy has been applied to vibrational imaging of a living fission yeast cell. We have successfully extracted only a vibrationally resonant CARS image from a characteristic spectral profile in the C-H stretching vibrational region. Using our simple but sensitive analysis, the vibrational contrast is significantly improved in comparison with a CARS imaging at a fixed Raman shift. The CARS image of a living yeast cell indicates several areas at which the signal is remarkably strong. They are considered to arise from mitochondria.

  18. Resonant absorption induced fast melting studied with mid-IR QCLs

    NASA Astrophysics Data System (ADS)

    Lu, Jie; Lv, Yankun; Ji, Youxin; Tang, Xiaoliang; Qi, Zeming; Li, Liangbin

    2017-02-01

    We demonstrate the use of a pump-probe setup based on two mid-infrared quantum cascade lasers (QCLs) to investigate the melting and crystallization of materials through resonant absorption. A combination of pump and probe beams fulfills the two-color synchronous detection. Furthermore, narrow linewidth advances the accuracy of measurements and the character of broad tuning range of QCLs enables wide applications in various sample and multiple structures. 1-Eicosene was selected as a simple model system to verify the feasibility of this method. A pulsed QCL was tuned to the absorption peak of CH2 bending vibration at 1467 cm-1 to resonantly heat the sample. The other QCL in continuous mode was tuned to 1643 cm-1 corresponding the C=C stretching vibration to follow the fast melting dynamics. By monitoring the transmission intensity variation of pump and probe beams during pump-probe experiments, the resonant absorption induced fast melting and re-crystallization of 1-Eicosene can be studied. Results show that the thermal effect and melting behaviors strongly depend on the pump wavelength (resonant or non-resonant) and energy, as well as the pump time. The realization and detection of melting and recrystallization can be performed in tens of milliseconds, which improves the time resolution of melting process study based on general mid-infrared spectrum by orders of magnitude. The availability of resonant heating and detections based on mid-infrared QCLs is expected to enable new applications in melting study.

  19. Resonant Photoemission and M_{2,3}-Absorption Spectra in Nickel Dichloride

    NASA Astrophysics Data System (ADS)

    Igarashi, J.

    Ni 3p-resonant photoemission and Ni M_{2,3}-absorption spectra are calculated in detail on a cluster of (NiCl_6)^{4-} with the use of the transition matrix elements evaluated on the Herman-Skillman potential in Ni atom. Overall spectral shape agrees well with experiment, allowing a determination of the parameters which characterize Ni 3d and Cl 3p states. Resonance behavior is discussed near the Ni 3p-core level photothreshold. The resonant enhancement is found to be larger for the peak with higher binding energy in the d^7-multiplets.

  20. Coal thickness gauge using RRAS techniques, part 1. [radiofrequency resonance absorption

    NASA Technical Reports Server (NTRS)

    Rollwitz, W. L.; King, J. D.

    1978-01-01

    A noncontacting sensor having a measurement range of 0 to 6 in or more, and with an accuracy of 0.5 in or better is needed to control the machinery used in modern coal mining so that the thickness of the coal layer remaining over the rock is maintained within selected bounds. The feasibility of using the radiofrequency resonance absorption (RRAS) techniques of electron magnetic resonance (EMR) and nuclear magnetic resonance (NMR) as the basis of a coal thickness gauge is discussed. The EMR technique was found, by analysis and experiments, to be well suited for this application.

  1. Mechanism of resonant perfect optical absorption in dielectric film supporting metallic grating structures.

    PubMed

    Chen, Xiumei; Yan, Xiaopeng; Li, Ping; Mou, Yongni; Wang, Wenqiang; Guan, Zhiqiang; Xu, Hongxing

    2016-08-22

    The mechanism of resonant perfect optical absorbers is quantitatively revealed by the coupled mode method for the air/grating/dielectric film/air four region system. The sufficient and necessary conditions of the perfect optical absorption are derived from the interface scattering coefficients analyses. The coupling of the Fabry-Perot modes in the grating slits and non-zero order quasi waveguide modes in the dielectric film play a key role for the perfect optical absorption when the light is incident from the grating side. The analytical sufficient and necessary conditions of the perfect optical absorption provide an efficient tool towards geometry design for the perfect optical absorption at the specific wavelengths. The advantages of a widely tunable perfect optical absorption wavelength, a high Q factor and the confined energy loss on metal surfaces make the air/grating/film/air structures promising for applications in sensing, modulation and detection.

  2. Enhancing two-color absorption, self-phase modulation, and Raman microscopy signatures in tissue with femtosecond laser pulse shaping

    NASA Astrophysics Data System (ADS)

    Fischer, Martin C.; Piletic, Ivan; Fu, Dan; Matthews, Thomas E.; Liu, Henry; Samineni, Prathyush; Li, Baolei; Warren, Warren S.

    2009-02-01

    Nonlinear microscopies (most commonly, two-photon fluorescence, second harmonic generation, and coherent anti-Stokes Raman scattering (CARS)) have had notable successes in imaging a variety of endogenous and exogenous targets in recent years. These methods generate light at a color different from any of the exciting laser pulses, which makes the signal relatively easy to detect. Our work has focused on developing microscopy techniques using a wider range of nonlinear signatures (two-photon absorption of nonfluorescent species, self phase modulation) which have some specific advantages - for example, in recent papers we have shown that we can differentiate between different types of melanin in pigmented lesions, image hemoglobin and its oxygenation, and measure neuronal activity. In general, these signatures do not generate light at a different color and we rely on the advantages of femtosecond laser pulse shaping methods to amplify the signals and make them visible (for example, using heterodyne detection of the induced signal with one of the co-propagating laser pulses). Here we extend this work to stimulated Raman and CARS geometries. In the simplest experiments, both colors arise from filtering a single fs laser pulse, then modulating afterwards; in other cases, we demonstrate that spectral reshaping can retain high frequency resolution in Raman and CARS geometries with femtosecond laser pulses.

  3. Absorption enhancement in amorphous silicon thin films via plasmonic resonances in nickel silicide nanoparticles

    NASA Astrophysics Data System (ADS)

    Hachtel, Jordan; Shen, Xiao; Pantelides, Sokrates; Sachan, Ritesh; Gonzalez, Carlos; Dyck, Ondrej; Fu, Shaofang; Kalnayaraman, Ramki; Rack, Phillip; Duscher, Gerd

    2013-03-01

    Silicon is a near ideal material for photovoltaics due to its low cost, abundance, and well documented optical properties. The sole detriment of Si in photovoltaics is poor absorption in the infrared. Nanoparticle surface plasmon resonances are predicted to increase absorption by scattering to angles greater than the critical angle for total internal reflection (16° for a Si/air interface), trapping the light in the film. Experiments confirm that nickel silicide nanoparticles embedded in amorphous silicon increases absorption significantly in the infrared. However, it remains to be seen if electron-hole pair generation is increased in the solar cell, or whether the light is absorbed by the nanoparticles themselves. The nature of the absorption is explored by a study of the surface plasmon resonances through electron energy loss spectrometry and scanning transmission electron microscopy experiments, as well as first principles density functional theory calculations. Initial experimental results do not show strong plasmon resonances on the nanoparticle surfaces. Calculations of the optical properties of the nickel silicide particles in amorphous silicon are performed to understand why this resonance is suppressed. Work supported by NSF EPS 1004083 (TN-SCORE).

  4. Prototype explosives detection system based on nuclear resonance absorption in nitrogen

    SciTech Connect

    Morgado, R.E.; Arnone, G.; Cappiello, C.C.; Gardner, S.D.; Hollas, C.L.; Ussery, L.E.; White, J.M.; Zahrt, J.D.; Krauss, R.A.

    1993-12-01

    A-prototype explosives detection system that was developed for experimental evaluation of a nuclear resonance absorption techniques is described. The major subsystems are a proton accelerator and beam transport, high-temperature proton target, an airline-luggage tomographic inspection station, and an image-processing/detection- alarm subsystem. The detection system performance, based on a limited experimental test, is reported.

  5. Surface-enhanced resonance Raman study of the photoreduction of methylviologen on a p-InP semiconductor electrode

    SciTech Connect

    Feng, Q.; Cotton, T.M.

    1986-03-13

    The redox reactions of methylviologen (MV) at a silver electrode and at a p-InP electrode have been studied by cyclic voltammetry and Raman spectroscopy. By deposition of a silver island overlayer onto a p-InP semiconductor electrode the surface enhancement effect was obtained, allowing the MV reduction products formed at the semiconductor electrode to be monitored in situ. The photovoltaic response on p-InP electrode was not perturbed by the presence of the silver overlayer. Surface-enhanced resonance Raman (SERR) spectroscopy has verified the adsorption of the products from the reduction reactions MV/sup 2 +/ + e/sup -/ ..-->.. MV/sup +/. and MV/sup +/. + e/sup -/ ..-->.. MV/sup 0/. The Raman spectrum of one-electron and two-electron (MV/sup 0/) reduced methylviologen was obtained by exhaustive electrolysis in acetonitrile solution to provide an assignment of the surface spectra. 31 references, 4 figures.

  6. A magnetic-field enriched surface-enhanced resonance Raman spectroscopy strategy towards the early diagnosis of malaria

    NASA Astrophysics Data System (ADS)

    Clement, Yuen; Liu, Quan

    2012-02-01

    Early malaria diagnosis is important because malaria disease can develop into fatal illness within hours upon the appearance of the first symptom. The low concentration of the diagnosis biomarker, hemozoin, at the early stage of malaria disease makes early diagnosis difficult. In this paper, we present a magnetic field-enriched surface-enhanced resonance Raman spectroscopy (SERRS) strategy for the sensitive detection of β - hematin crystals, which is equivalent to hemozoin in the characteristics of Raman spectrum, by using magnetic nanoparticles. We observe several orders of magnitude enhancement in the SERRS signal of enriched β - hematin in comparison to the Raman signal of β - hematin in the cases of SERRS alone or magnetic enrichment alone, showing the great potential of this method towards early malaria diagnosis.

  7. A magnetic-field enriched surface-enhanced resonance Raman spectroscopy strategy towards the early diagnosis of malaria

    NASA Astrophysics Data System (ADS)

    Yuen, Clement; Liu, Quan

    2012-03-01

    Early malaria diagnosis is important because malaria disease can develop into fatal illness within hours upon the appearance of the first symptom. The low concentration of the diagnosis biomarker, hemozoin, at the early stage of malaria disease makes early diagnosis difficult. In this paper, we present a magnetic field-enriched surface-enhanced resonance Raman spectroscopy (SERRS) strategy for the sensitive detection of β - hematin crystals, which is equivalent to hemozoin in the characteristics of Raman spectrum, by using magnetic nanoparticles. We observe several orders of magnitude enhancement in the SERRS signal of enriched β - hematin in comparison to the Raman signal of β - hematin in the cases of SERRS alone or magnetic enrichment alone, showing the great potential of this method towards early malaria diagnosis.

  8. Multiferroic Materials Bi1-xSmxFeO3:. a Study of Raman and Absorption Spectroscopies

    NASA Astrophysics Data System (ADS)

    Minh, Nguyen Van; Thang, Dao Viet

    Multiferroic Bi1-xSmxFeO3 (x = 0.00, 0.05, 0.1, 0.15, 0.2) ceramics were prepared by conventional solid state reaction method. X-ray diffraction measurement was carried out to characterize the crystal structure and to detect the impurities existing in these ceramics. The substitution of rare earth Sm for Bi was found to decrease the impurity phase in BiFeO3 ceramics. There is strong evidence that both lattice constants a and c of the unit cell become smaller as the Sm3+ content is increased. The effect of introducing Sm3+ is shown to decrease the optical band gap for doped sample Bi1-xSmxFeO3. Additionally, the temperature-dependent Raman measurement performed for the lattice dynamics study of Bi1-xSmxFeO3 samples reveals a strong band centered at around 1000-1300 cm-1 which is associated with the resonant enhancement of two-phonon Raman scattering in the multiferroic Bi1-xSmxFeO3 samples. This two-phonon signal is shown to broaden with increasing x. The Raman spectra at low wavenumbers are suggested to be related with magnon in this system.

  9. Near-resonant rovibronic Raman scattering from 0 g + ( bb) valence state via the D0 u + ion-pair state in iodine molecule

    NASA Astrophysics Data System (ADS)

    Baturo, V. V.; Cherepanov, I. N.; Lukashov, S. S.; Petrov, A. N.; Poretsky, S. A.; Pravilov, A. M.

    2016-12-01

    Near-resonant Raman scattering from the electronic excited {I_2}( {0_g^ + ( {bb} )xrightarrow{{hv}}D0_u^ + to X0_g^ + } ) state via the intermediate ion-pair D0 u + state to the X one is observed for the first time. The Raman scattering follows a laser pulse. Its intensity I R is inversely proportional to the squared value of detuning from the resonant D, 22, 51 ← 0 g +( bb), 7, 52 transition, (Δν2)2, according to the theory of near-resonant Raman scattering. The ratio of Raman D → X scattering intensity to that of the D0 u +, ν D = 22, J D = 51 → X0 g + luminescence, I R / I D‒ X < 1.5 × 10-4 for Δν2 > 0.5 cm-1. The Raman and luminescence spectra are found to be identical.

  10. Negative refraction using Raman transitions and chirality

    SciTech Connect

    Sikes, D. E.; Yavuz, D. D.

    2011-11-15

    We present a scheme that achieves negative refraction with low absorption in far-off resonant atomic systems. The scheme utilizes Raman resonances and does not require the simultaneous presence of an electric-dipole transition and a magnetic-dipole transition near the same wavelength. We show that two interfering Raman tran-sitions coupled to a magnetic-dipole transition can achieve a negative index of refraction with low absorption through magnetoelectric cross-coupling. We confirm the validity of the analytical results with exact numerical simulations of the density matrix. We also discuss possible experimental implementations of the scheme in rare-earth metal atomic systems.

  11. Normal mode analysis of Pyrococcus furiosus rubredoxin via nuclear resonance vibrational spectroscopy (NRVS) and resonance raman spectroscopy.

    PubMed

    Xiao, Yuming; Wang, Hongxin; George, Simon J; Smith, Matt C; Adams, Michael W W; Jenney, Francis E; Sturhahn, Wolfgang; Alp, Ercan E; Zhao, Jiyong; Yoda, Y; Dey, Abishek; Solomon, Edward I; Cramer, Stephen P

    2005-10-26

    We have used (57)Fe nuclear resonance vibrational spectroscopy (NRVS) to study the Fe(S(cys))(4) site in reduced and oxidized rubredoxin (Rd) from Pyrococcus furiosus (Pf). The oxidized form has also been investigated by resonance Raman spectroscopy. In the oxidized Rd NRVS, strong asymmetric Fe-S stretching modes are observed between 355 and 375 cm(-1); upon reduction these modes shift to 300-320 cm(-1). This is the first observation of Fe-S stretching modes in a reduced Rd. The peak in S-Fe-S bend mode intensity is at approximately 150 cm(-1) for the oxidized protein and only slightly lower in the reduced case. A third band occurs near 70 cm(-1) for both samples; this is assigned primarily as a collective motion of entire cysteine residues with respect to the central Fe. The (57)Fe partial vibrational density of states (PVDOS) were interpreted by normal mode analysis with optimization of Urey-Bradley force fields. The three main bands were qualitatively reproduced using a D(2)(d) Fe(SC)(4) model. A C(1) Fe(SCC)(4) model based on crystallographic coordinates was then used to simulate the splitting of the asymmetric stretching band into at least 3 components. Finally, a model employing complete cysteines and 2 additional neighboring atoms was used to reproduce the detailed structure of the PVDOS in the Fe-S stretch region. These results confirm the delocalization of the dynamic properties of the redox-active Fe site. Depending on the molecular model employed, the force constant K(Fe-S) for Fe-S stretching modes ranged from 1.24 to 1.32 mdyn/A. K(Fe-S) is clearly diminished in reduced Rd; values from approximately 0.89 to 1.00 mdyn/A were derived from different models. In contrast, in the final models the force constants for S-Fe-S bending motion, H(S-Fe-S), were 0.18 mdyn/A for oxidized Rd and 0.15 mdyn/A for reduced Rd. The NRVS technique demonstrates great promise for the observation and quantitative interpretation of the dynamical properties of Fe-S proteins.

  12. Resonant optical absorption and defect control in Ta3N5 photoanodes

    NASA Astrophysics Data System (ADS)

    Dabirian, A.; van de Krol, R.

    2013-01-01

    In this study, we explore resonance-enhanced optical absorption in Ta3N5 photoanodes for water splitting. By using a reflecting Pt back-contact and appropriate Ta3N5 film thickness, the resonance frequency can be tuned to energies just above the bandgap, where the optical absorption is normally weak. The resonance results in a significant improvement in the photoanode's incident photon-to-current efficiency. The Ta3N5 films are made by high-temperature nitridation of Ta2O5. The nitridation time is found to be critical, as extended nitridation result in the formation of nitrogen vacancies through thermal reduction. These insights give important clues for the development of efficient (oxy)nitride-based photoelectrodes.

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

    PubMed

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

    2016-04-01

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

  14. Surface-enhanced resonance Raman spectroscopy as an ancillary high-performance liquid chromatography detector for nitrophenol compounds

    SciTech Connect

    Ni, F.; Thomas, L.; Cotton, T.M. )

    1989-04-15

    In this study, the potential application of surface-enhanced resonance Raman scattering (SERRS) spectroscopy as an off-line secondary detector for HPLC has been evaluated. Four nitrophenol compounds, 2-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol, and 4,6-dinitrocresol were separated by isocratic reverse-phase high-performance liquid chromatography (RP-HPLC) and monitored with a conventional UV detector. Resonance Raman (RR) and SERRS spectroscopy were next used to provide the required specificity for distinguishing the nitrophenol compounds. The SERRS detection limit for both 2-nitrophenol and 4-nitrophenol was calculated to be 14 ppb and that for 2,4-dinitrophenol and 4,6-dinitrocresol was estimated to lie near the parts-per-billion level as well. This detection limit is 2-3 orders of magnitude lower than that obtained by RR spectroscopy.

  15. UV Resonance Raman Elucidation of the Terminal and Internal Peptide Bond Conformations of Crystalline and Solution Oligoglycines

    PubMed Central

    Bykov, Sergei V.; Asher, Sanford A.

    2010-01-01

    Spectroscopic investigations of macromolecules generally attempt to interpret the measured spectra in terms of the summed contributions of the different molecular fragments. This is the basis of the local mode approximation in vibrational spectroscopy. In the case of resonance Raman spectroscopy independent contributions of molecular fragments require both a local mode-like behavior and the uncoupled electronic transitions. Here we show that the deep UV resonance Raman spectra of aqueous solution phase oligoglycines show independent peptide bond molecular fragment contributions indicating that peptide bonds electronic transitions and vibrational modes are uncoupled. We utilize this result to separately determine the conformational distributions of the internal and penultimate peptide bonds of oligoglycines. Our data indicate that in aqueous solution the oligoglycine terminal residues populate conformations similar to those found in crystals (31-helices and β-strands), but with a broader distribution, while the internal peptide bond conformations are centered around the 31-helix Ramachandran angles. PMID:20657703

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

    PubMed

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

    2015-01-01

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

  17. A Potential Remote-Sensing Technique for Thermospheric Temperature with Ground-Based Resonant Atomic Oxygen Raman Lidar

    DTIC Science & Technology

    2005-01-01

    Journal of Atmospheric and Solar - Terrestrial Physics I (l111) Ill-Ill...2005.10.001 -T UTIO, STATEMENT A Approved for Public Release Distribution Unlimited 2 RD. Sharma, P.D. Dao / Journal of Atmospheric and Solar - Terrestrial Physics I...differential cross section (Measures, 1984). because it is not involved in the resonant Raman excitation. R.D. Sharma, P.D. Dao / Journal of Atmospheric and

  18. E{sub 1} Gap of Wurtzite InAs Single Nanowires Measured by Means of Resonant Raman Spectroscopy

    SciTech Connect

    Moeller, M.; Lima, M. M. Jr. de; Cantarero, A.; Dacal, L. C. O.; Iikawa, F.; Chiaramonte, T.; Cotta, M. A.

    2011-12-23

    Indium arsenide nanowires were synthesized with an intermixing of wurtzite and zincblende structure by chemical beam epitaxy with the vapor-liquid-solid mechanism. Resonant Raman spectroscopy of the transverse optical phonon mode at 215 cm{sup -1} reveals an E{sub 1} gap of 2.47 eV which is assigned to the electronic band gap at the A point in the indium arsenide wurtzite phase.

  19. DNA sequence detection using surface-enhanced resonance Raman spectroscopy in a homogeneous multiplexed assay.

    PubMed

    MacAskill, Alexandra; Crawford, David; Graham, Duncan; Faulds, Karen

    2009-10-01

    Detection of specific DNA sequences is central to modern molecular biology and also to molecular diagnostics where identification of a particular disease is based on nucleic acid identification. Many methods exist, and fluorescence spectroscopy dominates the detection technologies employed with different assay formats. This study demonstrates the use of surface-enhanced resonance Raman scattering (SERRS) to detect specific DNA sequences when coupled with modified SERRS-active probes that have been designed to modify the affinity of double- and single-stranded DNA for the surface of silver nanoparticles resulting in discernible differences in the SERRS which can be correlated to the specific DNA hybridization event. The principle of the assay lies on the lack of affinity of double-stranded DNA for silver nanoparticle surfaces; therefore, hybridization of the probe to the target results in a reduction in the SERRS signal. Use of locked nucleic acid (LNA) residues in the DNA probes resulted in greater discrimination between exact match and mismatches when used in comparison to unmodified labeled DNA probes. Polymerase chain reaction (PCR) products were detected using this methodology, and ultimately a multiplex detection of sequences relating to a hospital-acquired infection, namely, methicillin-resistant Staphylococcus aureus (MRSA), demonstrated the versatility and applicability of this approach to real-life situations.

  20. Resonance Raman Spectroscopic Evaluation of Skin Carotenoids as a Biomarker of Carotenoid Status for Human Studies

    PubMed Central

    Mayne, Susan T.; Cartmel, Brenda; Scarmo, Stephanie; Jahns, Lisa; Ermakov, Igor V.; Gellermann, Werner

    2013-01-01

    Resonance Raman Spectroscopy (RRS) is a non-invasive method that has been developed to assess carotenoid status in human tissues including human skin in vivo. Skin carotenoid status has been suggested as a promising biomarker for human studies. This manuscript describes research done relevant to the development of this biomarker, including its reproducibility, validity, feasibility for use in field settings, and factors that affect the biomarker such as diet, smoking, and adiposity. Recent studies have evaluated the response of the biomarker to controlled carotenoid interventions, both supplement-based and dietary [e.g., provision of a high-carotenoid fruit and vegetable (F/V)-enriched diet], demonstrating consistent response to intervention. The totality of evidence supports the use of skin carotenoid status as an objective biomarker of F/V intake, although in the cross-sectional setting, diet explains only some of the variation in this biomarker. However, this limitation is also a strength in that skin carotenoids may effectively serve as an integrated biomarker of health, with higher status reflecting greater F/V intake, lack of smoking, and lack of adiposity. Thus, this biomarker holds promise as both a health biomarker and an objective indicator of F/V intake, supporting its further development and utilization for medical and public health purposes. PMID:23823930

  1. Intermolecular hydrogen bonding in chlorine dioxide photochemistry: A time-resolved resonance Raman study

    NASA Astrophysics Data System (ADS)

    Philpott, Matthew P.; Hayes, Sophia C.; Thomsen, Carsten L.; Reid, Philip J.

    2001-01-01

    The geminate-recombination and vibrational-relaxation dynamics of chlorine dioxide (OClO) dissolved in ethanol and 2,2,2-trifluoroethanol (TFE) are investigated using time-resolved resonance Raman spectroscopy. Stokes spectra are measured as a function of time following photoexcitation using degenerate pump and probe wavelengths of 398 nm. For OClO dissolved in ethanol, subpicosecond geminate recombination occurs resulting in the reformation of ground-state OClO with a quantum yield of 0.5±0.1. Following recombination, intermolecular-vibrational relaxation of OClO occurs with a time constant of 31±10 ps. For OClO dissolved in TFE, recombination occurs with a time constant of 1.8±0.8 ps and a quantum yield of only 0.3±0.1. The intermolecular-vibrational-relaxation time constant of OClO in TFE is 79±27 ps. The reduced geminate-recombination quantum yield, delayed recombination, and slower vibrational relaxation for OClO in TFE is interpreted in terms of greater self-association of the solvent. Degenerate pump-probe experiments are also presented that demonstrate decay of the Cl-solvent charge-transfer complex on the ˜1-ns time scale in ethanol and TFE. This time is significantly longer than the abstraction times observed for other systems demonstrating that Cl hydrogen abstraction from alcohols occurs in the presence of a significant energy barrier.

  2. Resonance Raman interrogation of the consequences of heme rotational disorder in myoglobin and its ligated derivatives.

    PubMed

    Rwere, Freeborn; Mak, Piotr J; Kincaid, James R

    2008-12-02

    Resonance Raman spectroscopy is employed to characterize heme site structural changes arising from conformational heterogeneity in deoxyMb and ligated derivatives, i.e., the ferrous CO (MbCO) and ferric cyanide (MbCN) complexes. The spectra for the reversed forms of these derivatives have been extracted from the spectra of reconstituted samples. Dramatic changes in the low-frequency spectra are observed, where newly observed RR modes of the reversed forms are assigned using protohemes that are selectively deuterated at the four methyl groups or at the four methine carbons. Interestingly, while substantial changes in the disposition of the peripheral vinyl and propionate groups can be inferred from the dramatic spectral shifts, the bonds to the internal histidyl imidazole ligand and those of the Fe-CO and Fe-CN fragments are not significantly affected by the heme rotation, as judged by lack of significant shifts in the nu(Fe-N(His)), nu(Fe-C), and nu(C-O) modes. In fact, the apparent lack of an effect on these key vibrational parameters of the Fe-N(His), Fe-CO, and Fe-CN fragments is entirely consistent with previously reported equilibrium and kinetic studies that document virtually identical functional properties for the native and reversed forms.

  3. Sensitive molecular diagnostics using surface-enhanced resonance Raman scattering (SERRS)

    NASA Astrophysics Data System (ADS)

    Faulds, Karen; Graham, Duncan; McKenzie, Fiona; MacRae, Douglas; Ricketts, Alastair; Dougan, Jennifer

    2009-02-01

    Surface enhanced resonance Raman scattering (SERRS) is an analytical technique with several advantages over competitive techniques in terms of improved sensitivity and multiplexing. We have made great progress in the development of SERRS as a quantitative analytical method, in particular for the detection of DNA. SERRS is an extremely sensitive and selective technique which when applied to the detection of labelled DNA sequences allows detection limits to be obtained which rival, and in most cases, are better than fluorescence. Here the conditions are explored which will enable the successful detection of DNA using SERRS. The enhancing surface which is used is crucial and in this case suspensions of nanoparticles were used as they allow quantitative behaviour to be achieved and allow analogous systems to current fluorescence based systems to be made. The aggregation conditions required to obtain SERRS of DNA are crucial and herein we describe the use of spermine as an aggregating agent. The nature of the label which is used, be it fluorescent, positively or negatively charged also effects the SERRS response and these conditions are again explored here. We have clearly demonstrated the ability to identify the components of a mixture of 5 analytes in solution by using two different excitation wavelengths and also of a 6-plex using data analysis techniques. These conditions will allow the use of SERRS for the detection of target DNA in a meaningful diagnostic assay.

  4. Resonance Raman spectroscopic evaluation of skin carotenoids as a biomarker of carotenoid status for human studies.

    PubMed

    Mayne, Susan T; Cartmel, Brenda; Scarmo, Stephanie; Jahns, Lisa; Ermakov, Igor V; Gellermann, Werner

    2013-11-15

    Resonance Raman spectroscopy (RRS) is a non-invasive method that has been developed to assess carotenoid status in human tissues including human skin in vivo. Skin carotenoid status has been suggested as a promising biomarker for human studies. This manuscript describes research done relevant to the development of this biomarker, including its reproducibility, validity, feasibility for use in field settings, and factors that affect the biomarker such as diet, smoking, and adiposity. Recent studies have evaluated the response of the biomarker to controlled carotenoid interventions, both supplement-based and dietary [e.g., provision of a high-carotenoid fruit and vegetable (F/V)-enriched diet], demonstrating consistent response to intervention. The totality of evidence supports the use of skin carotenoid status as an objective biomarker of F/V intake, although in the cross-sectional setting, diet explains only some of the variation in this biomarker. However, this limitation is also a strength in that skin carotenoids may effectively serve as an integrated biomarker of health, with higher status reflecting greater F/V intake, lack of smoking, and lack of adiposity. Thus, this biomarker holds promise as both a health biomarker and an objective indicator of F/V intake, supporting its further development and utilization for medical and public health purposes.

  5. Accurate Simulation of Resonance-Raman Spectra of Flexible Molecules: An Internal Coordinates Approach.

    PubMed

    Baiardi, Alberto; Bloino, Julien; Barone, Vincenzo

    2015-07-14

    The interpretation and analysis of experimental resonance-Raman (RR) spectra can be significantly facilitated by vibronic computations based on reliable quantum-mechanical (QM) methods. With the aim of improving the description of large and flexible molecules, our recent time-dependent formulation to compute vibrationally resolved electronic spectra, based on Cartesian coordinates, has been extended to support internal coordinates. A set of nonredundant delocalized coordinates is automatically generated from the molecular connectivity thanks to a new general and robust procedure. In order to validate our implementation, a series of molecules has been used as test cases. Among them, rigid systems show that normal modes based on Cartesian and delocalized internal coordinates provide equivalent results, but the latter set is much more convenient and reliable for systems characterized by strong geometric deformations associated with the electronic transition. The so-called Z-matrix internal coordinates, which perform well for chain molecules, are also shown to be poorly suited in the presence of cycles or nonstandard structures.

  6. Quantitative methods for structural characterization of proteins based on deep UV resonance Raman spectroscopy.

    PubMed

    Shashilov, Victor A; Sikirzhytski, Vitali; Popova, Ludmila A; Lednev, Igor K

    2010-09-01

    Here we report on novel quantitative approaches for protein structural characterization using deep UV resonance Raman (DUVRR) spectroscopy. Specifically, we propose a new method combining hydrogen-deuterium (HD) exchange and Bayesian source separation for extracting the DUVRR signatures of various structural elements of aggregated proteins including the cross-beta core and unordered parts of amyloid fibrils. The proposed method is demonstrated using the set of DUVRR spectra of hen egg white lysozyme acquired at various stages of HD exchange. Prior information about the concentration matrix and the spectral features of the individual components was incorporated into the Bayesian equation to eliminate the ill-conditioning of the problem caused by 100% correlation of the concentration profiles of protonated and deuterated species. Secondary structure fractions obtained by partial least squares (PLS) and least squares support vector machines (LS-SVMs) were used as the initial guess for the Bayessian source separation. Advantages of the PLS and LS-SVMs methods over the classical least squares calibration (CLSC) are discussed and illustrated using the DUVRR data of the prion protein in its native and aggregated forms.

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

    PubMed Central

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

    2016-01-01

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

  8. Anomalous non-resonant microwave absorption in SmFeAs(O,F) polycrystalline sample

    NASA Astrophysics Data System (ADS)

    Onyancha, R. B.; Shimoyama, J.; Singh, S. J.; Hayashi, K.; Ogino, H.; Srinivasu, V. V.

    2017-02-01

    Here we present the non-resonant microwave absorption (NRMA) studies on SmFeAsO0.88F0.12 polycrystalline sample measured at 6.06 K with the magnetic field swept from -250 G to +250 G at a frequency of 9.45 GHz. It was observed that the (NRMA) line shape evolves as a function of microwave power. Again, the signal intensity increases from 22.83 μW to 0.710 mW where it reaches a maximum and quite remarkably it changed from 'normal' absorption to 'anomalous' absorption at 2.247 mW, then the intensity decreases with further increase of microwave power. The crossover from 'normal' to 'anomalous' NRMA absorption and its dependence on microwave power is a new phenomenon in iron pnictides superconductors and we have attributed this anomaly to come from non-hysteretic Josephson junction.

  9. Auger resonant Raman spectroscopy used to study the angular distributions of the Xe 4d{sub 5/2} {yields} 6p decay spectrum

    SciTech Connect

    Langer, B.; Berrah, N.; Farhat, A.

    1997-04-01

    Auger resonant Raman spectroscopy is a powerful tool for studying the resonant Auger decay processes with a resolution narrower than the natural lifetime width of the initial inner-shell hole state. This effect has been used to analyze branching ratios of resonantly excited atoms and molecules. In this paper, the authors present results of a study of angular distributions of the spectator decay lines of Xe following 4d{sub 5/2}{r_arrow}6p excitation using the Auger resonant Raman effect and highly resolved photons from the Advanced Light Source (ALS).

  10. Demonstration of composite signal enhancement from surface enhanced Raman spectroscopy in a liquid core optical ring resonator

    NASA Astrophysics Data System (ADS)

    White, Ian M.; Gohring, John; Fan, Xudong

    2007-09-01

    Surface enhanced Raman spectroscopy (SERS) utilizing silver colloids for localized plasmonic enhancement has been heavily researched due to its tremendous increase in the Raman signal of bio/chemical molecules. We demonstrate further enhancement by multiplying the SERS effect by the resonant enhancement of a ring resonator microcavity. The liquid core optical ring resonator (LCORR) offers a high-performance and practical design to obtain this composite enhancement for bio/chemical molecule detection. The LCORR integrates an array of optical ring resonators into a capillary-based microfluidic channel to form a novel bio/chemical sensing platform. The circular cross-section of the glass capillary acts as an optical ring resonator, with the evanescent field of the resonant light interacting with the sample passing through the capillary. The LCORR has already been well-studied for applications in label free biomolecule sensing. In this work, we utilize a silver colloid solution inside the capillary to perform SERS-based detection. In contrast to a typical SERS system where the incident light interacts with the colloid and target molecules only once, in the LCORR system, the tightly confined light resonates around the capillary wall, repeatedly interacting with the SERS system. Our experimental results show the increased enhancement due to the composite effect of the cavity resonance and the localized plasmonic effect of the nanoparticles inside the cavity. We have achieved detection of 3.3 nM R6G inside the LCORR. In addition to the excellent sensitivity, this detection system represents an advancement in the development of practical SERS bio/chemical sensors due to the arrayed nature of the sensors combined with the integrated microfluidics of the LCORR.

  11. Tunable absorption resonances in the ultraviolet for InP nanowire arrays.

    PubMed

    Aghaeipour, Mahtab; Anttu, Nicklas; Nylund, Gustav; Samuelson, Lars; Lehmann, Sebastian; Pistol, Mats-Erik

    2014-11-17

    The ability to tune the photon absorptance spectrum is an attracting way of tailoring the response of devices like photodetectors and solar cells. Here, we measure the reflectance spectra of InP substrates patterned with arrays of vertically standing InP nanowires. Using the reflectance spectra, we calculate and analyze the corresponding absorptance spectra of the nanowires. We show that we can tune absorption resonances for the nanowire arrays into the ultraviolet by decreasing the diameter of the nanowires. When we compare our measurements with electromagnetic modeling, we generally find good agreement. Interestingly, the remaining differences between modeled and measured spectra are attributed to a crystal-phase dependence in the refractive index of InP. Specifically, we find indication of significant differences in the refractive index between the modeled zinc-blende InP nanowires and the measured wurtzite InP nanowires in the ultraviolet. We believe that such crystal-phase dependent differences in the refractive index affect the possibility to excite optical resonances in the large wavelength range of 345 < λ < 390 nm. To support this claim, we investigated how resonances in nanostructures can be shifted in wavelength by geometrical tuning. We find that dispersion in the refractive index can dominate over geometrical tuning and stop the possibility for such shifting. Our results open the door for using crystal-phase engineering to optimize the absorption in InP nanowire-based solar cells and photodetectors.

  12. Resonant terahertz absorption by plasmons in grating-gate GaN HEMT structures

    NASA Astrophysics Data System (ADS)

    Muravjov, A. V.; Veksler, D. B.; Hu, X.; Gaska, R.; Pala, N.; Saxena, H.; Peale, R. E.; Shur, M. S.

    2009-05-01

    Pronounced resonant absorption and frequency dispersion associated with an excitation of collective 2D plasmons have been observed in terahertz (0.5-4THz) transmission spectra of grating-gate 2D electron gas AlGaN/GaN HEMT (high electron mobility transistor) structures at cryogenic temperatures. The resonance frequencies correspond to plasmons with wavevectors equal to the reciprocal-lattice vectors of the metal grating, which serves both as a gate electrode for the HEMT and a coupler between plasmons and incident terahertz radiation. The resonances are tunable by changing the applied gate voltage, which controls 2D electron gas concentration in the channel. The effect can be used for resonant detection of terahertz radiation and for "on-chip" terahertz spectroscopy.

  13. Electron Spin Resonance and optical absorption spectroscopic studies of manganese centers in aluminium lead borate glasses.

    PubMed

    SivaRamaiah, G; LakshmanaRao, J

    2012-12-01

    Electron Spin Resonance (ESR) and optical absorption studies of 5Al(2)O(3)+75H(3)BO(3)+(20-x)PbO+xMnSO(4) (where x=0.5, 1,1.5 and 2 mol% of MnSO(4)) glasses at room temperature have been studied. The ESR spectrum of all the glasses exhibits resonance signals with effective isotropic g values at ≈2.0, 3.3 and 4.3. The ESR resonance signal at isotropic g≈2.0 has been attributed to Mn(2+) centers in an octahedral symmetry. The ESR resonance signals at isotropic g≈3.3 and 4.3 have been attributed to the rhombic symmetry of the Mn(2+) ions. The zero-field splitting parameter (zfs) has been calculated from the intensities of the allowed hyperfine lines. The optical absorption spectrum exhibits an intense band in the visible region and it has been attributed to (5)E(g)→(5)T(2g) transition of Mn(3+)centers in an octahedral environment. The optical band gap and the Urbach energies have been calculated from the ultraviolet absorption edges.

  14. Transmission Loss and Absorption of Corrugated Core Sandwich Panels With Embedded Resonators

    NASA Technical Reports Server (NTRS)

    Allen, Albert R.; Schiller, Noah H.; Zalewski, Bart F.; Rosenthal, Bruce N.

    2014-01-01

    The effect of embedded resonators on the diffuse field sound transmission loss and absorption of composite corrugated core sandwich panels has been evaluated experimentally. Two 1.219 m × 2.438 m panels with embedded resonator arrangements targeting frequencies near 100 Hz were evaluated using non-standard processing of ASTM E90-09 acoustic transmission loss and ASTM C423-09a room absorption test measurements. Each panel is comprised of two composite face sheets sandwiching a corrugated core with a trapezoidal cross section. When inlet openings are introduced in one face sheet, the chambers within the core can be used as embedded acoustic resonators. Changes to the inlet and chamber partition locations allow this type of structure to be tuned for targeted spectrum passive noise control. Because the core chambers are aligned with the plane of the panel, the resonators can be tuned for low frequencies without compromising the sandwich panel construction, which is typically sized to meet static load requirements. Absorption and transmission loss performance improvements attributed to opening the inlets were apparent for some configurations and inconclusive for others.

  15. Dual-band microwave absorption properties of metamaterial absorber composed of split ring resonator on carbonyl iron powder composites

    NASA Astrophysics Data System (ADS)

    Lim, Jun-Hee; Ryu, Yo-Han; Kim, Sung-Soo

    2015-05-01

    This study investigated the dual-band absorption properties of metamaterial absorbers composed of a split ring resonator (SRR) on a grounded magnetic substrate. Polymer composites of carbonyl iron powders (CIP) of high permeability and magnetic loss were used as the substrate material. Computational tools were used to model the interaction between electromagnetic waves and materials with the SRR structure. For perpendicular polarization with an electric field (E) perpendicular to the SRR gap, dualband absorption peaks are predicted in the simulation result of reflection loss. Magnetic resonance resulting from antiparallel currents between the SRR and the ground plane is observed at the frequencies of two absorption peaks. The first strong absorption peak at the lower frequency (3.3 GHz) is due to magnetic resonance at the wire part of the SRR. The second absorption peak at the higher frequency (7.2 GHz) is due to magnetic resonance at the SRR split gap. The decreased capacitance with increased gap spacing moves the second absorption frequency to higher frequencies, while the first absorption peak is invariant with gap spacing. In the case of dual gaps at the opposite sides of the SRR, a single absorption peak is predicted due to the elimination of low-frequency resonance. For parallel polarization with the E-field parallel to the SRR gap, a single absorption peak is predicted, corresponding to magnetic resonance at the SRR wire.[Figure not available: see fulltext.

  16. Chromophore Structure in Lumirhodopsin and Metarhodopsin I by Time-Resolved Resonance Raman Microchip Spectroscopy†

    PubMed Central

    Pan, Duohai; Mathies, Richard A.

    2005-01-01

    Time-resolved resonance Raman microchip flow experiments have been performed on the lumirhodopsin (Lumi) and metarhodopsin I (Meta I) photointermediates of rhodopsin at room temperature to elucidate the structure of the chromophore in each species as well as changes in protein-chromophore interactions. Transient Raman spectra of Lumi and Meta I with delay times of 16 μs and 1 ms, respectively, are obtained by using a microprobe system to focus displaced pump and probe laser beams in a microfabricated flow channel and to detect the scattering. The fingerprint modes of both species are very similar and characteristic of an all-trans chromophore. Lumi exhibits a relatively normal hydrogen-outof-plane (HOOP) doublet at 951/959 cm-1, while Meta I has a single HOOP band at 957 cm-1. These results suggest that the transitions from bathorhodopsin to Lumi and Meta I involve a relaxation of the chromophore to a more planar all-trans conformation and the elimination of the structural perturbation that uncouples the 11H and 12H wags in bathorhodopsin. Surprisingly, the protonated Schiff base C=N stretching mode in Lumi (1638 cm-1) is unusually low compared to those in rhodopsin and bathorhodopsin, and the C=ND stretching mode shifts down by only 7 cm-1 in D2O buffer. This indicates that the Schiff base hydrogen bonding is dramatically weakened in the bathorhodopsin to Lumi transition. However, the C=ND stretching mode in Meta I is found at 1654 cm-1 and exhibits a normal deuteration-induced downshift of 24 cm-1, identical to that of the all-trans protonated Schiff base. The structural relaxation of the chromophore—protein complex in the bathorhodopsin to Lumi transition thus appears to drive the Schiff base group out of its hydrogen-bonded environment near Glu113, and the hydrogen bonding recovers to a normal solvated PSB value but presumably a different hydrogen bond acceptor with the formation of Meta I. PMID:11425321

  17. Synthesis, multi-nonlinear dielectric resonance and electromagnetic absorption properties of hcp-cobalt particles

    NASA Astrophysics Data System (ADS)

    Wen, Shulai; Liu, Ying; Zhao, Xiuchen; Cheng, Jingwei; Li, Hong

    2014-03-01

    Hcp-cobalt particles were successfully prepared by a liquid phase reduction method, and the microstructure, static magnetic properties, electromagnetic and microwave absorption properties of the cobalt particles with irregular shape were investigated in detail. The measured results indicate that the saturation magnetization was less than that of hcp-Co single crystals, and the coercivity was larger than that of bulk cobalt crystal. The permittivity presents multi-nonlinear dielectric resonance, which may result from the irregular shape containing parts of cutting angle of dodecahedron of cobalt particles. The real part of permeability decreases with the frequency, and the imaginary part has a wide resonant peak. The paraffin-based composite containing 70 wt% cobalt particles possessed strong absorption characteristics with a minimum RL of -38.97 dB at 10.81 GHz and an absorption band with RL under -10 dB from 8.72 to 13.26 GHz when the thickness is 1.8 mm, which exhibits excellent microwave absorption in middle and high frequency. The architectural design of material morphologies is important for improving microwave absorption properties toward future application.

  18. Engineered absorption enhancement and induced transparency in coupled molecular and plasmonic resonator systems.

    PubMed

    Adato, Ronen; Artar, Alp; Erramilli, Shyamsunder; Altug, Hatice

    2013-06-12

    Coupled plasmonic resonators have become the subject of significant research interest in recent years as they provide a route to dramatically enhanced light-matter interactions. Often, the design of these coupled mode systems draws intuition and inspiration from analogies to atomic and molecular physics systems. In particular, they have been shown to mimic quantum interference effects, such as electromagnetically induced transparency (EIT) and Fano resonances. This analogy also been used to describe the surface-enhanced absorption effect where a plasmonic resonance is coupled to a weak molecular resonance. These important phenomena are typically described using simple driven harmonic (or linear) oscillators (i.e., mass-on-a-spring) coupled to each other. In this work, we demonstrate the importance of an essential interdependence between the rate at which the system can be driven by an external field and its damping rate through radiative loss. This link is required in systems exhibiting time-reversal symmetry and energy conservation. Not only does it ensure an accurate and physically consistent description of resonant systems but leads directly to interesting new effects. Significantly, we demonstrate this dependence to predict a transition between EIT and electromagnetically induced absorption that is solely a function of the ratio of the radiative to intrinsic loss rates in coupled resonator systems. Leveraging the temporal coupled mode theory, we introduce a unique and intuitive picture that accurately describes these effects in coupled plasmonic/molecular and fully plasmonic systems. We demonstrate our approach's key features and advantages analytically as well as experimentally through surface-enhanced absorption spectroscopy and plasmonic metamaterial applications.

  19. Structure and reactivity of thiazolium azo dyes: UV-visible, resonance Raman, NMR, and computational studies of the reaction mechanism in alkaline solution.

    PubMed

    Abbott, Laurence C; Batchelor, Stephen N; Moore, John N

    2013-03-07

    UV-visible absorption, resonance Raman, and (1)H NMR spectroscopy, allied with density functional theory (DFT) calculations, have been used to study the structure, bonding, and alkaline hydrolysis mechanism of the cationic thiazloium azo dye, 2-[2-[4-(diethylamino)phenyl]diazenyl]-3-methyl-thiazolium (1a), along with a series of six related dyes with different 4-dialkylamino groups and/or other phenyl ring substituents (2a-c, 3a-c) and the related isothiazolium azo dye, 5-[2-[4-(dimethylamino)phenyl]diazenyl]-2-methyl-isothiazolium (4). These diazahemicyanine dyes are calculated to have a similar low-energy structure that is cis, trans at the (iso)thiazolium-azo group, and for which the calculated Raman spectra provide a good match with the experimental data; the calculations on these structures are used to assign and discuss the transitions giving rise to the experimental spectra, and to consider the bonding and its variation between the dyes. UV-visible, Raman, and NMR spectra recorded from minutes to several weeks after raising the pH of an aqueous solution of 1a to ca. 11.5 show that the dominant initial step in the reaction is loss of diethylamine to produce a quinonimine (ca. hours), with subsequent reactions occurring on longer time scales (ca. days to weeks); kinetic analyses give a rate constant of 2.6 × 10(-2) dm(3) mol(-1) s(-1) for reaction of 1a with OH(-). UV-visible spectra recorded on raising the pH of the other dyes in solution show similar changes that are attributed to the same general reaction mechanism, but with different rate constants for which the dependence on structure is discussed.

  20. Laser remote sensing of atmospheric temperature by observing resonant absorption of oxygen

    NASA Technical Reports Server (NTRS)

    Kalshoven, J. E., Jr.; Korb, C. L.; Schwemmer, G. K.; Dombrowski, M.

    1981-01-01

    A dual-frequency system is used to demonstrate the measurement of atmospheric temperature, through laser energy absorption monitoring at the center of an O2 resonant absorption line near 770 nm. It is shown that the average temperature of a 1 km path can be determined within 1.0 C, with a noise level of 0.3 C. An iterative algebraic expression for this method was developed, and is shown to be applicable in the troposphere; the effects of pressure and humidity on temperature determination were made clear by the algorithm and found to be small near the earth's surface.

  1. Dual structure of saturated absorption resonance at an open atomic transition

    NASA Astrophysics Data System (ADS)

    Vasil'ev, V. V.; Velichanskii, V. L.; Zibrov, S. A.; Sivak, A. V.; Brazhnikov, D. V.; Taichenachev, A. V.; Yudin, V. I.

    2011-05-01

    Experiments on open transitions of the D 1 line of alkali metals (Cs and Rb isotopes) reveal the dual structure of saturated absorption resonance in the signal of a high-intensity optical wave in the presence of a low-intensity counterpropagating wave. Theoretical analysis shows that the observed shape of the resonance is associated with the openness of the atomic transition as well as with the Doppler effect for atoms in a gas. The results are of general physical significance for nonlinear spectroscopy and can also find application in metrology (frequency and time standards on open transitions).

  2. Dual structure of saturated absorption resonance at an open atomic transition

    SciTech Connect

    Vasil'ev, V. V. Velichanskii, V. L. Zibrov, S. A.; Sivak, A. V.; Brazhnikov, D. V. Taichenachev, A. V. Yudin, V. I.

    2011-05-15

    Experiments on open transitions of the D{sub 1} line of alkali metals (Cs and Rb isotopes) reveal the dual structure of saturated absorption resonance in the signal of a high-intensity optical wave in the presence of a low-intensity counterpropagating wave. Theoretical analysis shows that the observed shape of the resonance is associated with the openness of the atomic transition as well as with the Doppler effect for atoms in a gas. The results are of general physical significance for nonlinear spectroscopy and can also find application in metrology (frequency and time standards on open transitions).

  3. Pion Absorption in 3, 4He and πN Resonances

    NASA Astrophysics Data System (ADS)

    Orphanos, L.; Källne, J.; Altemus, R.; Gugelot, P. C.; McCarthy, J. S.; Minehart, R. C.; Gram, P. A. M.; Höistad, B.; Morris, C. L.; Wadlinger, E. A.; Perdrisat, C.

    1981-06-01

    The cross sections of 3,4He(π-,n)2,3H have been measured at 285, 428, 525, and 575 MeV, extending the information on the energy dependence beyond the region previously known (50-300 MeV). The cross sections beyond the region of the Δ resonance are found to decrease less rapidly than that of the elementary πd-->pp process. This energy dependence suggests that pion absorption in a nucleus is associated with π+N (off-shell) scattering which includes I=12 πN resonances that are strongly suppressed in πd-->pp.

  4. Multiple-overtone resonance Raman scattering and fluorescence from I{sub 2} species adsorbed on silver surfaces

    SciTech Connect

    Sibbald, M.S.; Chumanov, G.; Small, G.; Cotton, T.M.

    1998-07-01

    A detailed excitation profile of a Raman progression consisting of up to six overtones and a fundamental band at 123 cm{sup {minus}1} observed from iodide adsorbed on an electrochemically roughened silver surface at 20 K is analyzed. The excitation profile was constructed from 77 spectra obtained by tuning the laser wavelength in {approximately}0.25 nm steps through the spectral range 409 nm{endash}433 nm. The shift between resonances in the excitation profile, corresponding to the spacing between vibronic levels in the excited state, is also equal to 123 cm{sup {minus}1} indicating that the ground state and excited state potential energy surfaces have the same shape. Only two distinct resonances spaced three vibrational quanta apart were evident in the profile for each band in the progression. Curve fitting of the Raman band shapes indicates that each overtone is composed of one sharp and one broad band, whereas the fundamental contains only one sharp component. The measured width of the fundamental was less than 2.5 cm{sup {minus}1} FWHM, limited by the instrument function. It is proposed that the sharp Raman bands represent a normal vibrational mode of a surface-adsorbed I{sub 2}-like species with the width determined by the intrinsic vibrational dephasing in the ground state. On the other hand, the broad Raman bands reflect vibronic coupling between different I{sub 2}-like species adsorbed on the same Ag cluster. The broad bandwidths result from both dephasing associated with the vibronic coupling and the intrinsic vibrational dephasing. Other weak emission bands are attributed to resonance fluorescence corresponding to direct transitions from higher vibronic levels of the excited state to the ground state. An emission at 429.9 nm is assigned to exciton recombination in small silver iodide clusters which are formed after spontaneous oxidation of the iodide-modified silver surface. {copyright} {ital 1998 American Institute of Physics.}

  5. Probing of local structures of thermal and photoinduced phases in rubidium manganese hexacyanoferrate by resonant Raman spectroscopy.

    PubMed

    Fukaya, Ryo; Asahara, Akifumi; Ishige, Shun; Nakajima, Makoto; Tokoro, Hiroko; Ohkoshi, Shin-ichi; Suemoto, Tohru

    2013-08-28

    Resonant couplings of the electronic states and the stretching vibrations of CN(-) ligands, which bridges metal ions, is investigated by resonance Raman spectroscopy for Rb(0.94)Mn[Fe(CN)6](0.98)·0.2H2O. Large excitation wavelength dependences over one order of magnitude were found for Raman peaks corresponding to different valence pairs of metal ions in the excitation wavelength range between 350 and 632 nm. In the thermal low-temperature phase, the CN(-) stretching modes due to the low-temperature-phase configuration (Fe(2+)-Mn(3+)) and the phase-boundary configuration (Fe(3+)-Mn(3+)) are coupled to the Fe(2+)-to-Mn(3+) intervalence transfer band and Jahn-Teller distorted Mn(3+) d-d transition band, respectively. In the photoinduced low-temperature phase, the Fe(3+)-Mn(3+) mode shows strong resonant enhancement with the CN(-)-to-Fe(3+) charge-transfer band, which exists in the high-temperature phase with a cubic structure. From these resonance behaviors, we conclude that the local lattice symmetry of the photoinduced phase is cubic in contrast with the tetragonal symmetry in the thermal low-temperature phase.

  6. Highly sensitive absorption measurements in lithium niobate using whispering gallery resonators

    NASA Astrophysics Data System (ADS)

    Leidinger, Markus; Buse, Karsten; Breunig, Ingo

    2015-02-01

    The absorption coefficient of undoped, congruently grown lithium niobate (LiNbO3) for ordinarily and extraordinarily polarized light is measured in the wavelength range from 390 to 2600 nm using whispering gallery resonators (WGRs). These monolithic cavities guide light by total internal reflection. Their high Q-factor provides several hundred meters of propagation for the coupled light in millimetre size resonators allowing for the measurement of absorption coefficients below 10-2 cm-1, where standard methods such as Fourier-transform or grating spectroscopy meet their limit. In this work the lowest measured value is 10-4 cm-1 at 1700 nm wavelength. Furthermore, the known OH- overtone at 1470 nm wavelength can be resolved clearly.

  7. The use of selected neutron absorption resonance filters to suppress spurious events on hot neutron spectrometers

    NASA Astrophysics Data System (ADS)

    Lançon, D.; Ewings, R. A.; Stewart, J. R.; Jiménez-Ruiz, M.; Rønnow, H. M.

    2015-04-01

    Resonant absorption can be used as a filter for high energy neutron spectroscopy. Here we report the transmission of eight thin foil filters: erbium, indium, iridium, dysprosium, hafnium, gadolinium, cadmium and samarium, measured using neutron time-of-flight techniques over a range of energies (1 meV to 10 eV). Measured transmission is converted into energy-dependent absorption cross-section which compares closely to tabulated values. Each resonance is characterized from 91 meV (samarium) to 2815 meV (gadolinium) by Lorentzian fits. Possibilities for the use of neutron filters depending on the type of spurious background are discussed and the performance is simulated for a specific example of a hot neutron triple axis spectrometer experiment.

  8. Theoretical study of Raman chirped adiabatic passage by X-ray absorption spectroscopy: Highly excited electronic states and rotational effects

    SciTech Connect

    Engin, Selma; Sisourat, Nicolas Selles, Patricia; Taïeb, Richard; Carniato, Stéphane

    2014-06-21

    Raman Chirped Adiabatic Passage (RCAP) is an efficient method to climb the vibrational ladder of molecules. It was shown on the example of fixed-in-space HCl molecule that selective vibrational excitation can thus be achieved by RCAP and that population transfer can be followed by X-ray Photoelectron spectroscopy [S. Engin, N. Sisourat, P. Selles, R. Taïeb, and S. Carniato, Chem. Phys. Lett. 535, 192–195 (2012)]. Here, in a more detailed analysis of the process, we investigate the effects of highly excited electronic states and of molecular rotation on the efficiency of RCAP. Furthermore, we propose an alternative spectroscopic way to monitor the transfer by means of X-ray absorption spectra.

  9. Comparative resonance Raman study of cytochrome c oxidase from beef heart and Paracoccus denitrificans.

    PubMed

    Heibel, G E; Hildebrandt, P; Ludwig, B; Steinrücke, P; Soulimane, T; Buse, G

    1993-10-12

    Well-resolved, Soret band excited resonance Raman spectra were measured from the fully oxidized and fully reduced cytochrome c oxidase from beef heart and Paracoccus denitrificans. The vibrational patterns in the marker band region (1450-1700 cm-1) were analyzed, and a complete assignment of heme a and heme a3 vibrational modes is presented, permitting a detailed structural comparison of the mammalian and bacterial enzymes. Similar frequencies of the porphyrin modes for the reduced heme a and the reduced and oxidized heme a3 are found, indicating a close relationship of the ground-state conformations in all oxidase species studied. In oxidized heme a, however, significant frequency differences are observed and interpreted in terms of a ruffled porphyrin structure in the three- and two-subunit forms of the Paracoccus enzyme compared to the planar heme a of beef heart oxidase. The structural distortions, which also perturb the conformation of the formyl substituent and its electronic coupling with the porphyrin, reflect the specific heme-protein interactions at heme a. Since in the fully reduced state heme a appears to be largely planar in all oxidase species, the redox-linked conformational transition requires a more drastic rearrangement of the heme a-protein interactions in the bacterial than in the mammalian oxidase. For both heme a and heme a3 in the reduced state and for heme a3 in the oxidize state, frequency, intensity, and bandwidth differences of the formyl stretching vibration and intensity differences of some porphyrin modes are noted between the three oxidase forms. The same modes are also affected by quaternary structure changes in the bovine oxidase caused by different detergents and isolation procedures. These effects are attributed to differences of the dielectric properties of the heme environment, due to subtle structural changes in the heme pockets, induced by protein-protein interactions of subunit III with subunits I and/or II.

  10. Spatially resolved confocal resonant Raman microscopic analysis of anode-grown Geobacter sulfurreducens biofilms.

    PubMed

    Lebedev, Nikolai; Strycharz-Glaven, Sarah M; Tender, Leonard M

    2014-02-03

    When grown on the surface of an anode electrode, Geobacter sulfurreducens forms a multi-cell thick biofilm in which all cells appear to couple the oxidation of acetate with electron transport to the anode, which serves as the terminal metabolic electron acceptor. Just how electrons are transported through such a biofilm from cells to the underlying anode surface over distances that can exceed 20 microns remains unresolved. Current evidence suggests it may occur by electron hopping through a proposed network of redox cofactors composed of immobile outer membrane and/or extracellular multi-heme c-type cytochromes. In the present work, we perform a spatially resolved confocal resonant Raman (CRR) microscopic analysis to investigate anode-grown Geobacter biofilms. The results confirm the presence of an intra-biofilm redox gradient whereby the probability that a heme is in the reduced state increases with increasing distance from the anode surface. Such a gradient is required to drive electron transport toward the anode surface by electron hopping via cytochromes. The results also indicate that at open circuit, when electrons are expected to accumulate in redox cofactors involved in electron transport due to the inability of the anode to accept electrons, nearly all c-type cytochrome hemes detected in the biofilm are oxidized. The same outcome occurs when a comparable potential to that measured at open circuit (-0.30 V vs. SHE) is applied to the anode, whereas nearly all hemes are reduced when an exceedingly negative potential (-0.50 V vs. SHE) is applied to the anode. These results suggest that nearly all c-type cytochrome hemes detected in the biofilm can be electrochemically accessed by the electrode, but most have oxidation potentials too negative to transport electrons originating from acetate metabolism. The results also reveal a lateral heterogeneity (x-y dimensions) in the type of c-type cytochromes within the biofilm that may affect electron transport to the

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

    NASA Astrophysics Data System (ADS)

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

    2004-10-01

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

  12. Effects of dispersion and absorption in resonant Bragg diffraction of x-rays.

    PubMed

    Lovesey, S W; Scagnoli, V; Dobrynin, A N; Joly, Y; Collins, S P

    2014-03-26

    Resonant diffraction of x-rays by crystals with anisotropic optical properties is investigated theoretically, to assess how the intensity of a Bragg spot is influenced by effects related to dispersion (birefringence) and absorption (dichroism). Starting from an exact but opaque expression, simple analytic results are found to expose how intensity depends on dispersion and absorption in the primary and secondary beams and, also, the azimuthal angle (rotation of the crystal about the Bragg wavevector). If not the full story for a given application, our results are more than adequate to explore consequences of dispersion and absorption in the intensity of a Bragg spot. Results are evaluated for antiferromagnetic copper oxide, and low quartz. For CuO, one of our results reproduces all salient features of a previously published simulation of the azimuthal-angle dependence of a magnetic Bragg peak. It is transparent in our analytic result that dispersion and absorption effects alone cannot reproduce published experimental data. Available data for the azimuthal-angle dependence of space-group forbidden reflections (0,0, l), with l ≠ 3n, of low quartz depart from symmetry imposed by the triad axis of rotation symmetry. The observed asymmetry can be induced by dispersion and absorption even though absorption coefficients are constant, independent of the azimuthal angle, in this class of reflections.

  13. Ultrafast photo-induced nuclear relaxation of a conformationally disordered conjugated polymer probed with transient absorption and femtosecond stimulated Raman spectroscopies.

    PubMed

    Yu, Wenjian; Donohoo-Vallett, Paul J; Zhou, Jiawang; Bragg, Arthur E

    2014-07-28

    A combination of transient absorption (TAS) and femtosecond stimulated Raman (FSRS) spectroscopies were used to interrogate the photo-induced nuclear relaxation dynamics of poly(3-cyclohexyl,4-methylthiophene) (PCMT). The large difference in inter-ring dihedral angles of ground and excited-state PCMT make it an ideal candidate for studying large-amplitude vibrational relaxation associated with exciton trapping. Spectral shifting in the S1 TA spectra on sub-ps timescales (110 ± 20 and 800 ± 100 fs) is similar to spectroscopic signatures of excited-state relaxation observed with related photoexcited conjugated polymers and which have been attributed to exciton localization and a combination of resonant energy transfer and torsional relaxation, respectively. Measurements made with both techniques reveal fast PCMT S1 decay and triplet formation (τS1 = 25-32 ps), which is similar to the excited-state dynamics of short oligothiophenes and highly twisted polyconjugated molecules. On ultrafast timescales FSRS of S1 PCMT offers a new perspective on the nuclear dynamics that underlie localization of excitons in photoexcited conjugated polymers: Spectral dynamics in the C=C stretching region (1400-1600 cm(-1)) include a red-shift of the in-phase C=C stretching frequency, as well as a change in the relative intensity of in-phase and out-of-phase stretch intensities on a timescale of ∼100 fs. Both changes indicate an ultrafast vibrational distortion that increases the conjugation length in the region of the localized excitation and are consistent with exciton self-localization or trapping. Wavelength-dependent excited-state FSRS measurements further demonstrate that the C=C stretching frequency provides a useful spectroscopic handle for interrogating the degree of delocalization in excited conjugated polymers given the selectivity achieved via resonance enhancement.

  14. Ultrafast photo-induced nuclear relaxation of a conformationally disordered conjugated polymer probed with transient absorption and femtosecond stimulated Raman spectroscopies

    SciTech Connect

    Yu, Wenjian; Donohoo-Vallett, Paul J.; Zhou, Jiawang; Bragg, Arthur E.

    2014-07-28

    A combination of transient absorption (TAS) and femtosecond stimulated Raman (FSRS) spectroscopies were used to interrogate the photo-induced nuclear relaxation dynamics of poly(3-cyclohexyl,4-methylthiophene) (PCMT). The large difference in inter-ring dihedral angles of ground and excited-state PCMT make it an ideal candidate for studying large-amplitude vibrational relaxation associated with exciton trapping. Spectral shifting in the S{sub 1} TA spectra on sub-ps timescales (110 ± 20 and 800 ± 100 fs) is similar to spectroscopic signatures of excited-state relaxation observed with related photoexcited conjugated polymers and which have been attributed to exciton localization and a combination of resonant energy transfer and torsional relaxation, respectively. Measurements made with both techniques reveal fast PCMT S{sub 1} decay and triplet formation (τ{sub S1} = 25–32 ps), which is similar to the excited-state dynamics of short oligothiophenes and highly twisted polyconjugated molecules. On ultrafast timescales FSRS of S{sub 1} PCMT offers a new perspective on the nuclear dynamics that underlie localization of excitons in photoexcited conjugated polymers: Spectral dynamics in the C=C stretching region (1400–1600 cm{sup −1}) include a red-shift of the in-phase C=C stretching frequency, as well as a change in the relative intensity of in-phase and out-of-phase stretch intensities on a timescale of ∼100 fs. Both changes indicate an ultrafast vibrational distortion that increases the conjugation length in the region of the localized excitation and are consistent with exciton self-localization or trapping. Wavelength-dependent excited-state FSRS measurements further demonstrate that the C=C stretching frequency provides a useful spectroscopic handle for interrogating the degree of delocalization in excited conjugated polymers given the selectivity achieved via resonance enhancement.

  15. Structure, spectra and antioxidant action of ascorbic acid studied by density functional theory, Raman spectroscopic and nuclear magnetic resonance techniques

    NASA Astrophysics Data System (ADS)

    Singh, Gurpreet; Mohanty, B. P.; Saini, G. S. S.

    2016-02-01

    Structure, vibrational and nuclear magnetic resonance spectra, and antioxidant action of ascorbic acid towards hydroxyl radicals have been studied computationally and in vitro by ultraviolet-visible, nuclear magnetic resonance and vibrational spectroscopic techniques. Time dependant density functional theory calculations have been employed to specify various electronic transitions in ultraviolet-visible spectra. Observed chemical shifts and vibrational bands in nuclear magnetic resonance and vibrational spectra, respectively have been assigned with the help of calculations. Changes in the structure of ascorbic acid in aqueous phase have been examined computationally and experimentally by recording Raman spectra in aqueous medium. Theoretical calculations of the interaction between ascorbic acid molecule and hydroxyl radical predicted the formation of dehydroascorbic acid as first product, which has been confirmed by comparing its simulated spectra with the corresponding spectra of ascorbic acid in presence of hydrogen peroxide.

  16. Structure, spectra and antioxidant action of ascorbic acid studied by density functional theory, Raman spectroscopic and nuclear magnetic resonance techniques.

    PubMed

    Singh, Gurpreet; Mohanty, B P; Saini, G S S

    2016-02-15

    Structure, vibrational and nuclear magnetic resonance spectra, and antioxidant action of ascorbic acid towards hydroxyl radicals have been studied computationally and in vitro by ultraviolet-visible, nuclear magnetic resonance and vibrational spectroscopic techniques. Time dependant density functional theory calculations have been employed to specify various electronic transitions in ultraviolet-visible spectra. Observed chemical shifts and vibrational bands in nuclear magnetic resonance and vibrational spectra, respectively have been assigned with the help of calculations. Changes in the structure of ascorbic acid in aqueous phase have been examined computationally and experimentally by recording Raman spectra in aqueous medium. Theoretical calculations of the interaction between ascorbic acid molecule and hydroxyl radical predicted the formation of dehydroascorbic acid as first product, which has been confirmed by comparing its simulated spectra with the corresponding spectra of ascorbic acid in presence of hydrogen peroxide.

  17. Effective time-independent studies on resonance Raman spectroscopy of trans-stilbene including the Duschinsky effect

    NASA Astrophysics Data System (ADS)

    Lin, Na; Barone, Vincenzo; Cappelli, Chiara; Zhao, Xian; Ruud, Kenneth; Santoro, Fabrizio

    2013-07-01

    We simulate the resonance Raman spectra of trans-stilbene using a recently developed time-independent method that allows computations of the full two-dimensional spectrum as a function of the incident and scattered frequencies, including both the Franck-Condon and the Herzberg-Teller contributions. The potential energy surfaces (PESs) of the ground and resonant states are described in the harmonic approximation using density functional theory PBE0/6-31+G(d,p) calculations in gas phase and in cyclohexane. The simulated spectra are in good agreement with the experimental data [J. Chem. Phys. 83, 5000 (1985)] measured at four different excitation wavelengths, and allow us to unambiguously assign the main experimental bands. We perform an extensive comparison of the performance of four different vertical or adiabatic models for the PES of the resonant state, dissecting the effects of nuclear displacements and Duschinsky mixings on the spectra.

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

    PubMed

    Guthmuller, Julien

    2016-02-14

    Sum-over-state (SOS) expressions to simulate absorption spectroscopy and resonance Raman (RR) scattering including Franck-Condon (FC) and Herzberg-Teller (HT) effects are described. Starting from the general SOS method, several simplified SOS formulae are derived. In particular, within the so-called independent mode displaced harmonic oscillator model, it is shown that including the vibronic structure in the absorption and RR spectra only requires the calculation of FC overlap integrals of the type θg0|θev, where g, e, and v stand for the electronic ground state, excited state, and vibrational quantum number, respectively. Additionally, an approximation of the latter approach is introduced, referred as the simplified Φe method, in which the FC factors are neglected. This method is advantageous from the computational point of view and it is demonstrated that it reproduces the main characteristics of the more involved approaches. The merits and drawbacks of the different methods are discussed by applying them to the prototypical compound of Rhodamine 6G. Overall, this work intends to unravel and clarify some differences in the SOS theories of RR scattering.

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

    NASA Astrophysics Data System (ADS)

    Guthmuller, Julien

    2016-02-01

    Sum-over-state (SOS) expressions to simulate absorption spectroscopy and resonance Raman (RR) scattering including Franck-Condon (FC) and Herzberg-Teller (HT) effects are described. Starting from the general SOS method, several simplified SOS formulae are derived. In particular, within the so-called independent mode displaced harmonic oscillator model, it is shown that including the vibronic structure in the absorption and RR spectra only requires the calculation of FC overlap integrals of the type <" separators=" θ g 0 | θ e v > , where g, e, and v stand for the electronic ground state, excited state, and vibrational quantum number, respectively. Additionally, an approximation of the latter approach is introduced, referred as the simplified Φe method, in which the FC factors are neglected. This method is advantageous from the computational point of view and it is demonstrated that it reproduces the main characteristics of the more involved approaches. The merits and drawbacks of the different methods are discussed by applying them to the prototypical compound of Rhodamine 6G. Overall, this work intends to unravel and clarify some differences in the SOS theories of RR scattering.

  20. Resonant microwave absorption in thermally deposited au nanoparticle films near percolation coverage.

    PubMed

    Obrzut, Jan; Douglas, Jack F; Kirillov, Oleg; Sharifi, Fred; Liddle, J Alexander

    2013-07-16

    We observe a resonant transition in the microwave absorption of thin thermally deposited Au nanoparticle films near the geometrical percolation transition pc where the films exhibit a 'fractal' heterogeneous geometry. Absorption of incident microwave radiation increases sharply near pc, consistent with effective medium theory predictions. Both the theory and our experiments indicate that the hierarchical structure of these films makes their absorption insensitive to the microwave radiation wavelength λ, so that this singular absorption of microwave radiation is observed over a broad frequency range between 100 MHz and 20 GHz. The interaction of electromagnetic radiation with randomly distributed conductive scattering particles gives rise to localized resonant modes, and our measurements indicate that this adsorption process is significantly enhanced for microwaves in comparison to ordinary light. In particular, above the percolation transition a portion of the injected microwave power is stored within the film until dissipated. Finally, we find that the measured surface conductivity can be quantitatively described at all Au concentrations by generalized effective medium theory, where the fitted conductivity percolation exponents and pc itself are consistent with known two-dimensional estimates. Our results demonstrate that microwave measurements provide a powerful means of remotely measuring the electromagnetic properties of highly heterogeneous conducting films, enabling purposeful engineering of the electromagnetic properties of thin films in the microwave frequency range through fabrication of 'disordered' films of conducting particles such as metal nanoparticles or carbon nanotubes.

  1. Absorption Spectra of Broadened Sodium Resonance Lines in Presence of Rare Gases

    SciTech Connect

    Chung, H-K; Shurgalin, M; Babb, J F

    2002-09-11

    The pressure broadening of alkali-metal lines is a fundamental problem with numerous applications. For example, the sodium resonance lines broadened by xenon are important in the production of broad spectra emitted in the HPS (High-Pressure Sodium) lamp and they potentially can be used for gas condition diagnostics. Broadened absorption lines of alkali-metal atoms are prominent in the optical spectra of brown dwarfs and understanding the broadening mechanism will help elucidate the chemical composition and atmospheric properties of those stars. The far-line wing spectra of sodium resonance lines broadened by rare gases are found to exhibit molecular characteristics such as satellites and hence the total absorption coefficients for vapors of Na atoms and perturbing rare gas atoms can be modeled as Na-RG (rare gas) molecular absorption spectra. In this work, using carefully chosen interatomic potentials for Na-RG molecules we carry out quantum-mechanical calculations for reduced absorption coefficients for vapors composed of Na-He, Na-Ar, and Na-Xe. Calculated spectra are compared to available experimental results and the agreement is good in the measured satellite positions and shapes.

  2. Enhanced Absorption in 2D Materials Via Fano- Resonant Photonic Crystals

    SciTech Connect

    Wang, Wenyi; Klotz, Andrey; Yang, Yuanmu; Li, Wei; Kravchenko, Ivan I.; Briggs, Dayrl P.; Bolotin, Kirill; Valentine, Jason

    2015-05-01

    The use of two-dimensional (2D) materials in optoelectronics has attracted much attention due to their fascinating optical and electrical properties. For instance, graphenebased devices have been employed for applications such as ultrafast and broadband photodetectors and modulators while transition metal dichalcogenide (TMDC) based photodetectors can be used for ultrasensitive photodetection. However, the low optical absorption of 2D materials arising from their atomic thickness limits the maximum attainable external quantum efficiency. For example, in the visible and NIR regimes monolayer MoS2 and graphene absorb only ~10% and 2.3% of incoming light, respectively. Here, we experimentally demonstrate the use of Fano-resonant photonic crystals to significantly boost absorption in atomically thin materials. Using graphene as a test bed, we demonstrate that absorption in the monolayer thick material can be enhanced to 77% within the telecommunications band, the highest value reported to date. We also show that the absorption in the Fano-resonant structure is non-local, with light propagating up to 16 μm within the structure. This property is particularly beneficial in harvesting light from large areas in field-effect-transistor based graphene photodetectors in which separation of photo-generated carriers only occurs ~0.2 μm adjacent to the graphene/electrode interface.

  3. Enhanced Absorption in 2D Materials Via Fano- Resonant Photonic Crystals

    DOE PAGES

    Wang, Wenyi; Klotz, Andrey; Yang, Yuanmu; ...

    2015-05-01

    The use of two-dimensional (2D) materials in optoelectronics has attracted much attention due to their fascinating optical and electrical properties. For instance, graphenebased devices have been employed for applications such as ultrafast and broadband photodetectors and modulators while transition metal dichalcogenide (TMDC) based photodetectors can be used for ultrasensitive photodetection. However, the low optical absorption of 2D materials arising from their atomic thickness limits the maximum attainable external quantum efficiency. For example, in the visible and NIR regimes monolayer MoS2 and graphene absorb only ~10% and 2.3% of incoming light, respectively. Here, we experimentally demonstrate the use of Fano-resonant photonicmore » crystals to significantly boost absorption in atomically thin materials. Using graphene as a test bed, we demonstrate that absorption in the monolayer thick material can be enhanced to 77% within the telecommunications band, the highest value reported to date. We also show that the absorption in the Fano-resonant structure is non-local, with light propagating up to 16 μm within the structure. This property is particularly beneficial in harvesting light from large areas in field-effect-transistor based graphene photodetectors in which separation of photo-generated carriers only occurs ~0.2 μm adjacent to the graphene/electrode interface.« less

  4. Signs of the Biological Effect of ~2 μm Low-Intensity Laser Radiation in Raman and Absorption Spectra of Blood

    NASA Astrophysics Data System (ADS)

    Batay, L. E.; Khodasevich, I. A.; Khodasevich, M. A.; Gorbunova, N. B.; Manina, E. Yu.

    2016-09-01

    Local exposure of experimental animals to low-intensity emission from a thulium laser (λ = 1.96 μm) leads to changes in the Raman and IR absorption spectra of blood. This indicates development of systemic effects caused by direct excitation of water molecules by radiation with wavelength ~2 μm, in particular modifi cation of the hemoglobin molecule.

  5. Broadband optical absorption by tunable Mie resonances in silicon nanocone arrays

    PubMed Central

    Wang, Z. Y.; Zhang, R. J.; Wang, S. Y.; Lu, M.; Chen, X.; Zheng, Y. X.; Chen, L. Y.; Ye, Z.; Wang, C. Z.; Ho, K. M.

    2015-01-01

    Nanostructure arrays such as nanowire, nanopillar, and nanocone arrays have been proposed to be promising antireflection structures for photovoltaic applications due to their great light trapping ability. In this paper, the optical properties of Si nanopillar and nanocone arrays in visible and infrared region were studied by both theoretical calculations and experiments. The results show that the Mie resonance can be continuously tuned across a wide range of wavelength by varying the diameter of the nanopillars. However, Si nanopillar array with uniform diameter exhibits only discrete resonance mode, thus can't achieve a high broadband absorption. On the other hand, the Mie resonance wavelength in a Si nanocone array can vary continuously as the diameters of the cross sections increase from the apex to the base. Therefore Si nanocone arrays can strongly interact with the incident light in the broadband spectrum and the absorbance by Si nanocone arrays is higher than 95% over the wavelength from 300 to 2000 nm. In addition to the Mie resonance, the broadband optical absorption of Si nanocone arrays is also affected by Wood-Rayleigh anomaly effect and metal impurities introduced in the fabrication process. PMID:25589290

  6. Broadband optical absorption by tunable Mie resonances in silicon nanocone arrays

    SciTech Connect

    Wang, Z. Y.; Zhang, R. J.; Wang, S. Y.; Lu, M.; Chen, X.; Zheng, Y. X.; Chen, L. Y.; Ye, Z.; Wang, C. Z.; Ho, K. M.

    2015-01-15

    Nanostructure arrays such as nanowire, nanopillar, and nanocone arrays have been proposed to be promising antireflection structures for photovoltaic applications due to their great light trapping ability. In this paper, the optical properties of Si nanopillar and nanocone arrays in visible and infrared region were studied by both theoretical calculations and experiments. The results show that the Mie resonance can be continuously tuned across a wide range of wavelength by varying the diameter of the nanopillars. However, Si nanopillar array with uniform diameter exhibits only discrete resonance mode, thus can't achieve a high broadband absorption. On the other hand, the Mie resonance wavelength in a Si nanocone array can vary continuously as the diameters of the cross sections increase from the apex to the base. Therefore Si nanocone arrays can strongly interact with the incident light in the broadband spectrum and the absorbance by Si nanocone arrays is higher than 95% over the wavelength from 300 to 2000 nm. In addition to the Mie resonance, the broadband optical absorption of Si nanocone arrays is also affected by Wood-Rayleigh anomaly effect and metal impurities introduced in the fabrication process.

  7. Broadband optical absorption by tunable Mie resonances in silicon nanocone arrays

    DOE PAGES

    Wang, Z. Y.; Zhang, R. J.; Wang, S. Y.; ...

    2015-01-15

    Nanostructure arrays such as nanowire, nanopillar, and nanocone arrays have been proposed to be promising antireflection structures for photovoltaic applications due to their great light trapping ability. In this paper, the optical properties of Si nanopillar and nanocone arrays in visible and infrared region were studied by both theoretical calculations and experiments. The results show that the Mie resonance can be continuously tuned across a wide range of wavelength by varying the diameter of the nanopillars. However, Si nanopillar array with uniform diameter exhibits only discrete resonance mode, thus can't achieve a high broadband absorption. On the other hand, themore » Mie resonance wavelength in a Si nanocone array can vary continuously as the diameters of the cross sections increase from the apex to the base. Therefore Si nanocone arrays can strongly interact with the incident light in the broadband spectrum and the absorbance by Si nanocone arrays is higher than 95% over the wavelength from 300 to 2000 nm. In addition to the Mie resonance, the broadband optical absorption of Si nanocone arrays is also affected by Wood-Rayleigh anomaly effect and metal impurities introduced in the fabrication process.« less

  8. Enhancing ferromagnetic resonance absorption for very thin insulating magnetic films with spin plasmonics

    SciTech Connect

    Chui, S. T.

    2015-05-14

    We consider enhancing the ferromagnetic resonance (FMR) absorption of very thin insulating magnetic films by placing it on top of a dielectric. We find that the signal is enhanced by at least an order of magnitude due to a new nonreciprocal interface resonance that is a mixture of the magnetic surface plasmon mode and a wave guide mode. This resonance occurs over a wide range of thicknesses of the dielectric that is still much less than the wavelength and is made possible by the negative magnetic susceptibility of the magnetic layer. The line width of absorption is reduced by an order of magnitude less than the Gilbert damping parameter. At some frequency, the group velocity of this resonance is negative. Experimentally, very thin yttrium iron garnet (YIG) films are grown on a Gadolinium Gallium Garnet (GGG) substrate which can be considered the dielectric. Our model applies to experiments performed in the YIG/GGG system. Indeed, our picture resolves the disagreement on the magnitude of the spin diffusion lengths obtained with the FMR and the Brillouin scattering techniques. It also provides for a way to make new adaptive thin film miniaturized photonic nonreciprocal devices with low loss.

  9. Influence of two-photon absorption on the dynamic behaviors of microring resonators.

    PubMed

    Li, Qiliang; Chen, Haowen; Xu, Jie; Hu, Miao; Zeng, Ran; Zhou, Xuefang; Li, Shuqin

    2017-04-01

    In this paper, we have investigated the influence of two-photon absorption (TPA) on the dynamic behaviors of all-pass and add-drop microring resonators by using two iterative methods along with the linear stability analysis method. While the incident field is above a certain value, the TPA coefficient has greater influence on the steady state for all-pass and add-drop microring resonators. We use the linear stability analysis method to analyze the stability of the steady state solutions and obtain stability conditions. Results obtained have shown that the change of TPA coefficient will lead to different dynamic behaviors; in addition, while the TPA coefficient is small and its change is slight, the dynamic behaviors of the microring resonators will not change much for most regions. At last, we observe the period windows and route from chaotic to period-N in some original chaotic regions due to the fluctuation of the TPA coefficient.

  10. 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…

  11. Nickel(II)-substituted azurin I from Alcaligenes xylosoxidans as characterized by resonance Raman spectroscopy at cryogenic temperature.

    PubMed

    Fitzpatrick, Marzena B; Czernuszewicz, Roman S

    2009-05-01

    Metal-substituted blue copper proteins (cupredoxins) have been successfully used to study the effect of metal-ion identity on their active-site properties, specifically the coordination geometry and metal-ligand bond strengths. In this work, low-temperature (77 K) resonance Raman (RR) spectra of the blue copper protein Alcaligenes xylosoxidans azurin I and its Ni(II) derivative are reported. A detailed analysis of all observed bands is presented and responsiveness to metal substitution is discussed in terms of structural and bonding changes. The native cupric site exhibits a RR spectrum characteristic of a primarily trigonal planar (type 1) coordination geometry, identified by the nu(Cu-S)(Cys) markers at 373, 399, 409, and 430 cm(-1). Replacement of Cu(II) with Ni(II) results in optical and RR spectra that reveal (1) a large hypsochromic shift in the main (Cys)S --> M(II) charge-transfer absorption from 622 to 440 nm, (2) greatly reduced metal-thiolate bonding interaction, indicated by substantially lower nu(Ni-S)(Cys) stretching frequencies, (3) elevation of the cysteine nu(C( beta )-S) stretching, amide III, and rho (s)(C( beta )H(2)) scissors vibrational modes, and (4) primarily four-coordinated, trigonally distorted tetrahedral geometry of the Ni(II) site that is marked by characteristic nu(Ni-S)(Cys) stretching RR bands at 347, 364, and 391 cm(-1). Comparisons of the electronic and vibrational properties between A. xylosoxidans azurin I and its closely structurally related azurin from Pseudomonas aeruginosa are made and discussed. For cupric azurins, the intensity-weighted average M(II)-S(Cys) stretching frequencies are calculated to be nu(Cu-S)(iwa) = 406.3 and 407.6 cm(-1), respectively. These values decreased to nu(Ni-S)(iwa) = 359.3 and 365.5 cm(-1), respectively, after Ni(II) --> Cu(II) exchange, suggesting that the metal-thiolate interactions are similar in the two native proteins but are much less alike in their Ni(II)-substituted forms.

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

    SciTech Connect

    Bateni, Ali; Somer, Mehmet E-mail: msomer@ku.edu.tr; Erdem, Emre E-mail: msomer@ku.edu.tr; Repp, Sergej; Weber, Stefan; Acar, Selcuk; Kokal, Ilkin; Häßler, Wolfgang

    2015-04-21

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

  13. Non-destructive studies of fuel pellets by neutron resonance absorption radiography and thermal neutron radiography

    NASA Astrophysics Data System (ADS)

    Tremsin, A. S.; Vogel, S. C.; Mocko, M.; Bourke, M. A. M.; Yuan, V.; Nelson, R. O.; Brown, D. W.; Feller, W. B.

    2013-09-01

    Many isotopes in nuclear materials exhibit strong peaks in neutron absorption cross sections in the epithermal energy range (1-1000 eV). These peaks (often referred to as resonances) occur at energies specific to particular isotopes, providing a means of isotope identification and concentration measurements. The high penetration of epithermal neutrons through most materials is very useful for studies where samples consist of heavy-Z elements opaque to X-rays and sometimes to thermal neutrons as well. The characterization of nuclear fuel elements in their cladding can benefit from the development of high resolution neutron resonance absorption imaging (NRAI), enabled by recently developed spatially-resolved neutron time-of-flight detectors. In this technique the neutron transmission of the sample is measured as a function of spatial location and of neutron energy. In the region of the spectra that borders the resonance energy for a particular isotope, the reduction in transmission can be used to acquire an image revealing the 2-dimensional distribution of that isotope within the sample. Provided that the energy of each transmitted neutron is measured by the neutron detector used and the irradiated sample possesses neutron absorption resonances, then isotope-specific location maps can be acquired simultaneously for several isotopes. This can be done even in the case where samples are opaque or have very similar transmission for thermal neutrons and X-rays or where only low concentrations of particular isotopes are present (<0.1 atom% in some cases). Ultimately, such radiographs of isotope location can be utilized to measure isotope concentration, and can even be combined to produce three-dimensional distributions using tomographic methods. In this paper we present the proof-of-principle of NRAI and transmission Bragg edge imaging performed at Flight Path 5 (FP5) at the LANSCE pulsed, moderated neutron source of Los Alamos National Laboratory. A set of urania mockup

  14. Raman spectroscopy of white wines.

    PubMed

    Martin, Coralie; Bruneel, Jean-Luc; Guyon, François; Médina, Bernard; Jourdes, Michael; Teissedre, Pierre-Louis; Guillaume, François

    2015-08-15

    The feasibility of exploiting Raman scattering to analyze white wines has been investigated using 3 different wavelengths of the incoming laser radiation in the near-UV (325 nm), visible (532 nm) and near infrared (785 nm). To help in the interpretation of the Raman spectra, the absorption properties in the UV-visible range of two wine samples as well as their laser induced fluorescence have also been investigated. Thanks to the strong intensity enhancement of the Raman scattered light due to electronic resonance with 325 nm laser excitation, hydroxycinnamic acids may be detected and analyzed selectively. Fructose and glucose may also be easily detected below ca. 1000 cm(-1). This feasibility study demonstrates the potential of the Raman spectroscopic technique for the analysis of white wines.

  15. Semiconductors Investigated by Time Resolved Raman Absorption and Photoluminescence Spectroscopy Using Femtoseond and Picosecond Laser Techniques.

    DTIC Science & Technology

    1984-03-01

    We report on the research performed during the period 1982-1983 under the auspices of AFOSR. The research effort follows two directions: (1) laser ... development : subpicosecond laser, application of anti-resonant cavity to Nd:glass, study of the emerald laser, and study of a new mode-locking dye for

  16. 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.

  17. Raman lasing in As₂S₃ high-Q whispering gallery mode resonators.

    PubMed

    Vanier, Francis; Rochette, Martin; Godbout, Nicolas; Peter, Yves-Alain

    2013-12-01

    We report the first observation of a nonlinear process in a chalcogenide microresonator. Raman scattering and stimulated Raman scattering leading to laser oscillation is observed in microspheres made of As₂S₃. The coupled pump power threshold is as low as 13 μW using a pump wavelength of 1550 nm. The quality factor of the chalcogenide microresonator is also the highest ever reported with Q>7×10(7).

  18. Surface-enhanced resonance Raman scattering spectroscopy applied to phytochrome and its model compounds. 2. Phytochrome and phycocyanin chromophores

    SciTech Connect

    Farrens, D.L.; Holt, R.E.; Rospendowski, B.N.; Song, Pillsoon; Cotton, T.M. )

    1989-12-20

    Surface-enhanced resonance Raman scattering (SERRS) spectra of phytochrome at 77 K are reported. The spectra reveal significant differences between Pr and Pfr forms of phytochrome. SERRS spectra of C-phycocyanin Z,Z,Z- and Z,Z,E-chromopeptide isomers at 77 K are also reported. The phycocyanin chromopeptide studies are used to provide a basis for interpreting the phytochrome SERRS spectra. The spectra indicate that photoisomerization of chromophores from C-phycocyanin chromopeptides (from a Z,Z,Z to a Z,Z,E configuration) is detectable with SERRS.

  19. Docking Prediction of a Water Soluble Porphyrin and Tubulin Assisted with Resonance Raman and Vibrational Mode Analysis

    NASA Astrophysics Data System (ADS)

    McMicken, Brady; Brancaleon, Lorenzo; Thomas, Robert; Parker, James

    2015-03-01

    The ability to modify protein conformation by controlling its partial unfolding may have practical applications such as diminishing its function or blocking its activity. One method used to induce partial unfolding of a protein involves the use of a photosensitizer non-covalently bound to a protein that triggers photochemical reactions upon irradiation leading to protein conformational changes. We are investigating the photoinduced conformational changes of tubulin mediated by a bound water-soluble porphyrin that acts as a photosensitizer. Analysis of how tubulin conformational changes affect its function including polymeric assembly forming microtubules is of interest to uncover the mechanism responsible for the structural change. Our approach to better understand the conformational change, we first plan to discover the binding location between the porphyrin and protein. Use of vibrational mode analysis using density functional theory and resonance Raman experiments targeting the porphyrin molecule will be used to correlate Raman peaks with vibrational modes. The relative intensities of the porphyrin bound to tubulin can be used to calculate the equilibrium geometry observed from Raman spectra. These data will provide the relative distortion of the porphyrin when bound to tubulin, which will subsequently be used in docking simulations to find the most likely binding configuration.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  1. Probing Nanoscale Ferroelectricity by Ultraviolet Raman Spectroscopy

    DTIC Science & Technology

    2006-09-15

    gap materials because the visible photon energy is much smaller than the band gap (10). Consequently, the absorption is extremely weak and the...UV ex- citation, the photon energy is above the band gaps of ferroelectrics, leading to a much stronger absorption and a shorter penetration depth...preventing light from entering the substrate. UV excitation near the band gap also leads to strong resonance enhancement of Raman sig- nals. This is

  2. Laser irradiations of advanced targets promoting absorption resonance for ion acceleration in TNSA regime

    NASA Astrophysics Data System (ADS)

    Torrisi, L.; Calcagno, L.; Giulietti, D.; Cutroneo, M.; Zimbone, M.; Skala, J.

    2015-07-01

    Advanced targets based on Au nanoparticles embedded in polymers films show high absorption coefficient in the UV-visible and infrared region. They can be employed to enhance the proton and ion acceleration from the laser-generated plasma in TNSA regime. In conditions of "p" polarized laser irradiations at 1015 W/cm2 intensity, in these films can be induced resonant absorption due to plasma wave excitation. Plasma on-line diagnostics is based on SiC detectors, Thomson spectrometry and X-ray streak camera imaging. Measurements of kinetic energy of accelerated ions indicate a significant increment using polymer targets containing gold nanoparticles and "p" polarized laser light with respect to pure polymers and unpolarized light irradiation.

  3. Resonant tube for measurement of sound absorption in gases at low frequency/pressure ratios

    NASA Technical Reports Server (NTRS)

    Zuckerwar, A. J.; Griffin, W. A.

    1980-01-01

    The paper describes a resonant tube for measuring sound absorption in gases, with specific emphasis on the vibrational relaxation peak of N2, over a range of frequency/pressure ratios from 0.1 to 2500 Hz/atm. The experimental background losses measured in argon agree with the theoretical wall losses except at few isolated frequencies. Rigid cavity terminations, external excitation, and a differential technique of background evaluation were used to minimize spurious contributions to the background losses. Room temperature measurements of sound absorption in binary mixtures of N2-CO2 in which both components are excitable resulted in the maximum frequency/pressure ratio in Hz/atm of 0.063 + 123m for the N2 vibrational relaxation peak, where m is mole percent of added CO2; the maximum ratio for the CO2 peak was 34,500 268m where m is mole percent of added N2.

  4. Dynamically tunable plasmon-induced absorption in resonator-coupled graphene waveguide

    NASA Astrophysics Data System (ADS)

    Wen, Mengting; Wang, Lingling; Zhai, Xiang; Lin, Qi; Xia, Shengxuan

    2016-11-01

    We demonstrate plasmon-induced absorption (PIA) in an ultra-compact graphene waveguide system which is composed of a single graphene sheet with two air cavities side-coupled to a graphene nanoribbon. By designing two coherent optical pathways, the pronounced PIA can be achieved due to the extreme destructive interference between the radiant and subradiant modes supported by the two graphene nanoribbons. The resonant strength shows strong dependence on the coupling distance between the two graphene nanoribbons and the resonance wavelength can be dynamically tuned by varying their Fermi energy. Furthermore, the group delay time up to -0.14 ps can be reached at the PIA window, suggesting unique fast-light feature. In addition, the double PIA phenomenon is also analyzed by introducing another graphene nanoribbon. Our results may pave the way for controlling the transmission of a light signal in the design of ultra-compact plasmonic devices.

  5. Dynamical rate theory of enzymatic reactions and triple-resonant coherent anti-Stokes Raman scattering microspectroscopy

    NASA Astrophysics Data System (ADS)

    Min, Wei

    Chapters 2-7 focus on physical enzymology. Despite its long history, recent single-molecule spectroscopy, among many others techniques, has generated new quantitative data that reveal unobserved features of protein dynamics and enzyme catalysis at unprecedented levels. Much of these are beyond the classic framework of transition state theory and Michalis-Menten (MM) enzyme kinetics. Due to the complexity of the problem, theoretical developments in this area have much lagged behind experiments. After an initial experimental characterization on single-molecule protein conformational fluctuations, we then develop a dynamical rate theory for enzyme catalyzed chemical reactions, from a statistical mechanics approach. Towards this goal, we formulate a two-dimensional (2D) multi-surface free energy description of the entire catalytic process that explicitly combines the concept of "fluctuating enzymes" with the MM enzyme kinetics. The outcome of this framework has two folds. On the rate theory side, going much beyond transition state theory, it connects conformational fluctuations to catalysis, allows for the interplay between energetics (e.g. Haldane's stain energy) and dynamics (e.g. Koshland's induced fit), and predicts the time dependence of single-enzyme catalysis. On the enzyme kinetics side, it gives mechanistic and unified understanding of MM and non-MM (both positive and negative cooperativity) kinetics of monomeric enzymes, in term of non-equilibrium steady state cycle on the 2D free energy surface. Chapters 8-11 present the principle and application of a new ultra-sensitive nonlinear optical microspectroscopy, femtosecond (fs) triple-resonant coherent anti-Stokes Raman scattering (CARS), in which the amplitude and phase of input fs laser pulses are optimally shaped to be in triple resonant with the molecular electronic and vibrational transitions to generate a coherent nonlinear signal beam at a new color with a highest possible efficiency. This technique

  6. Local disorder investigation in NiS(2-x)Se(x) using Raman and Ni K-edge x-ray absorption spectroscopies.

    PubMed

    Marini, C; Joseph, B; Caramazza, S; Capitani, F; Bendele, M; Mitrano, M; Chermisi, D; Mangialardo, S; Pal, B; Goyal, M; Iadecola, A; Mathon, O; Pascarelli, S; Sarma, D D; Postorino, P

    2014-11-12

    We report on Raman and Ni K-edge x-ray absorption investigations of a NiS(2-x)Se(x) (with x = 0.00, 0.50/0.55, 0.60, and 1.20) pyrite family. The Ni K-edge absorption edge shows a systematic shift going from an insulating phase (x = 0.00 and 0.50) to a metallic phase (x = 0.60 and 1.20). The near-edge absorption features show a clear evolution with Se doping. The extended x-ray absorption fine structure data reveal the evolution of the local structure with Se doping which mainly governs the local disorder. We also describe the decomposition of the NiS(2-x)Se(x) Raman spectra and investigate the weights of various phonon modes using Gaussian and Lorentzian profiles. The effectiveness of the fitting models in describing the data is evaluated by means of Bayes factor estimation. The Raman analysis clearly demonstrates the disorder effects due to Se alloying in describing the phonon spectra of NiS(2-x)Se(x) pyrites.

  7. RESONANT ABSORPTION OF TRANSVERSE OSCILLATIONS AND ASSOCIATED HEATING IN A SOLAR PROMINENCE. II. NUMERICAL ASPECTS

    SciTech Connect

    Antolin, P.; Okamoto, T. J.; Doorsselaere, T. Van; Yokoyama, T.

    2015-08-10

    Transverse magnetohydrodynamic (MHD) waves are ubiquitous in the solar atmosphere and may be responsible for generating the Sun’s million-degree outer atmosphere. However, direct evidence of the dissipation process and heating from these waves remains elusive. Through advanced numerical simulations combined with appropriate forward modeling of a prominence flux tube, we provide the observational signatures of transverse MHD waves in prominence plasmas. We show that these signatures are characterized by a thread-like substructure, strong transverse dynamical coherence, an out-of-phase difference between plane-of-the-sky motions and line-of-sight velocities, and enhanced line broadening and heating around most of the flux tube. A complex combination between resonant absorption and Kelvin–Helmholtz instabilities (KHIs) takes place in which the KHI extracts the energy from the resonant layer and dissipates it through vortices and current sheets, which rapidly degenerate into turbulence. An inward enlargement of the boundary is produced in which the turbulent flows conserve the characteristic dynamics from the resonance, therefore guaranteeing detectability of the resonance imprints. We show that the features described in the accompanying paper through coordinated Hinode and Interface Region Imaging Spectrograph observations match the numerical results well.

  8. Effects of core position of locally resonant scatterers on low-frequency acoustic absorption in viscoelastic panel

    NASA Astrophysics Data System (ADS)

    Zhong, Jie; Wen, Ji-Hong; Zhao, Hong-Gang; Yin, Jian-Fei; Yang, Hai-Bin

    2015-08-01

    Locally resonant sonic materials, due to their ability to control the propagation of low-frequency elastic waves, have become a promising option for underwater sound absorption materials. In this paper, the finite element method is used to investigate the absorption characteristics of a viscoelastic panel periodically embedded with a type of infinite-long non-coaxially cylindrical locally resonant scatterers (LRSs). The effect of the core position in the coating layer of the LRS on the low-frequency (500 Hz-3000 Hz) sound absorption property is investigated. With increasing the longitudinal core eccentricity e, there occur few changes in the absorptance at the frequencies below 1500 Hz, however, the absorptance above 1500 Hz becomes gradually better and the valid absorption (with absorptance above 0.8) frequency band (VAFB) of the viscoelastic panel becomes accordingly broader. The absorption mechanism is revealed by using the displacement field maps of the viscoelastic panel and the steel slab. The results show two typical resonance modes. One is the overall resonance mode (ORM) caused by steel backing, and the other is the core resonance mode (CRM) caused by LRS. The absorptance of the viscoelastic panel by ORM is induced mainly by the vibration of the steel slab and affected little by core position. On the contrary, with increasing the core eccentricity, the CRM shifts toward high frequency band and decouples with the ORM, leading to two separate absorption peaks and the broadened VAFB of the panel. Project supported by the National Natural Science Foundation of China (Grant No. 51275519).

  9. Geminate recombination and vibrational relaxation dynamics of aqueous chlorine dioxide: A time-resolved resonance Raman study

    NASA Astrophysics Data System (ADS)

    Hayes, Sophia C.; Philpott, Matthew J.; Reid, Philip J.

    1998-08-01

    The photochemical dynamics of aqueous chlorine dioxide (OClO) are investigated using time-resolved resonance Raman spectroscopy. Stokes and anti-Stokes spectra are measured as a function of time following photoexcitation of OClO using degenerate pump and probe wavelengths at 390 nm. The temporal evolution of OClO Stokes intensity is found to be consistent with the reformation of ground-state OClO by subpicosecond geminate recombination of the primary ClO and O photofragments. Anti-Stokes intensity is observed for transitions corresponding to the symmetric stretch of OClO demonstrating that upon geminate recombination, excess vibrational energy is deposited along this coordinate. Dissipation of this energy to the surrounding solvent occurs with a time constant of ˜9 ps. Finally, a delay in the appearance of OClO anti-Stokes intensity relative to geminate recombination is observed demonstrating that the excess vibrational energy available to OClO is initially deposited along the resonance Raman inactive asymmetric stretch coordinate with the exchange of energy between this coordinate and the symmetric stretch occurring with a time-constant of ˜5 ps.

  10. Understanding double-resonant Raman scattering in chiral carbon nanotubes: Diameter and energy dependence of the D mode

    NASA Astrophysics Data System (ADS)

    Herziger, Felix; Vierck, Asmus; Laudenbach, Jan; Maultzsch, Janina

    2015-12-01

    We present a theoretical model to describe the double-resonant scattering process in arbitrary carbon nanotubes (CNTs). We use this approach to investigate the defect-induced D mode in CNTs and unravel the dependence of the D -mode frequency on the CNT diameter and on the energy of the resonant optical transition. Our approach is based on the symmetry of the hexagonal lattice and geometric considerations; hence the method is independent of the exact model that is chosen to describe the electronic band structure or the phonon dispersion. We finally clarify the diameter dependence of this Raman mode that has been under discussion in the past and demonstrate that, depending on the experimental conditions, in general two different dependencies can be measured. We also prove that CNTs with an arbitrary chiral index can exhibit a D mode in their Raman spectrum, in contrast to previous symmetry-based arguments. Furthermore, we give a direct quantification of the curvature-induced phonon frequency corrections of the D mode in CNTs with respect to graphite.

  11. 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.

  12. 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.

  13. Avoiding Ethanol Presence in DNA Samples Enhances the Performance of Ultraviolet Resonance Raman Spectroscopy Analysis.

    PubMed

    Cammisuli, Francesca; Pascolo, Lorella; Morgutti, Marcello; Gessini, Alessandro; Masciovecchio, Claudio; D'Amico, Francesco

    2017-01-01

    Ethanol is an essential chemical reagent in DNA preparation as its use increases the yield of extraction. All methodologies for DNA isolation involve the use of ethanol in order to prevent DNA dissolution in water and to optimize the binding of DNA to chromatographic membranes. In this note, we show how the presence of ethanol traces in DNA aqueous solution affects ultraviolet Raman spectra, leading to possible misinterpretations. We report a simple method to remove the ethanol Raman features from the spectra, based on heating the DNA sample at 80 ℃, followed by a slow cooling procedure.

  14. Polarization control efficiency manipulation in resonance-mediated two-photon absorption by femtosecond spectral frequency modulation

    NASA Astrophysics Data System (ADS)

    Yao, Yunhua; Cheng, Wenjing; Zheng, Ye; Xu, Cheng; Liu, Pei; Jia, Tianqing; Qiu, Jianrong; Sun, Zhenrong; Zhang, Shian

    2017-04-01

    The femtosecond laser polarization modulation is considered as a very simple and efficient method to control the multi-photon absorption process. In this work, we theoretically and experimentally show that the polarization control efficiency in the resonance-mediated two-photon absorption can be artificially manipulated by modulating the femtosecond spectral frequency components. We theoretically demonstrate that the on- and near-resonant parts in the resonance-mediated two-photon absorption process depend on the different femtosecond spectral frequency components, and therefore their contributions in the whole excitation process can be controlled by properly designing the femtosecond spectral frequency components. The near-resonant two-photon absorption is correlated with the femtosecond laser polarization while the on-resonant two-photon absorption is independent of it, and thus the polarization control efficiency in the resonance-mediated two-photon absorption can be manipulated by the femtosecond spectral frequency modulation. We experimentally verify these theoretical results by performing the laser polarization control experiment in the Dy3+-doped glass sample under the modulated femtosecond spectral frequency components, and the experimental results show that the polarization control efficiency can be increased when the central spectral frequency components are cut off, while it is decreased when both the low and high spectral frequency components are cut off, which is in good agreement with the theoretical predictions. Our works can provide a feasible pathway to understand and control the resonance-mediated multi-photon absorption process under the femtosecond laser field excitation, and also may open a new opportunity to the related application areas.

  15. Controlling successive ionic layer absorption and reaction cycles to optimize silver nanoparticle-induced localized surface plasmon resonance effects on the paper strip

    NASA Astrophysics Data System (ADS)

    Lee, Jae-Chul; Kim, Wansun; Park, Hun-Kuk; Choi, Samjin

    2017-03-01

    This study investigates why a silver nanoparticle (SNP)-induced surface-enhanced Raman scattering (SERS) paper chip fabricated at low successive ionic layer absorption and reaction (SILAR) cycles leads to a high SERS enhancement factor (7 × 108) with an inferior nanostructure and without generating a hot spot effect. The multi-layered structure of SNPs on cellulose fibers, verified by magnified scanning electron microscopy (SEM) and analyzed by a computational simulation method, was hypothesized as the reason. The pattern of simulated local electric field distribution with respect to the number of SILAR cycles showed good agreement with the experimental Raman intensity, regardless of the wavelength of the excitation laser sources. The simulated enhancement factor at the 785-nm excitation laser source (2.8 × 109) was 2.5 times greater than the experimental enhancement factor (1.1 × 109). A 532-nm excitation laser source exhibited the highest maximum local electric field intensity (1.9 × 1011), particularly at the interparticle gap called a hot spot. The short wavelength led to a strong electric field intensity caused by strong electromagnetic coupling arising from the SNP-induced local surface plasmon resonance (LSPR) effects through high excitation energy. These findings suggest that our paper-based SILAR-fabricated SNP-induced LSPR model is valid for understanding SNP-induced LSPR effects.

  16. Controlling successive ionic layer absorption and reaction cycles to optimize silver nanoparticle-induced localized surface plasmon resonance effects on the paper strip.

    PubMed

    Lee, Jae-Chul; Kim, Wansun; Park, Hun-Kuk; Choi, Samjin

    2017-03-05

    This study investigates why a silver nanoparticle (SNP)-induced surface-enhanced Raman scattering (SERS) paper chip fabricated at low successive ionic layer absorption and reaction (SILAR) cycles leads to a high SERS enhancement factor (7×10(8)) with an inferior nanostructure and without generating a hot spot effect. The multi-layered structure of SNPs on cellulose fibers, verified by magnified scanning electron microscopy (SEM) and analyzed by a computational simulation method, was hypothesized as the reason. The pattern of simulated local electric field distribution with respect to the number of SILAR cycles showed good agreement with the experimental Raman intensity, regardless of the wavelength of the excitation laser sources. The simulated enhancement factor at the 785-nm excitation laser source (2.8×10(9)) was 2.5 times greater than the experimental enhancement factor (1.1×10(9)). A 532-nm excitation laser source exhibited the highest maximum local electric field intensity (1.9×10(11)), particularly at the interparticle gap called a hot spot. The short wavelength led to a strong electric field intensity caused by strong electromagnetic coupling arising from the SNP-induced local surface plasmon resonance (LSPR) effects through high excitation energy. These findings suggest that our paper-based SILAR-fabricated SNP-induced LSPR model is valid for understanding SNP-induced LSPR effects.

  17. Sound Absorption of a 2DOF Resonant Liner with Negative Bias Flow

    NASA Technical Reports Server (NTRS)

    Ahuja, K. K.; Cataldi, P.; Gaeta, R. J., Jr.

    2000-01-01

    This report describes an experimental study conducted to determine the effect of negative bias flow on the sound absorption of a two degree-of-freedom liner. The backwall for the liner was designed to act as a double-Helmholtz resonator so as to act as a hard wall at all frequencies except at its resonant frequencies. The effect of bias flow is investigated for a buried septum porosity of 2% and 19.5% for bias flow orifice Mach numbers up to 0.311. The bias flow appears to modify the resistance and reactance of the backwall alone at lower frequencies up to about 2 kHz, with marginal effects at higher frequencies. Absorption coefficients close to unity are achieved for a frequency range of 500 - 4000 Hz for the overall liner for a septum porosity of 2% and orifice Mach number of 0.128. Insertion loss tests performed in a flow duct facility for grazing flow Mach numbers up to 0.2 and septum Mach numbers up to 0.15 showed that negative bias flow can increase insertion loss by as much as 10 dB at frequencies in the range of 500 D 1400 Hz compared to no grazing flow. The effectiveness of the negative bias flow is diminished as the grazing flow velocity is increased.

  18. Proton emission from resonant laser absorption and self-focusing effects from hydrogenated structures

    NASA Astrophysics Data System (ADS)

    Cutroneo, M.; Torrisi, L.; Margarone, D.; Picciotto, A.

    2013-05-01

    Effects of resonant absorption and self-focusing are investigated by using fast and intense laser pulses. The ion emission and acceleration in the non-equilibrium laser-generated plasma are investigated at low and high intensities, from 1010 up to about 1016 W/cm2. The properties of plasma are strongly dependent on the time and space, laser intensity and wavelength. A special interest concerns the energetic and intense proton generation for the multiplicity use that proton beams have in different scientific fields (Nuclear Physics, Astrophysics, Bio-Medicine, Microelecronics, etc.). Investigations have been performed at INFN-LNS of Catania and at PALS Laboratory of Prague, by using thick and thin targets and different technique of ion analysis. The mechanisms of resonant absorption of the laser light, produced in special targets containing nanostructures with dimensions comparable with the laser wavelength, enhances the proton energy. The mechanisms of self-focusing, obtained by changing the laser focal distance from the target surface, increase the local intensity and consequently the high directional ion acceleration. Real-time ion detections were performed through Thomson parabola spectrometer (TPS), ion collectors (IC), SiC detectors and ion energy analyzer (IEA) employed in time-of-flight configuration (TOF). The energy and the amount of ions increase significantly when the two non-linear phenomena occurs, as will be described.

  19. Anharmonic resonance absorption of short laser pulses in clusters: A molecular dynamics simulation study

    NASA Astrophysics Data System (ADS)

    Mahalik, S. S.; Kundu, M.

    2016-12-01

    Linear resonance (LR) absorption of an intense 800 nm laser light in a nano-cluster requires a long laser pulse >100 fs when Mie-plasma frequency ( ω M ) of electrons in the expanding cluster matches the laser frequency (ω). For a short duration of the pulse, the condition for LR is not satisfied. In this case, it was shown by a model and particle-in-cell (PIC) simulations [Phys. Rev. Lett. 96, 123401 (2006)] that electrons absorb laser energy by anharmonic resonance (AHR) when the position-dependent frequency Ω [ r ( t ) ] of an electron in the self-consistent anharmonic potential of the cluster satisfies Ω [ r ( t ) ] = ω . However, AHR remains to be a debate and still obscure in multi-particle plasma simulations. Here, we identify AHR mechanism in a laser driven cluster using molecular dynamics (MD) simulations. By analyzing the trajectory of each MD electron and extracting its Ω [ r ( t ) ] in the self-generated anharmonic plasma potential, it is found that electron is outer ionized only when AHR is met. An anharmonic oscillator model, introduced here, brings out most of the features of MD electrons while passing the AHR. Thus, we not only bridge the gap between PIC simulations, analytical models, and MD calculations for the first time but also unequivocally prove that AHR process is a universal dominant collisionless mechanism of absorption in the short pulse regime or in the early time of longer pulses in clusters.

  20. Mapping the amide I absorption in single bacteria and mammalian cells with resonant infrared nanospectroscopy

    NASA Astrophysics Data System (ADS)

    Baldassarre, L.; Giliberti, V.; Rosa, A.; Ortolani, M.; Bonamore, A.; Baiocco, P.; Kjoller, K.; Calvani, P.; Nucara, A.

    2016-02-01

    Infrared (IR) nanospectroscopy performed in conjunction with atomic force microscopy (AFM) is a novel, label-free spectroscopic technique that meets the increasing request for nano-imaging tools with chemical specificity in the field of life sciences. In the novel resonant version of AFM-IR, a mid-IR wavelength-tunable quantum cascade laser illuminates the sample below an AFM tip working in contact mode, and the repetition rate of the mid-IR pulses matches the cantilever mechanical resonance frequency. The AFM-IR signal is the amplitude of the cantilever oscillations driven by the thermal expansion of the sample after absorption of mid-IR radiation. Using purposely nanofabricated polymer samples, here we demonstrate that the AFM-IR signal increases linearly with the sample thickness t for t \\gt 50 nm, as expected from the thermal expansion model of the sample volume below the AFM tip. We then show the capability of the apparatus to derive information on the protein distribution in single cells through mapping of the AFM-IR signal related to the amide-I mid-IR absorption band at 1660 cm-1. In Escherichia Coli bacteria we see how the topography changes, observed when the cell hosts a protein over-expression plasmid, are correlated with the amide I signal intensity. In human HeLa cells we obtain evidence that the protein distribution in the cytoplasm and in the nucleus is uneven, with a lateral resolution better than 100 nm.

  1. Resonant absorption of kink magnetohydrodynamic waves by a magnetic twist in coronal loops

    NASA Astrophysics Data System (ADS)

    Ebrahimi, Zanyar; Karami, Kayoomars

    2016-10-01

    There is ample evidence of twisted magnetic structures in the solar corona. This motivates us to consider the magnetic twist as the cause of Alfvén frequency continuum in coronal loops, which can support the resonant absorption as a rapid damping mechanism for the observed coronal kink magnetohydrodynamic (MHD) oscillations. We model a coronal loop with a straight cylindrical magnetic flux tube, which has constant but different densities in the interior and exterior regions. The magnetic field is assumed to be constant and aligned with the cylinder axis everywhere except for a thin layer near the boundary of the flux tube, which has an additional small magnetic field twist. Then, we investigate a number of possible instabilities that may arise in our model. In the thin tube thin boundary approximation, we derive the dispersion relation and solve it analytically to obtain the frequencies and damping rates of the fundamental (l = 1) and first/second overtone (l = 2, 3) kink (m = 1) MHD modes. We conclude that the resonant absorption by the magnetic twist can justify the rapid damping of kink MHD waves observed in coronal loops. Furthermore, the magnetic twist in the inhomogeneous layer can cause deviations from P1/P2 = 2 and P1/P3 = 3, which are comparable with the observations.

  2. RESONANT ABSORPTION OF TRANSVERSE OSCILLATIONS AND ASSOCIATED HEATING IN A SOLAR PROMINENCE. I. OBSERVATIONAL ASPECTS

    SciTech Connect

    Okamoto, Takenori J.; Pontieu, Bart De; Doorsselaere, Tom Van; Yokoyama, Takaaki

    2015-08-10

    Transverse magnetohydrodynamic waves have been shown to be ubiquitous in the solar atmosphere and can, in principle, carry sufficient energy to generate and maintain the Sun’s million-degree outer atmosphere or corona. However, direct evidence of the dissipation process of these waves and subsequent heating has not yet been directly observed. Here we report on high spatial, temporal, and spectral resolution observations of a solar prominence that show a compelling signature of so-called resonant absorption, a long hypothesized mechanism to efficiently convert and dissipate transverse wave energy into heat. Aside from coherence in the transverse direction, our observations show telltale phase differences around 180° between transverse motions in the plane-of-sky and line-of-sight velocities of the oscillating fine structures or threads, and also suggest significant heating from chromospheric to higher temperatures. Comparison with advanced numerical simulations support a scenario in which transverse oscillations trigger a Kelvin–Helmholtz instability (KHI) at the boundaries of oscillating threads via resonant absorption. This instability leads to numerous thin current sheets in which wave energy is dissipated and plasma is heated. Our results provide direct evidence for wave-related heating in action, one of the candidate coronal heating mechanisms.

  3. Structure-induced resonant tail-state regime absorption in polymer: fullerene bulk-heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Pfadler, Thomas; Kiel, Thomas; Stärk, Martin; Werra, Julia F. M.; Matyssek, Christian; Sommer, Daniel; Boneberg, Johannes; Busch, Kurt; Weickert, Jonas; Schmidt-Mende, Lukas

    2016-05-01

    In this work, we present resonant tail-state regime absorption enhanced organic photovoltaics. We combine periodically structured TiO2 bottom electrodes with P3HT-PCBM bulk-heterojunction solar cells in an inverted device configuration. The wavelength-scale patterns are transferred to the electron-selective bottom electrodes via direct laser interference patterning, a fast method compatible with roll-to-roll processing. Spectroscopic and optoelectronic device measurements suggest polarization-dependent absorption enhancement along with photocurrent generation unambiguously originating from the population of tail states. We discuss the effects underlying these absorption patterns with the help of electromagnetic simulations using the discontinuous Galerkin time domain method. For this, we focus on the total absorption spectra along with spatially resolved power loss densities. Our simulations stress the tunability of the absorption resonances towards arbitrary wavelength regions.

  4. Thermally activated cation ordering in ZnGa2Se4 single crystals studied by Raman scattering, optical absorption, and ab initio calculations.

    PubMed

    Vilaplana, R; Gomis, O; Pérez-González, E; Ortiz, H M; Manjón, F J; Rodríguez-Hernández, P; Muñoz, A; Alonso-Gutiérrez, P; Sanjuán, M L; Ursaki, V V; Tiginyanu, I M

    2013-04-24

    Order-disorder phase transitions induced by thermal annealing have been studied in the ordered-vacancy compound ZnGa2Se4 by means of Raman scattering and optical absorption measurements. The partially disordered as-grown sample with tetragonal defect stannite (DS) structure and I4¯2m space group has been subjected to controlled heating and cooling cycles. In situ Raman scattering measurements carried out during the whole annealing cycle show that annealing the sample to 400 °C results in a cation ordering in the sample, leading to the crystallization of the ordered tetragonal defect chalcopyrite (DC) structure with I4¯ space group. On decreasing temperature the ordered cation scheme of the DC phase can be retained at ambient conditions. The symmetry of the Raman-active modes in both DS and DC phases is discussed and the similarities and differences between the Raman spectra of the two phases emphasized. The ordered structure of annealed samples is confirmed by optical absorption measurements and ab initio calculations, that show that the direct bandgap of DC-ZnGa2Se4 is larger than that of DS-ZnGa2Se4.

  5. Difference in effect of temperature on absorption and Raman spectra between all-trans-β-carotene and all-trans-retinol

    NASA Astrophysics Data System (ADS)

    Qu, Guan-Nan; Li, Shuo; Sun, Cheng-Lin; Liu, Tian-Yuan; Wu, Yong-Ling; Sun, Shang; Shan, Xiao-Ning; Men, Zhi-Wei; Chen, Wei; Li, Zuo-Wei; Gao, Shu-Qin

    2012-12-01

    Temperature dependencies (81 °C-18 °C) ofvisible absorption and Raman spectra of all-trans-β-carotene and all-trans-retinol extremely diluted in dimethyl sulfoxide are investigated in order to clarify temperature effects on different polyenes. Their absorption spectra are identified to be redshifted with temperature decreasing. Moreover, all-trans-β-carotene is more sensitive to temperature due to the presence of a longer length of conjugated system. The characteristic energy responsible for the conformational changes in all-trans-β-carotene is smaller than that in all-trans-retinol. Both of the Raman scattering cross sections increase with temperature decreasing. The results are explained with electron—phonon coupling theory and coherent weakly damped electron—lattice vibrations model.

  6. Resonance-based metamaterial in the shallow sub-wavelength regime: negative refractive index and nearly perfect absorption

    NASA Astrophysics Data System (ADS)

    Trang Pham, Thi; Nguyen, Hoang Tung; Tuyen Le, Dac; Tong, Ba Tuan; Giang Trinh, Thi; Tuong Pham, Van; Vu, Dinh Lam

    2016-12-01

    The research on magnetic resonances in typical meta-atoms has led to the discovery of electromagnetic metamaterials (MMs). These new materials played a crucial role in achieving extraordinary phenomena as well as promised potential applications. In this paper, we numerically and experimentally investigated two different MM effects: the absorption and the negative refraction, which induced by magnetic resonances in a symmetric structure. The meta-atom sandwich model that includes two parallel flat rings separated by an insulating slab was designed. Firstly, three resonances in sub-wavelength range were demonstrated, revealing the negative permittivity and permeability effects. Notably, negative refractive index (NRI) was gained at the third-gap resonance, resulting from superposition of the rest of the electric resonance and the magnetic one accompanied by multi-plasmon. Moreover, the manipulation of the structural parameters could control the NRI behavior and, interestingly, a nearly perfect absorption peak arises in shallow sub-wavelength regime.

  7. Plasmon resonance and perfect light absorption in subwavelength trench arrays etched in gallium-doped zinc oxide film

    SciTech Connect

    Hendrickson, Joshua R. Leedy, Kevin; Cleary, Justin W.; Vangala, Shivashankar; Nader, Nima; Guo, Junpeng

    2015-11-09

    Near-perfect light absorption in subwavelength trench arrays etched in highly conductive gallium-doped zinc oxide films was experimentally observed in the mid infrared regime. At wavelengths corresponding to the resonant excitation of surface plasmons, up to 99% of impinging light is efficiently trapped and absorbed in the periodic trenches. Scattering cross sectional calculations reveal that each individual trench acts like a vertical split ring resonator with a broad plasmon resonance spectrum. The coupling of these individual plasmon resonators in the grating structure leads to enhanced photon absorption and significant resonant spectral linewidth narrowing. Ellipsometry measurements taken before and after device fabrication result in different permittivity values for the doped zinc oxide material, indicating that localized annealing occurred during the plasma etching process due to surface heating. Simulations, which incorporate a 50 nm annealed region at the zinc oxide surface, are in a good agreement with the experimental results.

  8. Microwave absorption of a TiO2@PPy hybrid and its nonlinear dielectric resonant attenuation mechanism

    NASA Astrophysics Data System (ADS)

    Jiang, Wanchun; Wang, Yu; Xie, Aming; Wu, Fan

    2016-09-01

    We report on a high-performance electromagnetic absorption material (TiO2@PPy) developed via a facile in situ polymerization process, where lower than  -60 dB maximum absorption and 6.56 dB effective absorption bandwidth (lower than  -10 dB) can be obtained under low thickness. The excellent electromagnetic wave absorption ability is attributed to the synthetic effect of improved impedance matching and the dual loss mechanism, which originates from the polarization relaxations of dipoles induced by vacancy defects and a conductive network constructed by aerogels. An equivalent circuit model is established to explicate the nonlinear dielectric resonant attenuation mechanism.

  9. Time-resolved postdischarge absolute silicon monoxide density measurement by resonant absorption spectroscopy in a nonthermal atmospheric plasma

    SciTech Connect

    Motret, Olivier; Coursimault, Fabien; Pouvesle, Jean-Michel

    2006-11-01

    In this study we present the technique of resonant absorption spectroscopy diagnostic developed to estimate the density of silicon monoxide (SiO) molecules during the postdischarge of an atmospheric dielectric barrier discharge plasma. The ultraviolet (0,0) rovibrational band of the SiO(A {sup 1}{pi}-X {sup 1}{sigma}{sup +}) electronic transition was investigated. Effective values of absorption coefficient and absorption cross section for the rotational transitions under consideration were calculated. The SiO concentration was estimated by comparison between experimental and computed spectra. The self-absorption in the probe reactor was taken into account in the computed spectra.

  10. Angle-tunable enhanced infrared reflection absorption spectroscopy via grating-coupled surface plasmon resonance.

    PubMed

    Petefish, Joseph W; Hillier, Andrew C

    2014-03-04

    Surface enhanced infrared absorption (SEIRA) spectroscopy is an attractive method for increasing the prominence of vibrational modes in infrared spectroscopy. To date, the majority of reports associated with SEIRA utilize localized surface plasmon resonance from metal nanoparticles to enhance electromagnetic fields in the region of analytes. Limited work has been performed using propagating surface plasmons as a method for SEIRA excitation. In this report, we demonstrate angle-tunable enhancement of vibrational stretching modes associated with a thin poly(methyl methacrylate) (PMMA) film that is coupled to a silver-coated diffraction grating. Gratings are fabricated using laser interference lithography to achieve precise surface periodicities, which can be used to generate surface plasmons that overlap with specific vibrational modes in the polymer film. Infrared reflection absorption spectra are presented for both bare silver and PMMA-coated silver gratings at a range of angles and polarization states. In addition, spectra were obtained with the grating direction oriented perpendicular and parallel to the infrared source in order to isolate plasmon enhancement effects. Optical simulations using the rigorous coupled-wave analysis method were used to identify the origin of the plasmon-induced enhancement. Angle-dependent absorption measurements achieved signal enhancements of more than 10-times the signal in the absence of the plasmon.

  11. Plasmon resonances of Ag(001) and Ag(111) studied by power density absorption and photoyield

    NASA Astrophysics Data System (ADS)

    Raseev, Georges

    2013-09-01

    This paper models the surface and bulk plasmon resonances in photoabsorption and photoelectron spectra (PES) of the Ag(001) and the Ag(111) surfaces in the region of 2.8-10 eV excited with a p or transverse magnetic linearly polarized laser incident at 45°. Using the recently developed vector potential from electron density-coupled integro-differential equations (VPED-CIDE, [1,2]) model, we calculate the electron escaping probability from the power density absorption, Feibelman's parameter d⊥, the reflectance and the Fermi PE cross section. In the PES experiment the work function is lowered from 4.5 to 2.8 eV by adsorption of sodium. In our model, this lowering is introduced by adding a phenomenological term to the DFT-LDA model potential of Chulkov et al. [3]. For both Ag(001) and Ag(111), the calculated observables display two plasmon resonances, the multipole surface at 3.70 eV and the bulk at 3.90 eV, in fair agreement with the experimental PES of Barman et al. [4,5] and the reflectance. Except for the Fermi PE cross section of Ag(001) which does not display the multipole surface plasmon resonance at 3.70 eV. This poor result is probably due to a poor calculation of the conduction band wave functions obtained from the Schrödinger equation using the modified DFT-LDA model potential of Chulkov et al.

  12. Intramolecular hydrogen bonding and excited state proton transfer in hydroxyanthraquinones as studied by electronic spectra, resonance Raman scattering, and transform analysis

    NASA Astrophysics Data System (ADS)

    Marzocchi, Mario P.; Mantini, Anna R.; Casu, Maurizio; Smulevich, Giulietta

    1998-01-01

    The scheme of energy levels previously proposed to describe dual excitation and emission associated to excited state intramolecular proton transfer (ESIPT) of some hydroxyanthraquinones (HAQ's) has been made more quantitative in the present paper. The zero-point energy and the frequency of the νOH mode for the HAQ's have been calculated on the basis of the Lippincott-Schroeder double-minimum potential for the O-H⋯O hydrogen bond. The second derivative absorption (D2) spectra show that the vibrational structures of the electronic excited state of HAQ's giving rise to ESIPT are characterized by the progression of the νOH stretching mode. The νOH mode in the ground state is observed as a very strong band in the vibrational structure of the short wavelength emission for HAQ's showing ESIPT. The combined resonance Raman band assignment of four hydroxyanthraquinones and transform analysis show that the visible transition involves the hydrogen bonded cycle and induces proton transfer in the excited state in most cases. On the basis of the isotopic effects, some vibrations of the hydrogen bonded cycle, namely the νC=O, δC=O, νCOH, and δOH modes, have been identified. The transform method, including the combined analysis of the absorption and D2 spectra in terms of sum-over-states, was checked by directly deriving the displacement parameters (Franck-Condon factors) of 1,4-DHAQ from the high resolution free-jet spectrum. The values of the displacement parameters of the νOH mode are quite large for the HAQ's showing ESIPT, while are negligible for 1,4-DHAQ. High values of the displacement parameters for the other vibrations of the hydrogen bonded cycle were found for all HAQ's.

  13. Shifting of infrared radiation using rotational raman resonances in diatomic molecular gases

    DOEpatents

    Kurnit, Norman A.

    1980-01-01

    A device for shifting the frequency of infrared radiation from a CO.sub.2 laser by stimulated Raman scattering in either H.sub.2 or D.sub.2. The device of the preferred embodiment comprises an H.sub.2 Raman laser having dichroic mirrors which are reflective for 16 .mu.m radiation and transmittive for 10 .mu.m, disposed at opposite ends of an interaction cell. The interaction cell contains a diatomic molecular gas, e.g., H.sub.2, D.sub.2, T.sub.2, HD, HT, DT and a capillary waveguide disposed within the cell. A liquid nitrogen jacket is provided around the capillary waveguide for the purpose of cooling. In another embodiment the input CO.sub.2 radiation is circularly polarized using a Fresnel rhomb .lambda./4 plate and applied to an interaction cell of much longer length for single pass operation.

  14. Near-field and confocal surface-enhanced resonance Raman spectroscopy at cryogenic temperatures.

    PubMed

    Anger, P; Feltz, A; Berghaus, T; Meixner, A J

    2003-03-01

    For laser spectroscopy at variable temperatures with high spatial resolution a combined scanning near-field optical and confocal microscope was developed. Rhodamine 6G (R6G) dye molecules dispersed on silver nano-particles or nano-clusters were investigated. For optical excitation of the molecules, either an aperture probe or a focused laser spot in confocal arrangement were employed. Raman spectra in the wavenumber range between 300 cm-1 and 3000 cm-1 at room temperatures down to 8.5 K were recorded. Many of the observed Raman lines can be associated with the structure of the adsorbed molecule. Intensity fluctuations in spectral sequences were observed down to 77 K and are indicative of single molecule sensitivity.

  15. 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.

  16. Estimating nanoparticle optical absorption with magnetic resonance temperature imaging and bioheat transfer simulation

    PubMed Central

    MacLellan, Christopher J.; Fuentes, David T.; Elliott, Andrew M.; Schwartz, Jon; Hazle, John D.; Stafford, R. Jason

    2014-01-01

    Purpose Optically activated nanoparticle-mediated heating for thermal therapy applications is an area of intense research. The ability to characterize the spatiotemporal heating potential of these particles for use in modeling under various exposure conditions can aid in the exploration of new approaches for therapy as well as more quantitative prospective approaches to treatment planning. The purpose of this research was to investigate an inverse solution to the heat equation, using magnetic resonance temperature imaging (MRTI) feedback, for providing optical characterization of two types of nanoparticles (gold-silica nanoshells and gold nanorods). Methods The optical absorption of homogeneous nanoparticle-agar mixtures was measured during exposure to an 808nm laser using real-time MRTI. A coupled finite element solution of heat transfer was registered with the data and used to solve the inverse problem. The L2 norm of the difference between the temperature increase in the model and MRTI was minimized using a pattern search algorithm by varying the absorption coefficient of the mixture. Results Absorption fractions were within 10% of literature values for similar nanoparticles. Comparison of temporal and spatial profiles demonstrated good qualitative agreement between the model and the MRTI. The weighted root mean square error was <1.5 σMRTI and the average Dice similarity coefficient for ΔT = 5°C isotherms was > 0.9 over the measured time interval. Conclusion This research demonstrates the feasibility of using an indirect method for making minimally invasive estimates of nanoparticle absorption that might be expanded to analyze a variety of geometries and particles of interest. PMID:24350668

  17. Pre-resonance enhancement of exceptional intensity in Aggregation-Induced Raman Optical Activity (AIROA) spectra of lutein derivatives

    NASA Astrophysics Data System (ADS)

    Zajac, G.; Lasota, J.; Dudek, M.; Kaczor, A.; Baranska, M.

    2017-02-01

    Recently reported new phenomenon of Aggregation-Induced Raman Optical Activity is demonstrated here for the first time in the pre-resonance conditions for lutein diacetate and 3‧-epi-lutein supramolecular self-assembles. We demonstrate that minor alterations in the lutein structure (e.g. acetylation of hydroxyl groups or different configuration at one of the chiral center) can lead to definitely different spectral profiles and optical properties due to formation of aggregates of different structure and type. Lutein forms only H-aggregates, lutein diacetate only J-aggregates, while 3‧-epi-lutein can occur in both forms simultaneously. Variety of aggregates' structures is so large that not only the type of aggregation is different, but also their chirality. It is remarkable that even in the pre-resonance conditions, aggregation of lutein derivatives can lead to the intense ROA signal, and moreover, 3‧-epi-lutein demonstrated the highest resonance ROA CID ratio that has ever been reported.

  18. Ligation and quaternary structure induced changes in the heme pocket of hemoglobin: a transient resonance Raman study.

    PubMed

    Friedman, J M; Stepnoski, R A; Stavola, M; Ondrias, M R; Cone, R L

    1982-04-27

    The extent to which ligation and quaternary structure modify the heme-heme pocket configuration is determined by generating and analyzing transient resonance Raman spectra from various photolyzed and partially photolyzed hemoglobins (Hb). From small frequently shifts in Raman band I (approximately 1355 cm-1) it is determined that ligation induces a configurational change about the heme. The extent to which ligation modifies the heme pocket is influenced by the quaternary structure. With respect to the structural parameter responsible for variations in the pi orbital electron density of the porphyrin, the degree of alteration of the heme pocket configuration relative to deoxy-Hb(T) follows the sequence: liganded Hb(R) greater than liganded Hb(R) + IHP greater than liganded Hb(T) [alpha chain greater than beta chain] greater than deoxy-Hb(R). This progression of configurations also forms a sequence with respect to the "retentiveness" of the heme pocket as reflected in the ligand dynamics associated with geminate recombination. The results indicate that the heme-heme pocket of the R-state Hb's, relative to those of the T-state species, favors ligand retention in a dynamic, as well as thermodynamic, sense. The analysis of these and other related data implicates a ligation and quaternary structure modulated electronic and/or electrostatic interaction between the pi system of the porphyrin and the surrounding heme pocket as the basis for this variation in ligand dynamics as well as for the energetics of cooperativity.

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

    SciTech Connect

    Sivadasan, A. K. Patsha, Avinash; Dhara, Sandip

    2015-04-27

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

  20. 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.

  1. The use of ultraviolet resonance Raman spectroscopy in the analysis of ionizing-radiation-induced damage in DNA.

    PubMed

    Shaw, C P; Jirasek, A

    2009-04-01

    Ultraviolet resonance Raman spectroscopy (UVRRS) was used to determine damage done in both calf-thymus DNA (CT-DNA) and a short stranded DNA oligomer (SS-DNA) due to ionizing radiation from a medical (60)Co radiation therapy unit used in the treatment of cancer. Spectra were acquired at incident UV wavelengths of 248, 257, and 264 nm in order to utilize the differences in UVRR cross-sections of the bases with wavelength. Through the analysis of difference spectra between irradiated and unirradiated DNA at each of the incident UV wavelengths, damage to CT- and SS-DNA was observed and identified. Significant radiation-induced increases in the difference spectra of the CT-DNA indicated disruption of the stable, stacked structure of its bases, as well as the disruption of Watson-Crick hydrogen bonds between the base pairs. Base unstacking was not as evident in the SS-DNA, while radiation-induced spectral decreases suggest disruption of the structure of the nucleotides. As demonstrated, UVRRS has the ability to highlight contributions from specific moieties with the use of varying incident UV wavelengths, thus enhancing the already information-rich content of the Raman spectra.

  2. A new combined nuclear magnetic resonance and Raman spectroscopic probe applied to in situ investigations of catalysts and catalytic processes

    NASA Astrophysics Data System (ADS)

    Camp, Jules C. J.; Mantle, Michael D.; York, Andrew P. E.; McGregor, James

    2014-06-01

    Both Raman and nuclear magnetic resonance (NMR) spectroscopies are valuable analytical techniques capable of providing mechanistic information and thereby providing insights into chemical processes, including catalytic reactions. Since both techniques are chemically sensitive, they yield not only structural information but also quantitative analysis. In this work, for the first time, the combination of the two techniques in a single experimental apparatus is reported. This entailed the design of a new experimental probe capable of recording simultaneous measurements on the same sample and/or system of interest. The individual datasets acquired by each spectroscopic method are compared to their unmodified, stand-alone equivalents on a single sample as a means to benchmark this novel piece of equipment. The application towards monitoring reaction progress is demonstrated through the evolution of the homogeneous catalysed metathesis of 1-hexene, with both experimental techniques able to detect reactant consumption and product evolution. This is extended by inclusion of magic angle spinning (MAS) NMR capabilities with a custom made MAS 7 mm rotor capable of spinning speeds up to 1600 Hz, quantified by analysis of the spinning sidebands of a sample of KBr. The value of this is demonstrated through an application involving heterogeneous catalysis, namely the metathesis of 2-pentene and ethene. This provides the added benefit of being able to monitor both the reaction progress (by NMR spectroscopy) and also the structure of the catalyst (by Raman spectroscopy) on the very same sample, facilitating the development of structure-performance relationships.

  3. Optical fibre probe NIR Raman measurements in ambient light and in combination with a tactile resonance sensor for possible cancer detection.

    PubMed

    Nyberg, Morgan; Ramser, Kerstin; Lindahl, Olof A

    2013-07-21

    First measurements on a combined instrument with a thin fibre optic Raman probe mounted inside a hollow tactile resonance sensor have been performed in ambient light on porcine tissue. The ambient fluorescent light was removed successfully from the spectra. The stiffness and the biomolecular composition of the tissue were analysed.

  4. Effects of quenching on electronic-resonance-enhanced coherent anti-Stokes Raman scattering of nitric oxide

    NASA Astrophysics Data System (ADS)

    Roy, Sukesh; Kulatilaka, Waruna D.; Naik, Sameer V.; Laurendeau, Normand M.; Lucht, Robert P.; Gord, James R.

    2006-09-01

    We investigate the effects of gas-mixture composition on the electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) signals of nitric oxide (NO). From previous laser-induced fluorescence (LIF) studies, quenching rates are known to change drastically, by factors of 400-800, in mixtures of CO2/O2/N2. The observed ERE-CARS signal remains constant to within 30% whereas LIF signals from NO are predicted to decrease by more than two orders of magnitudes in the same environments. This is very significant for using NO ERE-CARS in high-pressure combustion environments where the electronic quenching rate can vary rapidly as a function of both space and time.

  5. The first detection of the 3A g- state in carotenoids using resonance-Raman excitation profiles

    NASA Astrophysics Data System (ADS)

    Furuichi, Kentaro; Sashima, Tokutake; Koyama, Yasushi

    2002-04-01

    The singlet 3A g- state that had been theoretically predicted in shorter polyenes [P. Tavan and K. Schulten J. Chem. Phys. 85 (1986) 6602; Phys. Rev. B 36 (1987) 4337] was first identified in bacterial carotenoids by measurements of resonance-Raman excitation profiles. It is almost overlapped with the 1B u+ state in spheroidene (the number of conjugated double bonds, n=10), and located in-between the 1B u+ and 1B u- states in lycopene, anhydrorhodovibrin and spirilloxanthin ( n=11-13). The slopes when the 2A g--, 1B u-- and 3A g--state energies were expressed as linear functions of 1/(2 n+1) exhibited the ratio of 2:3.1:3.8 in excellent agreement with that theoretically predicted, 2:3.1:3.7.

  6. Detection and imaging of quorum sensing in Pseudomonas aeruginosa biofilm communities by surface-enhanced resonance Raman scattering

    NASA Astrophysics Data System (ADS)

    Bodelón, Gustavo; Montes-García, Verónica; López-Puente, Vanesa; Hill, Eric H.; Hamon, Cyrille; Sanz-Ortiz, Marta N.; Rodal-Cedeira, Sergio; Costas, Celina; Celiksoy, Sirin; Pérez-Juste, Ignacio; Scarabelli, Leonardo; La Porta, Andrea; Pérez-Juste, Jorge; Pastoriza-Santos, Isabel; Liz-Marzán, Luis M.

    2016-11-01

    Most bacteria in nature exist as biofilms, which support intercellular signalling processes such as quorum sensing (QS), a cell-to-cell communication mechanism that allows bacteria to monitor and respond to cell density and changes in the environment. As QS and biofilms are involved in the ability of bacteria to cause disease, there is a need for the development of methods for the non-invasive analysis of QS in natural bacterial populations. Here, by using surface-enhanced resonance Raman scattering spectroscopy, we report rationally designed nanostructured plasmonic substrates for the in situ, label-free detection of a QS signalling metabolite in growing Pseudomonas aeruginosa biofilms and microcolonies. The in situ, non-invasive plasmonic imaging of QS in biofilms provides a powerful analytical approach for studying intercellular communication on the basis of secreted molecules as signals.

  7. Detection and imaging of quorum sensing in Pseudomonas aeruginosa biofilm communities by surface-enhanced resonance Raman scattering

    PubMed Central

    Bodelón, Gustavo; Montes-García, Verónica; López-Puente, Vanesa; Hill, Eric H.; Hamon, Cyrille; Sanz-Ortiz, Marta N.; Rodal-Cedeira, Sergio; Costas, Celina; Celiksoy, Sirin; Pérez-Juste, Ignacio; Scarabelli, Leonardo; Porta, Andrea La; Pérez-Juste, Jorge; Pastoriza-Santos, Isabel

    2016-01-01

    Most bacteria in nature exist as biofilms, which support intercellular signaling processes such as quorum sensing (QS), a cell-to-cell communication mechanism that allows bacteria to monitor and respond to cell density and changes in the environment. Because QS and biofilms are involved in the ability of bacteria to cause disease, there is a need for the development of methods for the non-invasive analysis of QS in natural bacterial populations. Here, by using surface-enhanced resonance Raman scattering spectroscopy, we report rationally designed nanostructured plasmonic substrates for the in-situ, label-free detection of a QS signaling metabolite in growing Pseudomonas aeruginosa biofilms and microcolonies. The in situ, non-invasive plasmonic imaging of QS in biofilms provides a powerful analytical approach for studying intercellular communication on the basis of secreted molecules as signals. PMID:27500808

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

    PubMed Central

    Arefin, Md Shamsul

    2012-01-01

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

  9. Resonance Raman studies of blue copper proteins: effect of temperature and isotopic substitutions. Structural and thermodynamic implications

    SciTech Connect

    Blair, D.F.; Campbell, G.W.; Schoonover, J.R.; Chan, S.I.; Gray, H.B.; Malmstrom, B.G.; Pecht, I.; Swanson, B.I.; Woodruff, W.H.; Cho, W.K.; English, A.M.

    1985-01-01

    Resonance Raman spectra of the single-copper blue proteins azurin plastocyanin and stellacyanin and the multicopper oxidases laccase ascorbate oxidase and ceruloplasmin are reported. Cryoresonance Raman observations (10-77 K) are reported for selected azurins, stellacyanin, the plastocyanins, and the laccases. Isotope studies employing /sup 63/Cu//sup 65/Cu and H/D substitution are reported for selected azurins and stellacyanin, allowing identification of modes having significant copper-ligand (Cu-L) stretch and internal ligand deformation character. Principal conclusions include the following. The only Cu-L stretching mode near 400 cm/sup -1/ is the Cu-S(Cys) stretch, and the remainder of the elementary motions near this frequency are internal ligand deformations. All the observed modes near 400 cm/sup -1/ are highly mixed, and most derive their intensity from their fractional Cu-S(Cys) stretching character. The Cu-N(His) stretching motions are best identified with the ubiquitous peak(s) near 270 cm/sup -1/, although in azurin these modes have contributions from other coordinates. Internal histidine and cysteine motions contribute to the features near 400 cm/sup -1/. This is consistent with a single resonant electronic chromophore and extremely facile vibrational dephasing or other damping processes in the electronically excited state. Temperature effects upon the spectra suggest a significant temperature-dependent structure change at the plastocyanin active site, and a more subtle one in azurin. It is shown that the Cu-S(Cys) stretching frequency is closely correlated to the electron-transfer exothermicity for several proteins, thereby indicating the reduction potential can be fine tuned by the effects of polypeptide backbone structure on the copper-sulfur bond distance and the copper-ligand field. 41 references.

  10. A combination of dynamic light scattering and polarized resonance Raman scattering applied in the study of Arenicola Marina extracellular hemoglobin

    NASA Astrophysics Data System (ADS)

    Jernshøj, K. D.; Hassing, S.; Olsen, L. F.

    2013-08-01

    Arenicola Marina extracellular hemoglobin (Hbl Hb) is considered to be a promising candidate as a blood substitute. To entangle some of the properties of extracellular giant hexagonal bilayer hemoglobin (Hbl Hb) of Arenicola Marina, we combined polarized resonance Raman scattering (532 nm excitation) with dynamic light scattering (DLS) (632.8 nm). An analysis of the depolarization ratio of selected a2g skeletal modes of the heme in native Hbl Hb and porcine Hb, shows that the distortion of the heme group away from its ideal fourfold symmetry is much smaller for heme groups bound in the Hbl Hb than for heme groups bound in porcine Hb. Using DLS, the average hydrodynamic diameter (⟨dh⟩) of Hbl Hb was measured at pH = 5, 7, 8, 9, and 10. At pH = 5 to 7, the Hbl Hb was found in its native form with ⟨dh⟩ equal to 24.2 nm, while at pH = 8 and 9, a dissociation process starts to take place resulting in ⟨dh⟩ = 9 nm. At pH = 10, only large aggregates of fragmented Hbl Hb with ⟨dh⟩ larger than 1000 nm was detected, however, a comparison of the DLS results with the polarized resonance Raman scattering (RRS) revealed that the coupling between the fragments did not involve direct interaction between the heme groups, but also that the local heme environment seems to be comparable in the aggregates and in the native Hbl Hb. By comparing the unpolarized RRS results obtained for erythrocytes (RBC) with those for Hbl Hb, led us to the important conclusion that Hbl Hb is much easier photolyzed than porcine RBC.

  11. Resonance Raman spectroscopic investigation of the light-harvesting chromophore in escherichia coli photolyase and Vibrio cholerae cryptochrome-1.

    PubMed

    Sokolova, Olga; Cecala, Christine; Gopal, Anand; Cortazar, Frank; McDowell-Buchanan, Carla; Sancar, Aziz; Gindt, Yvonne M; Schelvis, Johannes P M

    2007-03-27

    Photolyases and cryptochromes are flavoproteins that belong to the class of blue-light photoreceptors. They usually bind two chromophores: flavin adenine dinucleotide (FAD), which forms the active site, and a light-harvesting pigment, which is a 5,10-methenyltetrahydrofolate polyglutamate (MTHF) in most cases. In Escherichia coli photolyase (EcPhr), the MTHF cofactor is present in substoichiometric amounts after purification, while in Vibrio cholerae cryptochrome-1 (VcCry1) the MTHF cofactor is bound more strongly and is present at stoichiometric levels after purification. In this paper, we have used resonance Raman spectroscopy to monitor the effect of loss of MTHF on the protein-FAD interactions in EcPhr and to probe the protein-MTHF interactions in both EcPhr and VcCry1. We find that removal of MTHF does not perturb protein-FAD interactions, suggesting that it may not affect the physicochemical properties of FAD in EcPhr. Our data demonstrate that the pteridine ring of MTHF in EcPhr has different interactions with the protein matrix than that of MTHF in VcCry1. Comparison to solution resonance Raman spectra of MTHF suggests that the carbonyl of its pteridine ring in EcPhr experiences stronger hydrogen bonding and a more polar environment than in VcCry1, but that hydrogen bonding to the pteridine ring amine hydrogens is stronger in VcCry-1. These differences in hydrogen bonding may account for the higher binding affinity of MTHF in VcCry1 compared to EcPhr.

  12. A combination of dynamic light scattering and polarized resonance Raman scattering applied in the study of Arenicola Marina extracellular hemoglobin.

    PubMed

    Jernshøj, K D; Hassing, S; Olsen, L F

    2013-08-14

    Arenicola Marina extracellular hemoglobin (Hbl Hb) is considered to be a promising candidate as a blood substitute. To entangle some of the properties of extracellular giant hexagonal bilayer hemoglobin (Hbl Hb) of Arenicola Marina, we combined polarized resonance Raman scattering (532 nm excitation) with dynamic light scattering (DLS) (632.8 nm). An analysis of the depolarization ratio of selected a(2g) skeletal modes of the heme in native Hbl Hb and porcine Hb, shows that the distortion of the heme group away from its ideal fourfold symmetry is much smaller for heme groups bound in the Hbl Hb than for heme groups bound in porcine Hb. Using DLS, the average hydrodynamic diameter () of Hbl Hb was measured at pH = 5, 7, 8, 9, and 10. At pH = 5 to 7, the Hbl Hb was found in its native form with equal to 24.2 nm, while at pH = 8 and 9, a dissociation process starts to take place resulting in = 9 nm. At pH = 10, only large aggregates of fragmented Hbl Hb with larger than 1000 nm was detected, however, a comparison of the DLS results with the polarized resonance Raman scattering (RRS) revealed that the coupling between the fragments did not involve direct interaction between the heme groups, but also that the local heme environment seems to be comparable in the aggregates and in the native Hbl Hb. By comparing the unpolarized RRS results obtained for erythrocytes (RBC) with those for Hbl Hb, led us to the important conclusion that Hbl Hb is much easier photolyzed than porcine RBC.

  13. Resonance-induced absorption enhancement in colloidal quantum dot solar cells using nanostructured electrodes.

    PubMed

    Mahpeykar, Seyed Milad; Xiong, Qiuyang; Wang, Xihua

    2014-10-20

    The application of nanostructured indium-doped tin oxide (ITO) electrodes as diffraction gratings for light absorption enhancement in colloidal quantum dot solar cells is numerically investigated using finite-difference time-domain (FDTD) simulation. Resonant coupling of the incident diffracted light with supported waveguide modes in light absorbing layer at particular wavelengths predicted by grating far-field projection analysis is shown to provide superior near-infrared light trapping for nanostructured devices as compared to the planar structure. Among various technologically feasible nanostructures, the two-dimensional nano-branch array is demonstrated as the most promising polarization-independent structure and proved to be able to maintain its performance despite structural imperfections common in fabrication.

  14. Magnetic resonance imaging of acoustic streaming: absorption coefficient and acoustic field shape estimation.

    PubMed

    Madelin, Guillaume; Grucker, Daniel; Franconi, Jean-Michel; Thiaudiere, Eric

    2006-07-01

    In this study, magnetic resonance imaging (MRI) is used to visualize acoustic streaming in liquids. A single-shot spin echo sequence (HASTE) with a saturation band perpendicular to the acoustic beam permits the acquisition of an instantaneous image of the flow due to the application of ultrasound. An average acoustic streaming velocity can be estimated from the MR images, from which the ultrasonic absorption coefficient and the bulk viscosity of different glycerol-water mixtures can be deduced. In the same way, this MRI method could be used to assess the acoustic field and time-average power of ultrasonic transducers in water (or other liquids with known physical properties), after calibration of a geometrical parameter that is dependent on the experimental setup.

  15. Resonant two-photon absorption of extreme-ultraviolet free-electron-laser radiation in helium

    SciTech Connect

    Nagasono, Mitsuru; Suljoti, Edlira; Pietzsch, Annette; Hennies, Franz; Wellhoefer, Michael; Hoeft, Jon-Tobias; Martins, Michael; Wurth, Wilfried; Foehlisch, Alexander; Treusch, Rolf; Feldhaus, Josef; Schneider, Jochen R.

    2007-05-15

    We have investigated the nonlinear response of helium to intense extreme-ultraviolet radiation from the free-electron laser in Hamburg (FLASH). We observe a spectral feature between 24 and 26 eV electron kinetic energy in photoemission which shows a quadratic fluence dependence. The feature is explained as a result of subsequent processes involving a resonant two-photon absorption process into doubly excited levels of even parity (N=5 and 6), radiative decay to the doubly excited states in the vicinity of the He{sup +} (N=2) ionization threshold and finally the photoionization of the inner electron by the radiation of the next microbunches. This observation suggests that even-parity states, which have been elusive to be measured with the low pulse energy of synchrotron radiation sources, can be investigated with the intense radiation of FLASH. This also demonstrates a first step to bring nonlinear spectroscopy into the xuv and soft-x-ray regime.

  16. Analysis of Pu Isotopes in Melted Fuel by Neutron Resonance Transmission: Examination by Linear Absorption Model

    NASA Astrophysics Data System (ADS)

    Kitatani, F.; Harada, H.; Takamine, J.; Kureta, M.; Seya, M.

    2014-04-01

    We have been studying the feasibility of neutron resonance transmission analysis (NRTA) for quantifying nuclear materials (Pu/U isotopes) in particle-like debris of melted fuel for nuclear material accountability and safeguards. The achievable measurement accuracy of NRTA was examined using a linear absorption model for the sample which contain substances other than nuclear fuel materials, such as boron and iron. The impurities (boron and iron etc.) in melted fuel are from the support structure and criticality control materials of the reactor core, and should be included to study the feasibility of NRTA for actual application. Neutron transmission spectra were calculated using the total neutron cross-sections in JENDL-4.0. The transmission spectra together with their uncertainties were evaluated. The study showed quantitatively that the statistical uncertainty in the determination of atomic number density of each isotope depends on the impurity density in the sample. The optimal thickness of the sample was determined for various impurity densities.

  17. Sound Absorption of a 2DOF Resonant Liner with Negative Bias Flow

    NASA Technical Reports Server (NTRS)

    Ahuja, K. K.; Cataldi, P.; Gaeta, R. J., Jr.; Jones, Mike (Technical Monitor)

    2000-01-01

    This report describes an experimental study conducted to determine the effect of negative bias flow on the sound absorption of a two degree-of-freedom liner. The backwall for the liner was designed to act as a double-Helmholtz resonator so as to act as a hard wall at all frequencies except at its resonant frequencies. All normal incident impedance data presented herein was acquired in an impedance tube. The effect of bias flow is investigated for a buried septum porosity of 2% and 19.5% for bias flow orifice mach numbers up to 03 11. As a porous backwall is needed for the flow to pass through, the effect of bias flow on this backwall all had to be evaluated first. The bias flow appears to modify the resistance and reactance of the backwall alone at lower frequencies up to about 2 kHz, with marginal effects at higher frequencies. Absorption coefficients close to unity are achieved for a frequency range of 500-4000 Hz for the overall liner for a septum porosity of 2% and orifice mach number of 0.128. Insertion loss tests performed in a flow duct facility for grazing flow Mach numbers up to 0.2 and septum mach numbers up to 0.15 showed that negative bias flow can increase insertion loss by as much as 10 dB at frequencies in the range of 500 - 1400 Hz compared to no grazing flow. The effectiveness of the negative bias flow is diminished as the grazing flow velocity is increased.

  18. Hydrogen bonding of sulfur ligands in blue copper and iron-sulfur proteins: detection by resonance raman spectroscopy

    SciTech Connect

    Mino, Y.; Loehr, T.M.; Wada, K.; Matsubara, H.; Sanders-Loehr, J.

    1987-12-15

    The resonance Raman spectrum of the blue copper protein azurin from Alcaligenes denitrificans exhibits nine vibrational modes between 330 and 460 cm/sup -1/, seven of which shift 0.4-3.0 cm/sup -1/ to lower energy after incubation of the protein in D/sub 2/O. These deuterium-dependent shifts have been previously ascribed to exchangeable protons on imidazole ligands or to exchangeable protons on amide groups which are hydrogen bonded to the cysteine thiolate ligands (a feature common to all blue copper proteins of known structure). In order to distinguish between these two possibilities, a systematic investigation of Fe/sub 2/S/sub 2/(Cys)/sub 4/-containing proteins was undertaken. Extensive hydrogen bonding between sulfur ligands and the polypeptide backbone had been observed in the crystal structure of ferredoxin from Spirulina platensis. The resonance Raman spectrum of this protein is typical of a chloroplast-type ferredoxin and exhibits deuterium-dependent shifts of -0.3 to -0.5 cm/sup -1/ in the Fe-S modes at 283, 367, and 394 cm/sup -1/ and -0.6 to -0.8 cm/sup -1/ in the Fe-S modes at 328 and 341 cm/sup -1/. Considerably greater deuterium sensitivity is observed in the Raman spectra of spinach ferredoxin and bovine adrenodoxin, particularly for the symmetric stretching vibration of the Fe/sub 2/S/sub 2/ moiety at approx. 390 cm/sup -1/. This feature decreases of 9.8 and 1.1 cm/sup -1/, respectively, for the two oxidized proteins in D/sub 2/O and by 1.8 cm/sup -1/ for reduced adrenodoxin in D/sub 2/O. These results suggest that the bridging sulfido groups may be more extensively hydrogen bonded in spinach ferredoxin and adrenodoxin than in S. platensis ferredoxin, with a further increase in hydrogen-bond strength in the reduced form of adrenodoxin.

  19. The source-driven dissipative nonlinear Schroedinger model of resonance absorption

    SciTech Connect

    Larroche, O.; Pesme, D. )

    1990-08-01

    A source-driven dissipative nonlinear Schroedinger (NLS) equation is numerically studied, characterized by a nonlinearity parameter and a dissipative length, governing the generation of finite-amplitude, localized electrostatic plasma waves by resonance absorption of light in an inhomogeneous plasma. It is shown that as the nonlinearity parameter is increased a transition to chaos occurs through a quasiperiodic scenario. In the chaotic regime, it is shown from statistical diagnostics that as the dissipation length is increased, the system shifts from a convective regime governed by the competition between pumping and convection of the waves due to the inhomogeneity to a dissipative regime governed by the competition between pumping and a scale-length-dependent absorption mechanism, which approximately models Landau damping. The scaling laws obtained show that the turbulent state can be described in both regimes as a set of NLS solitons, interacting through the pumping and damping mechanisms.For a vanishing density gradient, the system admits a homogeneous limit, which is found to be chaotic and dissipative.

  20. Studying metal ion-protein interactions: electronic absorption, circular dichroism, and electron paramagnetic resonance.

    PubMed

    Quintanar, Liliana; Rivillas-Acevedo, Lina

    2013-01-01

    Metal ions play a wide range of important functional roles in biology, and they often serve as cofactors in enzymes. Some of the metal ions that are essential for life are strongly associated with proteins, forming obligate metalloproteins, while others may bind to proteins with relatively low affinity. The spectroscopic tools presented in this chapter are suitable to study metal ion-protein interactions. Metal sites in proteins are usually low symmetry centers that differentially absorb left and right circularly polarized light. The combination of electronic absorption and circular dichroism (CD) in the UV-visible region allows the characterization of electronic transitions associated with the metal-protein complex, yielding information on the geometry and nature of the metal-ligand interactions. For paramagnetic metal centers in proteins, electron paramagnetic resonance (EPR) is a powerful tool that provides information on the chemical environment around the unpaired electron(s), as it relates to the electronic structure and geometry of the metal-protein complex. EPR can also probe interactions between the electron spin and nuclear spins in the vicinity, yielding valuable information on some metal-ligand interactions. This chapter describes each spectroscopic technique and it provides the necessary information to design and implement the study of metal ion-protein interactions by electronic absorption, CD, and EPR.

  1. Efficient Non-Resonant Absorption of Electromagnetic Beams in Thin Cylindrical Targets: Experimental Evidence

    NASA Astrophysics Data System (ADS)

    Akhmeteli, Andrey; Kokodiy, Nikolay; Safronov, Boris; Balkashin, Valeriy; Priz, Ivan; Tarasevitch, Alexander

    2014-03-01

    A theoretical possibility of non-resonant, fast, and efficient (up to 40 percent) heating of very thin conducting cylindrical targets by broad electromagnetic beams was predicted in [Akhmeteli, arXiv:physics/0405091 and 0611169] based on rigorous solution of the diffraction problem. The diameter of the cylinder can be orders of magnitude smaller than the wavelength (for the transverse geometry) or the beam waist (for the longitudinal geometry) of the electromagnetic radiation. This can be used for numerous applications, such as pumping of active media of short-wavelength lasers, e.g., through efficient heating of nanotubes with laser radiation. Experimental confirmation of the above results is presented [Akhmeteli, Kokodiy, Safronov, Balkashin, Priz, Tarasevitch, arXiv:1109.1626 and 1208.0066]. Significant (up to 6%) absorption of microwave power focused on a thin fiber (the diameter is three orders of magnitude less than the wavelength) by an ellipsoidal reflector is demonstrated experimentally. For the longitudinal geometry, significant absorption (10%) of the power of a wide CO2 laser beam propagating along a thin wire is demonstrated experimentally (the diameter of the wire is two orders of magnitude less than the beam waist width).

  2. SPATIAL DAMPING OF PROPAGATING KINK WAVES DUE TO RESONANT ABSORPTION: EFFECT OF BACKGROUND FLOW

    SciTech Connect

    Soler, R.; Goossens, M.; Terradas, J.

    2011-06-20

    Observations show the ubiquitous presence of propagating magnetohydrodynamic (MHD) kink waves in the solar atmosphere. Waves and flows are often observed simultaneously. Due to plasma inhomogeneity in the direction perpendicular to the magnetic field, kink waves are spatially damped by resonant absorption. The presence of flow may affect the wave spatial damping. Here, we investigate the effect of longitudinal background flow on the propagation and spatial damping of resonant kink waves in transversely nonuniform magnetic flux tubes. We combine approximate analytical theory with numerical investigation. The analytical theory uses the thin tube (TT) and thin boundary (TB) approximations to obtain expressions for the wavelength and the damping length. Numerically, we verify the previously obtained analytical expressions by means of the full solution of the resistive MHD eigenvalue problem beyond the TT and TB approximations. We find that the backward and forward propagating waves have different wavelengths and are damped on length scales that are inversely proportional to the frequency as in the static case. However, the factor of proportionality depends on the characteristics of the flow, so that the damping length differs from its static analog. For slow, sub-Alfvenic flows the backward propagating wave gets damped on a shorter length scale than in the absence of flow, while for the forward propagating wave the damping length is longer. The different properties of the waves depending on their direction of propagation with respect to the background flow may be detected by the observations and may be relevant for seismological applications.

  3. Multipitched Diffraction Gratings for Surface Plasmon Resonance-Enhanced Infrared Reflection Absorption Spectroscopy.

    PubMed

    Petefish, Joseph W; Hillier, Andrew C

    2015-11-03

    We demonstrate the application of metal-coated diffraction gratings possessing multiple simultaneous pitch values for surface enhanced infrared absorption (SEIRA) spectroscopy. SEIRA increases the magnitude of vibrational signals in infrared measurements by one of several mechanisms, most frequently involving the enhanced electric field associated with surface plasmon resonance (SPR). While the majority of SEIRA applications to date have employed nanoparticle-based plasmonic systems, recent advances have shown how various metals and structures lead to similar signal enhancement. Recently, diffraction grating couplers have been demonstrated as a highly tunable platform for SEIRA. Indeed, gratings are an experimentally advantageous platform due to the inherently tunable nature of surface plasmon excitation at these surfaces since both the grating pitch and incident angle can be used to modify the spectral location of the plasmon resonance. In this work, we use laser interference lithography (LIL) to fabricate gratings possessing multiple pitch values by subjecting photoresist-coated glass slides to repetitive exposures at varying orientations. After metal coating, these gratings produced multiple, simultaneous plasmon peaks associated with the multipitched surface, as identified by infrared reflectance measurements. These plasmon peaks could then be coupled to vibrational modes in thin films to provide localized enhancement of infrared signals. We demonstrate the flexibility and tunability of this platform for signal enhancement. It is anticipated that, with further refinement, this approach might be used as a general platform for broadband enhancement of infrared spectroscopy.

  4. Exchange coupling controlled ferrite with dual magnetic resonance and broad frequency bandwidth in microwave absorption.

    PubMed

    Jia, Jingguo; Liu, Chuyang; Ma, Ning; Han, Gaorong; Weng, Wenjian; Du, Piyi

    2013-08-01

    Ti-doped barium ferrite powders BaFe12-x Ti x O19 (x = 0, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 and 0.8) were synthesized by the sol-gel method. The phase structure and morphology were analyzed by x-ray diffraction (XRD) and scanning electron microscopy, respectively. The powders were also studied for their magnetic properties and microwave absorption. Results show that the Ti-doped barium ferrites (BFTO) exist in single phase and exhibit hexagonal plate-like structure. The anisotropy field Ha of the BFTO decreases almost linearly with the increase in Ti concentration, which leads to a shift of the natural resonance peak toward low frequency. Two natural resonance peaks appear, which can be assigned to the double values of the Landé factor g that are found to be ∼2.0 and ∼2.3 in the system and can be essentially attributed to the existence of Fe(3+) ions and the exchange coupling effect between Fe(3+) and Fe(2+) ions, respectively. Such a dual resonance effect contributes a broad magnetic loss peak and thus a high attenuation constant, and leads to a dual reflection loss (RL) peak over the frequency range between 26.5 and 40 GHz. The high attenuation constants are between 350 and 500 at peak position. The optimal RL reaches around -45 dB and the practicable frequency bandwidth is beyond 11 GHz. This suggests that the BFTO powders could be used as microwave absorbing materials with extraordinary properties.

  5. Exchange coupling controlled ferrite with dual magnetic resonance and broad frequency bandwidth in microwave absorption

    PubMed Central

    Jia, Jingguo; Liu, Chuyang; Ma, Ning; Han, Gaorong; Weng, Wenjian; Du, Piyi

    2013-01-01

    Ti-doped barium ferrite powders BaFe12−xTixO19 (x = 0, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 and 0.8) were synthesized by the sol–gel method. The phase structure and morphology were analyzed by x-ray diffraction (XRD) and scanning electron microscopy, respectively. The powders were also studied for their magnetic properties and microwave absorption. Results show that the Ti-doped barium ferrites (BFTO) exist in single phase and exhibit hexagonal plate-like structure. The anisotropy field Ha of the BFTO decreases almost linearly with the increase in Ti concentration, which leads to a shift of the natural resonance peak toward low frequency. Two natural resonance peaks appear, which can be assigned to the double values of the Landé factor g that are found to be ∼2.0 and ∼2.3 in the system and can be essentially attributed to the existence of Fe3+ ions and the exchange coupling effect between Fe3+ and Fe2+ ions, respectively. Such a dual resonance effect contributes a broad magnetic loss peak and thus a high attenuation constant, and leads to a dual reflection loss (RL) peak over the frequency range between 26.5 and 40 GHz. The high attenuation constants are between 350 and 500 at peak position. The optimal RL reaches around −45 dB and the practicable frequency bandwidth is beyond 11 GHz. This suggests that the BFTO powders could be used as microwave absorbing materials with extraordinary properties. PMID:27877595

  6. Quantum Interference Effects in Resonant Raman Spectroscopy of Single- and Triple-Layer MoTe2 from First-Principles.

    PubMed

    Miranda, Henrique P C; Reichardt, Sven; Froehlicher, Guillaume; Molina-Sánchez, Alejandro; Berciaud, Stéphane; Wirtz, Ludger

    2017-03-02

    We present a combined experimental and theoretical study of resonant Raman spectroscopy in single- and triple-layer MoTe2. Raman intensities are computed entirely from first-principles by calculating finite differences of the dielectric susceptibility. In our analysis, we investigate the role of quantum interference effects and the electron-phonon coupling. With this method, we explain the experimentally observed intensity inversion of the A1(') vibrational modes in triple-layer MoTe2 with increasing laser photon energy. Finally, we show that a quantitative comparison with experimental data requires the proper inclusion of excitonic effects.

  7. Magnetic assistance highly sensitive protein assay based on surface-enhanced resonance Raman scattering.

    PubMed

    Chen, Lei; Hong, Wonjin; Guo, Zhinan; Sa, Youngjo; Wang, Xu; Jung, Young Mee; Zhao, Bing

    2012-02-15

    A simple and effective surface-enhanced Raman scattering (SERS)-based protocol for the detection of protein-small molecule interactions has been developed. We employed silver-coated magnetic particles (AgMNPs), which can provide high SERS activity as a protein carrier to capture a small molecule. Combining magnetic separation and the SERS method for protein detection, highly reproducible SERS spectra of a protein-small molecule complex can be obtained with high sensitivity. This time-saving method employs an external magnetic field to induce the AgMNPs to aggregate to increase the amount of atto610-biotin/avidin complex in a unit area with the SERS enhancement. Because of the contribution of the AgMNP aggregation to the SERS, this protocol has great potential for practical high-throughput detection of the protein-small molecule complex and the antigen-antibody immunocomplex.

  8. Observation of x-ray resonant Raman scattering: The early days

    SciTech Connect

    Sparks, C.J.

    1995-12-31

    My early observation of Raman scattering came as a serendipitous by-product of our efforts to achieve the best possible signal for x-ray fluorescent analysis. We were also investigating the x-ray spectrum produced by a monochromatic x-ray beam striking metal targets which might contribute to the inelastic background. This background could contaminate the very weak diffusively distributed elastically scattered radiation associated with defects in the perfect periodicity of crystals. Energy analysis of the x-ray spectra created by monochromatic Cu K{sub {alpha}} and Mo K{sub {alpha}} radiation impinging on highly pure metal targets showed an inelastically scattered intensity related to the energy difference between the exciting radiation and the nearest bound state. Confirmation of these observations and availability of synchrotron radiation has led to wide application of this new x-ray spectroscopy in atomic physics including its use as a probe of the unoccupied density of states.

  9. Off-resonant squeezed vacuum effects on a driven two-level atom: absorption and intensity harmonics

    NASA Astrophysics Data System (ADS)

    Hassan, S. S.; Frege, O. M.; Nayak, N.

    1995-07-01

    The resonance fluorescence system of a coherently driven two-level atom in the presence of a broadband squeezed vacuum field whose central frequency is not in resonance with either the driving field frequency or the atomic transition frequency is analyzed. Solutions of the Bloch equations of the system are presented in terms of continued fractions for arbitrary strength of the coherent driving field. Numerical results are presented for the first-harmonic quadrature components of the absorption spectrum and the fluorescent intensity. The effects of the squeezed vacuum field detuning on the absorption spectrum result in hole burning or a dip structure in the weak-field case and two absorption-amplification peaks in the strong-field case. Results are sensitive to the relative phase of the squeezed vacuum.

  10. Resonant absorption in semiconductor nanowires and nanowire arrays: Relating leaky waveguide modes to Bloch photonic crystal modes

    SciTech Connect

    Fountaine, Katherine T.; Whitney, William S.; Atwater, Harry A.

    2014-10-21

    We present a unified framework for resonant absorption in periodic arrays of high index semiconductor nanowires that combines a leaky waveguide theory perspective and that of photonic crystals supporting Bloch modes, as array density transitions from sparse to dense. Full dispersion relations are calculated for each mode at varying illumination angles using the eigenvalue equation for leaky waveguide modes of an infinite dielectric cylinder. The dispersion relations along with symmetry arguments explain the selectivity of mode excitation and spectral red-shifting of absorption for illumination parallel to the nanowire axis in comparison to perpendicular illumination. Analysis of photonic crystal band dispersion for varying array density illustrates that the modes responsible for resonant nanowire absorption emerge from the leaky waveguide modes.

  11. Structural characterization of titania by X-ray diffraction, photoacoustic, Raman spectroscopy and electron paramagnetic resonance spectroscopy.

    PubMed

    Kadam, R M; Rajeswari, B; Sengupta, Arijit; Achary, S N; Kshirsagar, R J; Natarajan, V

    2015-02-25

    A titania mineral (obtained from East coast, Orissa, India) was investigated by X-ray diffraction (XRD), photoacoustic spectroscopy (PAS), Raman and Electron Paramagnetic Resonance (EPR) studies. XRD studies indicated the presence of rutile (91%) and anatase (9%) phases in the mineral. Raman investigation supported this information. Both rutile and anatase phases have tetragonal structure (rutile: space group P4(2)/mnm, a=4.5946(1) Å, c=2.9597(1) Å, V=62.48(1) (Å)(3), Z=2; anatase: space group I4(1)/amd, 3.7848(2) Å, 9.5098(11) Å, V=136.22(2) (Å)(3), Z=4). The deconvoluted PAS spectrum showed nine peaks around 335, 370, 415,485, 555, 605, 659, 690,730 and 785 nm and according to the ligand field theory, these peaks were attributed to the presence of V(4+), Cr(3+), Mn(4+) and Fe(3+) species. EPR studies revealed the presence of transition metal ions V(4+)(d(1)), Cr(3+)(d(3)), Mn(4+)(d(3)) and Fe(3+)(d(5)) at Ti(4+) sites. The EPR spectra are characterized by very large crystal filed splitting (D term) and orthorhombic distortion term (E term) for multiple electron system (s>1) suggesting that the transition metal ions substitute the Ti(4+) in the lattice which is situated in distorted octahedral coordination of oxygen. The possible reasons for observation of unusually large D and E term in the EPR spectra of transition metal ions (S=3/2 and 5/2) are discussed.

  12. PiezoForce and Contact Resonance Microscopy Correlated with Raman Spectroscopy applied to a Non-linear Optical Material and to a Lithium Battery Material

    NASA Astrophysics Data System (ADS)

    Lewis, Aaron; Zeltzer, Gabi; Zinoviev, Oleg; Roth, Michael; Roling, Bernhard; Lewis, Aaron; Dekhter, Rimma

    2014-03-01

    A non-linear optical material (KTP) and a lithium-ion conductive glass ceramic (LICGC) for lithium batteries have been studied with Raman Spectroscopy on-line with Piezo Force and Contact Resonance Microscopies. This is allowed by a unique design of the scanned probe microscopy platform used in these studies and the electrical probes that have been developed that keep the optical axis completely free from above so that such combinations are feasible. The integration allows the investigation of alterations in the strain induced in the chemical structure of the materials as a result of the induction of piezo force. The combination of chemical characterization with both piezo force and contact resonance [1] microscopy allows for the monitoring of structural and ionic changes using Raman scattering correlated with these modalities. In KTP, it has been seen that the largest changes take place in TiO6 octahedral structure symmetric and antisymmetric stretch in the interfaces between the regions of the poling of the structure. In the LICGC, defined Raman changes are observed that are related to the contact resonance frequency. The combination adds considerable insight into both the techniques of Piezo Force Microscopy and Contact Resonance Microscopy.

  13. Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study.

    PubMed

    Kumar, Venkatraman Ravi; Rajkumar, Nagappan; Ariese, Freek; Umapathy, Siva

    2015-10-08

    The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR(3)) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (μs). Interestingly, TR(3) spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ, assigned to nπ* and ππ* of which the ππ* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (∼2 ns) between the T(2)(1(3)nπ*) and T(1)(1(3)ππ*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents [ J. Chem. Phys. 2015 , 142 , 24305 ] suggest that the lowest nπ* and ππ* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

  14. Double resonant absorption measurement of acetylene symmetric vibrational states probed with cavity ring down spectroscopy

    NASA Astrophysics Data System (ADS)

    Karhu, J.; Nauta, J.; Vainio, M.; Metsälä, M.; Hoekstra, S.; Halonen, L.

    2016-06-01

    A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring-down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene, ν 1 + ν 2 + ν 3 + ν4 1 + ν5 - 1 in the normal mode notation. Single-photon transitions to this state from the vibrational ground state are forbidden. Ten lines of the newly measured state are observed and fitted with the linear least-squares method to extract the band parameters. The vibrational term value was measured to be at 9775.0018(45) cm-1, the rotational parameter B was 1.162 222(37) cm-1, and the quartic centrifugal distortion parameter D was 3.998(62) × 10-6 cm-1, where the numbers in the parenthesis are one-standard errors in the least significant digits.

  15. Temperature induced changes in resonance Raman spectra intensity of all-trans-β-carotene: changes in the fundamental, combination and overtone modes.

    PubMed

    Liu, Tianyuan; Xu, Shengnan; Li, Zuowei; Wang, Mengzhou; Sun, Chenglin

    2014-10-15

    The resonance Raman spectra of the fundamental, combination and overtone modes around the CC and CC stretches of all-trans-β-carotene in 1,2-dichloroethane solution are obtained from the 293K to 83K temperature range. The results indicate that the intensity of the fundamentals in the liquid and solid phases generally increases as the temperature decreases, except for the liquid-solid phase transition, which exhibits a decreasing trend. The Raman intensities ratio between the fundamentals υ1 and υ2, combinations (overtones) and the fundamentals both increases with decreasing temperature. The Raman bandwidths of the CC bonds gradually become narrow as the temperature decreases. These varieties of relative intensity are analyzed using the coherent weakly damped electron-lattice vibration mode, the effective conjugation length mode as well as the theory of electron-phonon interaction in this work.

  16. The effect of chemical variations on the structural polarity of relaxor ferroelectrics studied by resonance Raman spectroscopy.

    PubMed

    Rohrbeck, A; de la Flor, G; Aroyo, M I; Gospodinov, M; Bismayer, U; Mihailova, B

    2016-11-30

    Resonance Raman spectroscopy was applied to doped PbSc0.5Ta0.5O3 and PbSc0.5Nb0.5O3 relaxor ferroelectrics, to better understand the effect of composition disorder on the mesoscopic-scale polar order in complex perovskite-type (ABO3) ferroelectrics. The excitation photon energy used was 3.8 eV, which is slightly above the energy gap and corresponds to the maximum of the optical dielectric permittivity. Group-theory analysis reveals that the resonance Raman scattering (RRS) observed under these conditions is allowed only in polar crystal classes. Therefore, RRS is dominated by the atomic dynamics of nanoregions with coherent polar distortions, which considerably facilitates the comparison of polar order in various compounds. The results show that A-site doping (Ba(2+), Sr(2+), La(3+), Bi(3+)) has significantly stronger effect on the structural polarity than the introduction of a third element at the B site (Nb(5+) or Sn(4+) doped in PbSc0.5Ta0.5O3). The A-site substitution by cations that in contrast to Pb(2+) have isotropic outermost electron shells disturbs the system of lone-pair electrons, thus reducing the correlation length of coupled polar distortions and the strength of the electric field associated with the mean polarization of polar nanoregions. A-site doping with larger cations (Ba(2+)) augments the polar deformation of the individual BO6 octahedra due to local elastic fields. As a result, such A-site doping intensifies the initial structural polarity at high temperatures and prevails the enlargement of the polar fraction at low temperatures. A-site doping with smaller cations (Sr(2+), La(3+)), regardless if they are isovalent or aliovalent to Pb(2+), increases the correlation length of antiferrodistortive order (BO6 tilts), which in turn assists the development of double-perovskite structure with coherent local polar distortions. A-site doping with aliovalent cations (Bi(3+)) having the same outermost electron shell and ionic radius as the host A

  17. The effect of chemical variations on the structural polarity of relaxor ferroelectrics studied by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Rohrbeck, A.; de la Flor, G.; Aroyo, M. I.; Gospodinov, M.; Bismayer, U.; Mihailova, B.

    2016-11-01

    Resonance Raman spectroscopy was applied to doped PbSc0.5Ta0.5O3 and PbSc0.5Nb0.5O3 relaxor ferroelectrics, to better understand the effect of composition disorder on the mesoscopic-scale polar order in complex perovskite-type (ABO3) ferroelectrics. The excitation photon energy used was 3.8 eV, which is slightly above the energy gap and corresponds to the maximum of the optical dielectric permittivity. Group-theory analysis reveals that the resonance Raman scattering (RRS) observed under these conditions is allowed only in polar crystal classes. Therefore, RRS is dominated by the atomic dynamics of nanoregions with coherent polar distortions, which considerably facilitates the comparison of polar order in various compounds. The results show that A-site doping (Ba2+, Sr2+, La3+, Bi3+) has significantly stronger effect on the structural polarity than the introduction of a third element at the B site (Nb5+ or Sn4+ doped in PbSc0.5Ta0.5O3). The A-site substitution by cations that in contrast to Pb2+ have isotropic outermost electron shells disturbs the system of lone-pair electrons, thus reducing the correlation length of coupled polar distortions and the strength of the electric field associated with the mean polarization of polar nanoregions. A-site doping with larger cations (Ba2+) augments the polar deformation of the individual BO6 octahedra due to local elastic fields. As a result, such A-site doping intensifies the initial structural polarity at high temperatures and prevails the enlargement of the polar fraction at low temperatures. A-site doping with smaller cations (Sr2+, La3+), regardless if they are isovalent or aliovalent to Pb2+, increases the correlation length of antiferrodistortive order (BO6 tilts), which in turn assists the development of double-perovskite structure with coherent local polar distortions. A-site doping with aliovalent cations (Bi3+) having the same outermost electron shell and ionic radius as the host A-site Pb2+ cations leads to

  18. A copper(II) complex with a Cu-S₈ bond. Attenuated total reflectance, electron paramagnetic resonance, resonance Raman and atoms-in-molecule calculations.

    PubMed

    Shee, Nirmal K; Adekunle, Florence A O; Verma, Ravi; Kumar, Devesh; Datta, Dipankar

    2015-12-05

    Green [Cu(1,10-phenanthroline)2OH2](ClO4)2 (1) reacts with yellow elemental sulfur at room temperature in methanol to yield turquoise blue [Cu(1,10-phenanthro-line)2(S8)](ClO4)2 (2). A comparative study of the EPR spectra of 1 and 2 in solid state and in methanol glass indicates that the S8 unit in 2 is bound to the metal. High level DFT calculations show that the cation in 2 is five coordinate, distorted square pyramidal with S8 occupying the apical position. The crucial Cu(II)-S bond is around 2.9Å. Such long Cu(II)-S bonds occur in oxidized plastocyanin where it is considered to be bonding. Presence of a weak Cu-S8 bond is revealed in the resonance Raman spectra of 2. Satisfactory matching of the calculated and experimental IR spectra vindicates the theoretically derived structure of the cation in 2.

  19. Resonant photoemission and X-ray absorption spectroscopies of lithiated magnetite thin film

    NASA Astrophysics Data System (ADS)

    Tsuchiya, Takashi; Kawamura, Kinya; Namiki, Wataru; Furuichi, Shoto; Takayanagi, Makoto; Minohara, Makoto; Kobayashi, Masaki; Horiba, Koji; Kumigashira, Hiroshi; Terabe, Kazuya; Higuchi, Tohru

    2017-04-01

    Resonant photoemission spectroscopy (RPES) and X-ray absorption spectroscopy (XAS) were used to investigate the effect of lithiation on the electronic structure of Fe3O4 thin film relevant to the operation mechanism of nanoionic devices to enable magnetic property tuning. Comparison of the Fe 2p XAS spectrum for lithiated Fe3O4 (Li-Fe3O4) with that for pristine Fe3O4 clearly demonstrated that the number of Fe2+ ions at octahedral B sites is increased by lithiation. The valence band RPES spectra of Li-Fe3O4 further showed that lithiation increases the density of states near the Fermi level originating Fe2+ ions at octahedral B sites. These findings agree well with the observed decrease in the saturation magnetization in the magnetization-magnetic field (M-H) loop of Li-Fe3O4 thin film, indicating that minority spins (down spins) increase (i.e., total spins decrease) due to lithiation. The variation in the number of Fe2+ ions at B sites is suggested to be an underlying operating mechanism of a nanoionics-based magnetic property tuning device.

  20. Dual-modality probe intended for prostate cancer detection combining Raman spectroscopy and tactile resonance technology--discrimination of normal human prostate tissues ex vivo.

    PubMed

    Nyberg, M; Jalkanen, V; Ramser, K; Ljungberg, B; Bergh, A; Lindahl, O A

    2015-04-01

    Prostate cancer is the most common cancer for men in the western world. For the first time, a dual-modality probe, combining Raman spectroscopy and tactile resonance technology, has been used for assessment of fresh human prostate tissue. The study investigates the potential of the dual-modality probe by testing its ability to differentiate prostate tissue types ex vivo. Measurements on four prostates show that the tactile resonance modality was able to discriminate soft epithelial tissue and stiff stroma (p < 0.05). The Raman spectra exhibited a strong fluorescent background at the current experimental settings. However, stroma could be discerned from epithelia by integrating the value of the spectral background. Combining both parameters by a stepwise analysis resulted in 100% sensitivity and 91% specificity. Although no cancer tissue was analysed, the results are promising for further development of the instrument and method for discriminating prostate tissues and cancer.

  1. Sensitive marker bands for the detection of spin states of heme in surface-enhanced resonance Raman scattering spectra of metmyoglobin.

    PubMed

    Kitahama, Yasutaka; Egashira, Masatoshi; Suzuki, Toshiaki; Tanabe, Ichiro; Ozaki, Yukihiro

    2014-12-21

    Surface-enhanced resonance Raman scattering (SERRS) spectra of myoglobin (Mb) with various ligands were measured. In the resonance Raman scattering (RRS) spectra, peaks at around 1610 and 1640 cm(-1) have so far been used to discriminate between the heme iron in a high or low spin state. In the SERRS spectra, however, the spin state cannot be distinguished by the corresponding peaks. Alternatively, the intensity ratio of the SERRS peak at 1560 cm(-1) to that at 1620 cm(-1) was applied to detect the spin states sensitively (1.5 × 10(5) times compared with the RRS); namely, a high ratio was obtained from met-Mb in the high spin state at pH ≤ 7 except for in a strong acid solution. The different marker bands between the SERRS and RRS spectra may be due to the enhancement order from the surface selection rule.

  2. Absorption Lineshapes in Two-Dimensional Electron Spin Resonance and the Effects of Slow Motions in Complex Fluids

    NASA Astrophysics Data System (ADS)

    Saxena, Sunil; Freed, Jack H.

    1997-02-01

    A methodology for obtaining pure absorption two-dimensional electron spin resonance spectra is presented for the case of large inhomogeneous broadening and/or slow motions. For slow motions, the spectra consist of "complex Lorentzians" superimposed with complex weighting factors, presenting a challenge to obtaining absorption spectra. It is shown how absorption-type spectra can be recovered for the two-pulse COSY and SECSY experiments in such cases. For three-pulse 2D ELDOR experiments, absorption lineshapes can be obtained for the autopeaks, whereas the cross peaks would be of mixed-mode character, in general. However, for practical cases the dispersive components in the cross peaks will be relatively small. Theoretical and experimental absorption spectra are provided to illustrate the method and to show the improved resolution obtained from absorption lineshapes. In particular, the variation in linewidths across a SECSY spectrum, which is a key component in elucidating motional dynamics, is clearly rendered in the pure absorption mode. A convenient method for introducing the necessary phase corrections for the slow-motional spectra is also provided.

  3. 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

  4. Effects of pressure variations on electronic-resonance-enhanced coherent anti-Stokes Raman scattering of nitric oxide

    NASA Astrophysics Data System (ADS)

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

    2007-06-01

    The effects of pressure variations on the electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) signal of nitric oxide (NO) were studied at pressures ranging from 0.1 to 8 bar. ERE-CARS signals were recorded in a gas cell filled with a mixture of 300 ppm NO in N 2 buffer gas at room temperature. The ERE-CARS signal was found to increase with rising pressure up to 2 bar and to remain nearly constant thereafter. The spectra recorded at different cell pressures were modeled using a modified version of the Sandia CARSFT code. Laser-saturation effects were accounted for by systematically varying the theoretical ultraviolet probe-laser linewidth. Excellent agreement was obtained between theory and experiment for the pressure-scaling behavior of the ERE-CARS signal of NO. This finding, along with a negligible influence of electronic quenching on the ERE-CARS signal, provides strong incentive for the application of ERE-CARS to measurements of NO concentrations in high-pressure combustion environments.

  5. Raman and nuclear magnetic resonance investigation of alkali metal vapor interaction with alkene-based anti-relaxation coating

    NASA Astrophysics Data System (ADS)

    Tretiak, O. Yu.; Blanchard, J. W.; Budker, D.; Olshin, P. K.; Smirnov, S. N.; Balabas, M. V.

    2016-03-01

    The use of anti-relaxation coatings in alkali vapor cells yields substantial performance improvements compared to a bare glass surface by reducing the probability of spin relaxation in wall collisions by several orders of magnitude. Some of the most effective anti-relaxation coating materials are alpha-olefins, which (as in the case of more traditional paraffin coatings) must undergo a curing period after cell manufacturing in order to achieve the desired behavior. Until now, however, it has been unclear what physicochemical processes occur during cell curing, and how they may affect relevant cell properties. We present the results of nondestructive Raman-spectroscopy and magnetic-resonance investigations of the influence of alkali metal vapor (Cs or K) on an alpha-olefin, 1-nonadecene coating the inner surface of a glass cell. It was found that during the curing process, the alkali metal catalyzes migration of the carbon-carbon double bond, yielding a mixture of cis- and trans-2-nonadecene.

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

    PubMed

    Leona, Marco

    2009-09-01

    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 microm 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).

  7. Single v. multiple measures of skin carotenoids by resonance Raman spectroscopy as a biomarker of usual carotenoid status.

    PubMed

    Scarmo, Stephanie; Cartmel, Brenda; Lin, Haiqun; Leffell, David J; Ermakov, Igor V; Gellermann, Werner; Bernstein, Paul S; Mayne, Susan T

    2013-09-14

    Resonance Raman spectroscopy (RRS) is a non-invasive method of assessing carotenoid status in the skin, which has been suggested as an objective indicator of fruit/vegetable intake. The present study assessed agreement and identified predictors of single v. multiple RRS measures of skin carotenoid status. A total of seventy-four participants had their skin carotenoid status measured in the palm of the hand by RRS at six time points over 6 months. Questionnaires were administered to collect information on demographic, lifestyle and dietary data. Mean age of the participants was 36.6 years, 62.2% were female, 83.8% Caucasian and 85.1% were non-smoking at baseline. There was a good agreement between a single measure of skin carotenoids by RRS and multiple measures (weighted κ = 0.80; 95% CI 0.72, 0.88). The same variables were significantly associated with carotenoid status based on single or multiple measures, including a positive association with intake of total carotenoids (P< 0.01) and an inverse association with season of measurement (P≤ 0.05). The exception was recent sun exposure, which emerged as a significant predictor of lower carotenoid status only when using multiple RRS measures (P≤ 0.01). A single RRS measure was reasonably accurate at classifying usual skin carotenoid status. Researchers using RRS may want to take into account other factors that are associated with the biomarker, including season of measurement and recent sun exposure.

  8. 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

  9. 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.

  10. Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics

    DOE PAGES

    Kunnus, Kristjan; Josefsson, Ida; Rajkovic, Ivan; ...

    2016-10-07

    Here, ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbitalmore » and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)5 in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given—which will be covered experimentally by upcoming transform-limited x-ray sources.« less

  11. Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics

    SciTech Connect

    Kunnus, Kristjan; Josefsson, Ida; Rajkovic, Ivan; Schreck, Simon; Quevedo, Wilson; Beye, Martin; Grübel, Sebastian; Scholz, Mirko; Nordlund, Dennis; Zhang, Wenkai; Hartsock, Robert W.; Gaffney, Kelly J.; Schlotter, William F.; Turner, Joshua J.; Kennedy, Brian; Hennies, Franz; Techert, Simone; Wernet, Philippe; Odelius, Michael; Föhlisch, Alexander

    2016-10-07

    Here, ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbital and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)5 in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given—which will be covered experimentally by upcoming transform-limited x-ray sources.

  12. New Light on NO Bonding in Fe(III) Heme Proteins from Resonance Raman Spectroscopy and DFT Modeling

    PubMed Central

    Soldatova, Alexandra V.; Ibrahim, Mohammed; Olson, John S.; Czernuszewicz, Roman S.; Spiro, Thomas G.

    2010-01-01

    Visible and ultraviolet resonance Raman (RR) spectra are reported for FeIII(NO) adducts of myoglobin variants with altered polarity in the distal heme pockets. The stretching frequencies of the FeIII–NO and N–O bonds, νFeN and νNO, are negatively correlated, consistent with backbonding. However, the correlation shifts to lower νNO for variants lacking a distal histidine. DFT modeling reproduces the shifted correlations, and shows the shift to be associated with the loss of a lone-pair donor interaction from the distal histidine that selectively strengthens the N–O bond. However, when the model contains strongly electron-withdrawing substituents at the heme β-positions, νFeN and νNO become positively correlated. This effect results from FeIII–N–O bending, which is induced by lone pair donation to the NNO atom. Other mechanisms for bending are discussed, which likewise lead to a positive νFeN/νNO correlation, including thiolate ligation in heme proteins and electron-donating meso-substituents in heme models. The νFeN/νNO data for the Fe(III) complexes are reporters of heme pocket polarity and the accessibility of lone pair, Lewis base donors. Implications for biologically important processes, including NO binding, reductive nitrosylation and NO reduction, are discussed. PMID:20218710

  13. Subunit-Selective Interrogation of CO Recombination in Carbonmonoxy Hemoglobin by Isotope-Edited Time-resolved Resonance Raman Spectroscopy†

    PubMed Central

    Balakrishnan, Gurusamy; Zhao, Xiaojie; Podstawska, Edyta; Proniewicz, Leonard M.; Kincaid, James R.; Spiro, Thomas G.

    2009-01-01

    Hemoglobin is an allosteric tetrameric protein made up of αβ hetero-dimers. The α and β chains are similar, but are chemically and structurally distinct. To investigate dynamical differences between the chains, we have prepared tetramers in which the chains are isotopically distinguishable, via reconstitution with 15N-heme. Ligand recombination and heme structural evolution, following HbCO dissociation, was monitored with chain selectivity by resonance Raman (RR) spectroscopy. For α but not for β chains, the frequency of the ν4 porphyrin breathing mode increased on the microsecond time scale. This increase is a manifestation of proximal tension in the Hb T-state, and its time course is parallel to the formation of T contacts, as determined previously by UVRR spectroscopy. Despite the localization of proximal constraint in the α chains, geminate recombination was found to be equally probable in the two chains, with yields of 39 ± 2 %. We discuss the possibility that this equivalence is coincidental, in the sense that it arises from the evolutionary pressure for cooperativity, or that it reflects mechanical coupling across the αβ interface, evidence for which has emerged from UVRR studies of site-mutants. PMID:19245215

  14. Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics

    NASA Astrophysics Data System (ADS)

    Kunnus, Kristjan; Josefsson, Ida; Rajkovic, Ivan; Schreck, Simon; Quevedo, Wilson; Beye, Martin; Grübel, Sebastian; Scholz, Mirko; Nordlund, Dennis; Zhang, Wenkai; Hartsock, Robert W.; Gaffney, Kelly J.; Schlotter, William F.; Turner, Joshua J.; Kennedy, Brian; Hennies, Franz; Techert, Simone; Wernet, Philippe; Odelius, Michael; Föhlisch, Alexander

    2016-10-01

    Ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbital and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)5 in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given—which will be covered experimentally by upcoming transform-limited x-ray sources.

  15. Single v. multiple measures of skin carotenoids by resonance Raman spectroscopy as a biomarker of usual carotenoid status

    PubMed Central

    Scarmo, Stephanie; Cartmel, Brenda; Lin, Haiqun; Leffell, David J.; Ermakov, Igor V.; Gellermann, Werner; Bernstein, Paul S.; Mayne, Susan T.

    2013-01-01

    Resonance Raman spectroscopy (RRS) is a non-invasive method of assessing carotenoid status in the skin, which has been suggested as an objective indicator of fruit/vegetable intake. The present study assessed agreement and identified predictors of single v. multiple RRS measures of skin carotenoid status. A total of seventy-four participants had their skin carotenoid status measured in the palm of the hand by RRS at six time points over 6 months. Questionnaires were administered to collect information on demographic, lifestyle and dietary data. Mean age of the participants was 36.6 years, 62.2% were female, 83.8% Caucasian and 85.1% were non-smoking at baseline. There was a good agreement between a single measure of skin carotenoids by RRS and multiple measures (weighted κ = 0.80; 95% CI 0.72, 0.88). The same variables were significantly associated with carotenoid status based on single or multiple measures, including a positive association with intake of total carotenoids (P<0.01) and an inverse association with season of measurement (P≤0.05). The exception was recent sun exposure, which emerged as a significant predictor of lower carotenoid status only when using multiple RRS measures (P≤0.01). A single RRS measure was reasonably accurate at classifying usual skin carotenoid status. Researchers using RRS may want to take into account other factors that are associated with the biomarker, including season of measurement and recent sun exposure. PMID:23351238

  16. 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.

  17. Microwave resonant and zero-field absorption study of doped magnetite prepared by a co-precipitation method.

    PubMed

    Aphesteguy, Juan Carlos; Jacobo, Silvia E; Lezama, Luis; Kurlyandskaya, Galina V; Schegoleva, Nina N

    2014-06-19

    Fe3O4 and ZnxFe3-xO4 pure and doped magnetite magnetic nanoparticles (NPs) were prepared in aqueous solution (Series A) or in a water-ethyl alcohol mixture (Series B) by the co-precipitation method. Only one ferromagnetic resonance line was observed in all cases under consideration indicating that the materials are magnetically uniform. The shortfall in the resonance fields from 3.27 kOe (for the frequency of 9.5 GHz) expected for spheres can be understood taking into account the dipolar forces, magnetoelasticity, or magnetocrystalline anisotropy. All samples show non-zero low field absorption. For Series A samples the grain size decreases with an increase of the Zn content. In this case zero field absorption does not correlate with the changes of the grain size. For Series B samples the grain size and zero field absorption behavior correlate with each other. The highest zero-field absorption corresponded to 0.2 zinc concentration in both A and B series. High zero-field absorption of Fe3O4 ferrite magnetic NPs can be interesting for biomedical applications.

  18. A 2A2<--X 2B1 absorption and Raman spectra of the OClO molecule: A three-dimensional time-dependent wave packet study

    NASA Astrophysics Data System (ADS)

    Sun, Zhigang; Lou, Nanquan; Nyman, Gunnar

    2005-02-01

    Time-dependent wave packet calculations of the (A 2A2←X 2B1) absorption and Raman spectra of the OClO molecule are reported. The Fourier grid Hamiltonian method in three dimensions is employed. The X 2B1 ground state ab initio potential energy surface reported by Peterson [J. Chem. Phys. 109, 8864 (1998)] is used together with his corresponding A 2A2 state surface or the revised surface of the A 2A2 state by Xie and Guo [Chem. Phys. Lett. 307, 109 (1999)]. Radau coordinates are used to describe the vibrations of a nonrotating OClO molecule. The split-operator method combined with fast Fourier transform is applied to propagate the wave function. We find that the ab initio A 2A2 potential energy surface better reproduces the detailed structures of the absorption spectrum at long wavelength, while the revised surface of the A 2A2 state, consistent with the work of Xie and Guo, better reproduces the overall shape and the energies of the vibrational levels. Both surfaces of the A 2A2 state can reasonably reproduce the experimental Raman spectra but neither does so in detail for the numerical model employed in the present work.

  19. Symmetry-dependent exciton-phonon coupling in 2D and bulk MoS2 observed by resonance Raman scattering.

    PubMed

    Carvalho, Bruno R; Malard, Leandro M; Alves, Juliana M; Fantini, Cristiano; Pimenta, Marcos A

    2015-04-03

    This work describes a resonance Raman study performed on samples with one, two, and three layers (1L, 2L, 3L), and bulk MoS2, using more than 30 different laser excitation lines covering the visible range, and focusing on the intensity of the two most pronounced features of the Raman scattering spectrum of MoS2 (E2g(1) and A1g bands). The Raman excitation profiles of these bands were obtained experimentally, and it is found that the A1g feature is enhanced when the excitation laser is in resonance with A and B excitons of MoS2, while the E2g1 feature is shown to be enhanced when the excitation laser is close to 2.7 eV. We show from the symmetry analysis of the exciton-phonon interaction that the mode responsible for the E2g(1) resonance is identified as the high energy C exciton recently predicted [D. Y. Qiu, F. H. da Jornada, and S. G. Louie, Phys. Rev. Lett. 111, 216805 (2013)].

  20. The effects of proton-beam quality on the production of gamma rays for nuclear resonance absorption in nitrogen

    SciTech Connect

    Graybill, R.; Morgado, R.E.; Cappiello, C.C.

    1994-05-01

    The authors describe a method for performing nuclear-resonance absorption with the proton beam from a radio-frequency quadrupole (RFQ) linear accelerator. The objective was to assess the suitability of the pulsed beam from an RFQ to image nitrogen compared to electrostatic accelerators. This choice of accelerator results in trade-offs in performance and complexity, in return for the prospect of higher average current. In spite of a reduced resonance attenuation coefficient in nitrogen, they successfully produced three-dimensional tomographic images of real explosives in luggage the first time the unoptimized system was operated. The results and assessments of the initial laboratory measurements are reported.

  1. Tri-layered composite plasmonic structure with a nanohole array for multiband enhanced absorption at visible to NIR frequencies: plasmonic and metamaterial resonances

    NASA Astrophysics Data System (ADS)

    Behera, Gangadhar; Ramakrishna, S. Anantha

    2016-02-01

    A tri-layered composite structure of gold/ZnS/gold, with the top gold layer patterned into a periodic array of circular holes, was fabricated by laser interference lithography and lift-off processes. This plasmonic composite absorbing structure showed a series of enhanced absorption peaks across the visible to NIR frequencies with an peak absorption exceeding 95% at 0.52 μm wavelength. These absorption peaks were reproduced in electromagnetic simulations of the structures. The peaks are shown to arise from the various resonances of the system: the localized surface plasmon resonances of the holes, the surface plasmon polaritons on the various interfaces and the shape dependent electromagnetic resonances of the holes. The measured angular dispersion of the absorption peaks indicated the SPP origin of the resonances while the computer simulations of the electromagnetic fields could be used to understand the nature of the localized resonances.

  2. 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.

  3. Resonant metallic nanostructure for enhanced two-photon absorption in a thin GaAs p-i-n diode

    SciTech Connect

    Portier, Benjamin; Pardo, Fabrice; Péré-Laperne, Nicolas; Steveler, Emilie; Dupuis, Christophe; Bardou, Nathalie; Lemaître, Aristide; Pelouard, Jean-Luc; Vest, Benjamin; Jaeck, Julien; Rosencher, Emmanuel; Haïdar, Riad

    2014-07-07

    Degenerate two-photon absorption (TPA) is investigated in a 186 nm thick gallium arsenide (GaAs) p-i-n diode embedded in a resonant metallic nanostructure. The full device consists in the GaAs layer, a gold subwavelength grating on the illuminated side, and a gold mirror on the opposite side. For TM-polarized light, the structure exhibits a resonance close to 1.47 μm, with a confined electric field in the intrinsic region, far from the metallic interfaces. A 109 times increase in photocurrent compared to a non-resonant device is obtained experimentally, while numerical simulations suggest that both gain in TPA-photocurrent and angular dependence can be further improved. For optimized grating parameters, a maximum gain of 241 is demonstrated numerically and over incidence angle range of (−30°; +30°).

  4. Resonance Raman study of Bacillus subtilis NO synthase-like protein: similarities and differences with mammalian NO synthases.

    PubMed

    Santolini, Jérôme; Roman, Miruna; Stuehr, Dennis J; Mattioli, Tony A

    2006-02-07

    Bacterial NO synthase (NOS)-like proteins such as that from Bacillus subtilis (bsNOS) share a high degree of structural homology with the oxygenase domain of mammalian NOSs (mNOSs), but biochemical studies have yet failed to establish that they are specifically capable of producing NO. To better understand the actual function and role of bacterial NOSs, the structure and environment of bsNOS heme were examined with resonance Raman (RR) and ATR-FTIR spectroscopies. We analyzed the structural effects of l-arginine (Arg) and tetrahydrobiopterin (H(4)B) binding on several key complexes (ferric, ferrous, ferrous-CO, and ferric-NO) and characterized the bonding properties of the proximal cysteine ligand. While our study fully confirms the similarity between bsNOS and mNOS heme pocket structures, our results also highlight important differences. (i) Contrary to other NOSs, resting native ferric bsNOS exhibits an exclusive five-coordinate high-spin iron status. (ii) The nu(Fe)(-)(CO) and nu(CO) mode frequencies of the bsNOS Fe(II)CO complexes indicate a weaker electrostatic interaction between Arg and CO. (iii) bsNOS is characterized by a stronger Fe-S bond (nu(Fe)(-)(S) = 342 cm(-)(1)), a lower nu(4) frequency, and a negative shift in the nu(Fe)(-)(CO)/nu(CO) correlation. (iv) The effects of H(4)B on bsNOS heme structure are minor compared to the ones reported on mNOS. These results suggest distinct distal heme environments between mNOS and bsNOS, greater electron-donation properties of bsNOS cysteine proximal ligand, and the absence of a significant influence of H(4)B on bsNOS heme properties. These subtle structural differences may reflect changes in the chemistry and physiological role of bacterial NOSs.

  5. Density functional theory based studies on the nature of Raman and resonance Raman scattering of nerve agent bound to gold and oxide-supported gold clusters: a plausible way of detection.

    PubMed

    Majumdar, D; Roszak, Szczepan; Leszczynski, Jerzy

    2010-04-01

    A detailed theoretical investigation has been carried out at the density functional level of theories to investigate the nature of Raman intensities of the -P=O stretching mode of a model nerve agent DFP (diisopropylfluorophosphate) when bound to different gold (Au(8), Au(20)) and oxide-supported gold (MgO...Au(4), CaO...Au(4), TiO(2)...Au(4), Al(2)O(3)...Au(4), M(16)O(16)...Au(8), and [M(16)O(15)...Au(8)](2+), M = Ca, Mg) clusters. All of these clusters and the DFP-bound clusters are fully optimized, and the computed energetics shows that DFP attaches itself weakly to these clusters. The normal Raman spectra calculations on these clusters show that there is substantial enhancement of the -P=O stretching mode of DFP compared to the isolated species. This enhancement has been found to be due to the polarization of the -P=O bond of DFP when bound to the clusters. Significant enhancement in intensity has been observed in the case of Au(n)...DFP (n = 8, 20), M(16)O(16)...Au(8)...DFP, and [M(16)O(15)...Au(8)](2+)...DFP (M = Ca, Mg) clusters. The resonance Raman calculations on the Au(n)...DFP (n = 8, 20) reveals that this enhancement could be made quite large and selective, which is a feature that is unique to the nerve agents and could be used as a property for detecting them.

  6. Proof of principle of a high-spatial-resolution, resonant-response γ-ray detector for Gamma Resonance Absorption in 14N

    NASA Astrophysics Data System (ADS)

    Brandis, M.; Goldberg, M. B.; Vartsky, D.; Friedman, E.; Kreslo, I.; Mardor, I.; Dangendorf, V.; Levi, S.; Mor, I.; Bar, D.

    2011-02-01

    The development of a mm-spatial-resolution, resonant-response detector based on a micrometric glass capillary array filled with liquid scintillator is described. This detector was developed for Gamma Resonance Absorption (GRA) in 14N. GRA is an automatic-decision radiographic screening technique that combines high radiation penetration (the probe is a 9.17 MeV γ-ray) with very good sensitivity and specificity to nitrogenous explosives. Detailed simulation of the detector response to electrons and protons generated by the 9.17 MeV γ-rays was followed by a proof-of-principle experiment, using a mixed γ-ray and neutron source. Towards this, a prototype capillary detector was assembled, including the associated filling and readout systems. Simulations and experimental results indeed show that proton tracks are distinguishable from electron tracks at relevant energies, based on a criterion that combines track length and light intensity per unit length.

  7. Extended x-ray absorption fine structure and micro-Raman spectra of Bridgman grown Cd1-xZnxTe ternary alloys

    NASA Astrophysics Data System (ADS)

    Talwar, Devki N.; Feng, Zhe Chuan; Lee, Jyh-Fu; Becla, P.

    2014-03-01

    We have performed low-temperature micro-Raman scattering and extended x-ray absorption fine-structure (EXAFS) measurements on the Bridgman-grown bulk zinc-blende Cd1-x Zn x Te (1.0 ≧̸ x ≧̸ 0.03) ternary alloys to comprehend their structural and lattice dynamical properties. The micro-Raman results are carefully appraised to authenticate the classical two-phonon mode behavior insinuated by far-infrared (FIR) reflectivity study. The composition-dependent EXAFS experiments have revealed a bimodal distribution of the nearest-neighbor bond lengths—its analysis by first-principles bond-orbital model enabled us to estimate the lattice relaxations around Zn/Cd atoms in CdTe/ZnTe to help evaluate the necessary force constant variations for constructing the impurity-perturbation matrices. The simulated results of impurity vibrational modes by average-t-matrix Green’s function (ATM-GF) theory has put our experimental findings of the gap mode ˜153 cm-1 near x ≈ 1 on a much firmer ground.

  8. Spaceborne profiling of atmospheric temperature and particle extinction with pure rotational Raman lidar and of relative humidity in combination with differential absorption lidar: performance simulations

    SciTech Connect

    Di Girolamo, Paolo; Behrendt, Andreas; Wulfmeyer, Volker

    2006-04-10

    The performance of a spaceborne temperature lidar based on the pure rotational Raman (RR) technique in the UV has been simulated. Results show that such a system deployed onboard a low-Earth-orbit satellite would provide global-scale clear-sky temperature measurements in the troposphere and lower stratosphere with precisions that satisfy World Meteorological Organization (WMO) threshold observational requirements for numerical weather prediction and climate research applications. Furthermore, nighttime temperature measurements would still be within the WMO threshold observational requirements in the presence of several cloud structures. The performance of aerosol extinction measurements from space, which can be carried out simultaneously with temperature measurements by RR lidar, is also assessed. Furthermore, we discuss simulations of relative humidity measurements from space obtained from RR temperature measurements and water-vapor data measured with the differential absorption lidar (DIAL) technique.

  9. Experimental observation of microwave absorption and electron heating due to the two plasmon decay instability and resonance absorption

    SciTech Connect

    Rasmussen, D.A.

    1981-01-01

    The interaction of intense microwaves with an inhomogeneous plasma is studied in two experimental devices. In the first device an investigation was made of microwave absorption and electron heating due to the parametric decay of microwaves into electron plasma waves (Two Plasmon Decay instability, TPDI), modeling a process which can occur near the quarter critical surface in laser driven pellets. P-polarized microwave (f = 1.2 GHz, P/sub 0/ less than or equal to 12 kW) are applied to an essentially collisionless, inhomogeneous plasma, in an oversized waveguide, in the U.C. Davis Prometheus III device. The initial density scale length near the quarter critical surface is quite long (L/lambda/sub De/ approx. = 3000 or k/sub 0/L approx. = 15). The observed threshold power for the TPDI is quite low (P/sub T/approx. = 0.1 kW or v/sub os//v/sub e/ approx. = 0.1). Near the threshold the decay waves only occur near the quarter critical surface. As the incident power is increased above threshold, the decay waves spread to lower densities, and for P/sub 0/ greater than or equal to lkW, (v/sub os//v/sub e/ greater than or equal to 0.3) suprathermal electron heating is strong for high powers (T/sub H/ less than or equal to 12 T/sub e/ for P/sub 0/ less than or equal to 8 kW or v/sub os//v/sub e/ less than or equal to 0.9).

  10. Study on the interaction between fluoroquinolones and erythrosine by absorption, fluorescence and resonance Rayleigh scattering spectra and their application

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Liu, Zhongfang; Liu, Jiangtao; Liu, Shaopu; Shen, Wei

    2008-03-01

    In pH 4.4-4.5 Britton-Robinson (BR) buffer solution, fluoroquinolone antibiotics (FLQs) including ciprofloxacin (CIP), norfloxacin (NOR), levofloxacin (LEV) and lomefloxacin (LOM) could react with erythrosine (Ery) to form 1:1 ion-association complexes, which not only resulted in the changes of the absorption spectra and the quenching of fluorescence, but also resulted in the great enhancement of resonance Rayleigh scattering (RRS). These offered some indications of the determination of fluoroquinolone antibiotics by spectrophotometric, fluorescence and resonance Rayleigh scattering methods. The detection limits for fluoroquinolone antibiotics were in the range of 0.097-0.265 μg/mL for absorption methods, 0.022-0.100 μg/mL for fluorophotometry and 0.014-0.027 μg/mL for RRS method, respectively. Among them, the RRS method had the highest sensitivity. In this work, the spectral characteristics of the absorption, fluorescence and RRS, the optimum conditions of the reactions and the properties of the analytical chemistry were investigated. The methods have been successfully applied to determination of some fluoroquinolone antibiotics in human urine samples and tablets. Taking CIP-Ery system as an example, the charge distribution, the enthalpy of formation and the mean polarizability were calculated by density function theory (DFT) method. In addition, the reasons for the enhancement of scattering spectra were discussed.

  11. The power absorption and the penetration depth of electromagnetic radiation in lead telluride under cyclotron resonance conditions

    NASA Astrophysics Data System (ADS)

    Özalp, S.; Güngör, A.

    1999-10-01

    Cyclotron resonance absorption in n- and p-type PbTe was observed by Nii and was analysed under classical skin effect conditions. When the values of DC magnetic field corresponding to peaks are plotted against the field directions, a close fit is obtained between the calculated and observed results based on the assumption of a <1 1 1> ellipsoids of revolution model for the both conduction and valance band extrema. From the best fit mt=0.024 m0 and 0.03 m0 for the transverse effective masses and K= ml/ mt=9.8 and 12.2 for the anisotropic mass rations are obtained for the conduction and valance band, respectively. The observed absorption curve shows weak structures at low magnetic field. They are supposed to be due to second harmonics of Azbel'-Kaner cyclotron resonance. However, it turns out to be unnecessary to introduce other bands to explain the experimental results. The applicability of the classical magneto-optical theory is examined by calculating the power absorption coefficient and penetration depth as a function of DC magnetic field.

  12. 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.

  13. Resonance Femtosecond-Stimulated Raman Spectroscopy without Actinic Excitation Showing Low-Frequency Vibrational Activity in the S2 State of All-Trans β-Carotene.

    PubMed

    Quick, Martin; Dobryakov, Alexander L; Kovalenko, Sergey A; Ernsting, Nikolaus P

    2015-04-02

    Raman scattering with stimulating femtosecond probe pulses (FSR) was used to observe vibrational activity of all-trans β-carotene in n-hexane. The short-lived excited electronic state S2 was accessed in two ways: (i) by transient FSR after an actinic pulse to populate the S2 state, exploiting resonance from an Sx ← S2 transition, and (ii) by FSR without actinic excitation, using S2 ↔ S0 resonance exclusively and narrow-band Raman/broad-band femtosecond probe pulses only. The two approaches have nonlinear optical susceptibilities χ((5)) and χ((3)), respectively. Both methods show low-frequency bands of the S2 state at 200, 400, and ∼600 cm(-1), which are reported for the first time. With (ii) the intensities of low-frequency vibrational resonances in S2 are larger compared to those in S0, implying strong anharmonicities/mode mixing in the excited state. In principle, for short-lived electronic states, the χ((3)) method should allow the best characterization of low-frequency modes.

  14. Water-vapor absorption line measurements in the 940-nm band by using a Raman-shifted dye laser

    NASA Technical Reports Server (NTRS)

    Chu, Zhiping; Wilkerson, Thomas D.; Singh, Upendra N.

    1993-01-01

    We report water-vapor absorption line measurements that are made by using the first Stokes radiation (930-982 nm) with HWHM 0.015/cm generated by a narrow-linewidth, tunable dye laser. Forty-five absorption line strengths are measured with an uncertainty of 6 percent and among them are fourteen strong lines that are compared with previous measurements for the assessment of spectral purity of the light source. Thirty air-broadened linewidths are measured with 8 percent uncertainty at ambient atmospheric pressure with an average of 0.101/cm. The lines are selected for the purpose of temperature-sensitive or temperature-insensitive lidar measurements. Results for these line strengths and linewidths are corrected for broadband radiation and finite laser linewidth broadening effects and compared with the high-resolution transmission molecular absorption.

  15. 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.

  16. Resonant Cavity Enhanced On-Chip Raman Spectrometer Array with Precisely Positioned Metallic Nano-Gaps for Single Molecule Detection

    DTIC Science & Technology

    2011-03-22

    fabricated multi-segment gold nanowires with different diameters using electroplating, and formed nanogaps from 5nm to 50nm by sacrificial chemical etching...electroplating, and formed nanogaps from 5nm to 50nm by sacrificial chemical etching. Surface enhanced Raman scattering (SERS) characterization using these...nanowires with different diameters using electroplating, and formed nanogaps from 5nm to 50nm by sacrificial chemical etching. Surface enhanced Raman

  17. Non-resonant below-bandgap two-photon absorption in quantum dot solar cells

    SciTech Connect

    Li, Tian; Dagenais, Mario

    2015-04-27

    We study the optically nonlinear sub-bandgap photocurrent generation facilitated by an extended tailing distribution of states in an InAs/GaAs quantum dots (QDs) solar cell. The tailing states function as both the energy states for low energy photon absorption and the photocarriers extraction pathway. One of the biggest advantages of our method is that it can clearly differentiate the photocurrent due to one-photon absorption (1PA) process and two-photon absorption (2PA) process. Both 1PA and 2PA photocurrent generation efficiency in an InAs/GaAs QD device operated at 1550 nm have been quantitatively evaluated. A two-photon absorption coefficient β = 5.7 cm/GW is extracted.

  18. Selective Two-Photon Absorptive Resonance Femtosecond-Laser Electronic-Excitation Tagging (STARFLEET) Velocimetry in Flow and Combustion Diagnostics

    NASA Technical Reports Server (NTRS)

    Jiang, Naibo; Halls, Benjamin R.; Stauffer, Hans U.; Roy, Sukesh; Danehy, Paul M.; Gord, James R.

    2016-01-01

    Selective Two-Photon Absorptive Resonance Femtosecond-Laser Electronic-Excitation Tagging (STARFLEET), a non-seeded ultrafast-laser-based velocimetry technique, is demonstrated in reactive and non-reactive flows. STARFLEET is pumped via a two-photon resonance in N2 using 202.25-nm 100-fs light. STARFLEET greatly reduces the per-pulse energy required (30 µJ/pulse) to generate the signature FLEET emission compared to the conventional FLEET technique (1.1 mJ/pulse). This reduction in laser energy results in less energy deposited in the flow, which allows for reduced flow perturbations (reactive and non-reactive), increased thermometric accuracy, and less severe damage to materials. Velocity measurements conducted in a free jet of N2 and in a premixed flame show good agreement with theoretical velocities and further demonstrate the significantly less-intrusive nature of STARFLEET.

  19. Luminescence, electronic absorption and vibrational IR and Raman studies of binary and ternary cerium ortho-, pyro- and meta-phosphates doped with Pr 3+ ions

    NASA Astrophysics Data System (ADS)

    Szczygieł, I.; Macalik, L.; Radomińska, E.; Znamierowska, T.; Mączka, M.; Godlewska, P.; Hanuza, J.

    2007-05-01

    The broad class of polycrystalline ortho-[Ba 3Ce(PO 4) 3, Ca 3Ce(PO 4) 3, Ba 6Ce(PO 4) 5, K 3Ce(PO 4) 2. Na 3Ce(PO 4) 2, Na 3- xK xCe(PO 4) 2 ( x = 0.5, 1.5 and 2.5)], pyro-[NaCeP 2O 7] and meta-[NaCe(PO 3) 4, KCe(PO 3) 4, K 2Ce(PO 3) 5] phosphates was prepared in the solid state reaction. The Pr 3+ ions have been used as active probe for studies of the spectroscopic properties of these materials. Optical absorption, emission as well as infrared and Raman spectroscopic methods have been applied to characterise the properties and structure of the compounds studied. Their electronic spectra were discussed in terms of the Ce 3+ ion spectroscopic characteristics. The 2F 5/2 → 2F 7/2 transition appears in the typical for this ion region, i.e., at about 2000 cm -1. The absorption bands in the range 25,000-50,000 cm -1 have been assigned to the 4f 1 → 5d 1 transitions of the cerium ion. The role of these transitions in the radiative and radiation-less energy transfer mechanism was discussed. This paper discusses also the emission of Ce 3+ and Pr 3+ and Stokes shift.

  20. Energy conversion within infrared plasmonic absorption metamaterials for multi-band resonance

    NASA Astrophysics Data System (ADS)

    Li, Yongqian; Su, Lei; Xu, Xiaolun; Zhang, Chenglin; Wang, Binbin

    2015-05-01

    The energy conversion within the cross-shaped plasmonic absorber metamaterials (PAM) was investigated theoretically and numerically in the infrared range based on the Poynting's theorem of electromagnetic energy. From the microscopic details, the heat generation owing to the electric current accounts for the majority of the energy conversion, while the magnetic resonance plays a negligible role. The PAMs possess three distinct resonant peaks standing independently, which are attributed to the polarization sensitive excitation of plasmonic resonance. Field redistribution and enhancement associated with multiplex resonant electromagnetic wave passing through the PAM medium provided insight into the energy conversion processes inside the nanostructure. The research results will assist the design of novel plasmon enhanced infrared detectors with multiple-band detection.