Temperature-dependent polarization of resonance Raman scattering in CdS

Temperature-dependent polarization of the 4658 Å—3LO Raman line was studied together with that of the 4727 Å—2LO Raman line in resonance Raman scattering (RRS) in CdS. Temperature-dependent polarization is strongly related to the A-exciton in CdS as a resonant intermediate state. Experimental results are well understood when RRS around the A-exciton is considered as the inelastic scattering of exciton—polaritons by LO phonons.     

CW measurements of resonance Raman profiles,line‐widths,and cross‐sections of fluorescent dyes: application to Nile Blue A in water and ethanol

The aim of this work is to illustrate the power of recently developed methods for measuring resonance Raman scattering (RRS) spectra of efficient fluorophores (using a standard continuous wave excitation and a charge‐coupled device (CCD)‐based Raman spectrometer), by applying them to a detailed study of a specific fluorophore: Nile Blue A. A combination of methods are used to measure the RRS properties of Nile Blue A in water (quantum yield (QY) of 4%) and ethanol (QY of 22%) at excitation wavelengths between 514 and 647 nm, thus covering both pre‐resonance and RRS conditions. Standard Raman measurements are used in situations where the fluorescence background is small enough to clearly observe the Raman peaks, while the recently introduced polarization‐difference RRS and continuously shifted Raman scattering are used closer to (or at) resonance. We show that these relatively straightforward methods allow us to determine the Raman cross‐sections of the most intense Raman peaks and provide an accurate measurement of their line‐width; even for broadenings as low as ∼ 4 cm ^{− 1}. Moreover, the obtained Raman excitation profiles agree well with those derived from the optical absorption by a simple optical transform model. This study demonstrates the possibility of routine RRS measurements using standard Raman spectrometers, as opposed to more complicated time‐resolved techniques. Copyright © 2013 John Wiley & Sons, Ltd.     

Observation of general behaviour of Resonance Raman Spectra in the model system KBr(MnO-4)

Employing KBr(MnO^-₄) crystals as model specimens, the authors have observed for the first time the theoretically predicted peculiarities of the impurity resonance Raman scattering (RRS) resulting from excitation to a vibronic-structured absorption band, those peculiarities being the sharp irregularity of the RRS spectrum in case of excitation to Frank-Condon sublevel, the strong dependence of the spectrum on excitation frequency, the temperature dependences of the RRS line intensity which are significantly different for different orders of scattering. The observational data have been compared with calculations of cross-sections for multi-phonon RRS.     

Stimulated resonance Raman scattering of Rhodamine B

Stimulated resonance Raman scattering (SRRS) of the Rhodamine B (RhB) in the methanol (CH₃OH) or ethanol (C₂H₅OH) solutions have been observed. SRRS from RhB can be distinguished from the amplified spontaneous emission (ASE) of RhB with increasing the input laser energy. When the RhB is dissolved in the methanol or ethanol (10^?3 mol/L), the RhB have the different peak wavelengths of SRRS, ASE, fluorescence and absorption, respectively. SRRS can be amplified by the ASE gain when the SRRS is near the peak of the ASE, and the peak wavelength of SRRS coincides with the maximal intensity wavelength of ASE.     

Pressure-tuned resonance Raman scattering and photoluminescence studies on MBE grown bulk GaAs at theE 0 gap

Hydrostatic pressure has been used to tune in resonance Raman scattering (RRS) in bulk GaAs. Using a diamond anvil cell, both the photoluminescence peak (PL) and the 2 LO and LO-phonon Raman scattered intensities have been monitored, to establish RRS conditions. When theE ₀ gap of GaAs matchesħω _S orħω _L, the 2 LO and LO-phonon intensity, respectively, exhibit resonance Raman scattering maxima, at pressures determined byħω _L. With 647.1 nm radiation (ħω _L = 1.916 eV), a sharp and narrow resonance peak at 3.75 GPa is observed for the 2 LO-phonon. At this pressure the 2 LO-phonon goes through its maximum intensity, and falls right on top of the PL peak, revealing thatħω _S(2 LO) =E ₀. This is the condition for “outgoing” resonance. Experiments with other excitation energies (ħω _L) show, that the 2 LO resonance peak-pressure moves to higher pressure with increasingħω _L, and the shift follows precisely theE ₀ gap. Thus, the 2 LO RRS is an excellent probe to follow theE ₀ gap, far beyond the Γ-X cross-over point. A brief discussion of the theoretical expression for resonance Raman cross section is given, and from this the possibility of a double resonance condition for the observed 2 LO resonance is suggested. The LO-phonon resonance occurs at a pressure whenħω _L ≈E ₀, but the pressure-induced transparency of the GaAs masks the true resonance profile.     

Silver nanoparticle coverage dependence of surface-enhanced Raman scattering

We report surface-enhanced Raman scattering (SERS) from 4-mercaptopyridine adsorbed on nanotextured silver surfaces as the coverage of silver is varied. The degree of surface enhancement is strongly dependent on silver coverage and correlated to the extinction of the surface at the Raman excitation wavelength, that extinction being determined by multiparticle surface plasmon resonances. The coverage dependence of the Raman intensity is consistent with signals being dominated by molecules at junctions inside nanoparticle aggregates where electromagnetic energy is localized into “hot spots” by interactions of the incident and scattered fields with the surface plasmons. The Raman intensity drops precipitously near the conductivity percolation threshold because these hot spots are destroyed when conducting paths allow plasmons to propagate. Our approach to substrate preparation provides clean surfaces with average enhancements ≥10⁷, an order of magnitude larger than typical for SERS. PACS 78.67.-n; 78.68.+m; 33.20.Fb     

Surface enhanced Raman spectroscopy of palladium

Large enhancements in the Raman scattering signals have been observed from molecules and ions adsorbed on a palladium surface. The largest enhancement factor is in the order of 10⁵. Results will be discussed in terms of theoretical models on the surface enhanced Raman scattering process.     

High-resolution study of x-ray resonant Raman scattering at the K edge of silicon

We report on the first high-resolution measurements of the K x-ray resonant Raman scattering (RRS) in Si. The measured x-ray RRS spectra, interpreted using the Kramers-Heisenberg approach, revealed spectral features corresponding to electronic excitations to the conduction and valence bands in silicon. The total cross sections for the x-ray RRS at the 1s absorption edge and the 1s-3p excitation were derived. The Kramers-Heisenberg formalism was found to reproduce quite well the x-ray RRS spectra, which is of prime importance for applications of the total-reflection x-ray fluorescence technique.     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Cooperative and quantum phenomena in experiments involved in the study of ordinary and stimulated Raman scattering of light

Results are presented of experimental studies of Raman scattering (RS) of light and of stimulated Raman scattering (SRS) of light, in which the quantum and cooperative properties of these phenomena are manifested. Experiments are described, revealing for the first time ever the connection between the integral intensity of the RS and SRS spectra and Brownian motion of molecules in condensed media. A number of experimental properties of RS and SRS are interpreted as results of collective behavior of molecules in condensed media. Spatial energy quantization of SRS energy is observed for the first time following excitation by 10^–9- and 10^-12-sec pulses. The experimental results are discussed in the Conclusion in light of the existing theoretical premises. New properties of RS and SRS are demonstrated and an explanation of their physical nature is proposed.Optics Division, lebedev Physics Institute. Translated from Preprint No. 103, Lebedev Physics Institute, Academy of Sciences of the USSR, Moscow, 1991.     

The stimulated Raman scattering competition between solute and solvent in Rhodamine B solution

The competition between the stimulated resonance Raman scattering (SRRS) of Rhodamine B (RhB) and the stimulated Raman scattering (SRS) of ethanol (C₂H₅OH) is observed at the RhB in C₂H₅OH solution. For different concentrations of the solution, the peak wavelengths of the SRRS, the amplified spontaneous emission (ASE), the fluorescence and the absorption of RhB are different. The SRRS of RhB and the SRS of C₂H₅OH are simultaneously generated when the concentration of the solution is 10^-5 mol/L and the energy of the excitation laser is 20.4 mJ. Otherwise, only either the SRRS of RhB or the SRS of C₂H₅OH is generated. The SRRS can be amplified by the ASE gain when the SRRS is near the peak of the ASE, and the peak wavelength of the SRRS coincides with the wavelength of the maximal intensity ASE.     

Quantum-mechanical analysis of resonance Raman scattering spectra of the uracil molecule

A direct quantum-mechanical calculation of the relative intensities of lines in the resonance Raman scattering (RRS) spectra of uracil is performed by a method developed earlier by the authors on the basis of the adiabatic model in the Herzberg-Teller approximation [1]. It is shown that the main regularities in the intensity distribution of spectra can be explained only by taking into account the vibronic mixing of electronic states and the contribution to the scattering tensor components from the excited electronic states adjacent to the resonance state. The calculated results are in satisfactory agreement with the results of experimental studies of the RRS spectra of uracil excited by laser radiation at 266, 240, 218, and 200 nm.     

Charge transfer effects in surface enhanced Raman scattering

Surface enhanced Raman scattering (SERS) due to charge transfer interactions between the adsorbed molecule and the metal surface is analyzed using the semiempirical Wolfsberg-Helmholz method¹ to relate the molecule-surface interactions and the resulting charge transfer states to the overlap integrals between the metal conduction-band orbitals and an acceptor or donor molecular orbital of the molecule. Calculations for the model system of ethylene adsorbed on silver (approximated as a simple cubic metal with tight binding wave functions constructed from Ag 5s valence orbitals), with charge-transfer excitation of an electron from the metal to the antibonding ethylene π orbital, show that charge-transfer Raman enhancements of the order of 10 to 1000 are possible if the charge-transfer band is partially resonant with the exciting radiation. The net enhancement is the product of the charge-transfer gain and the electrodynamic enhancement due to plasmon resonances at surface roughness elements. Symmetric vibrations usually will be enhanced substantially more than nonsymmetric ones by charge-transfer because, in contrast to non-resonant Raman scattering, the vibrational coupling is primarily Franck- Condon (due to differences in the equilibrium nuclear configurations of the ground and excited charge transfer states and the resulting nonorthogonality of different vibrational sublevels of these states) rather than Herzberg-Teller (due to vibrationally induced changes in the electronic wave functions). The charge-transfer mechanism is selective with the most enhanced vibrations involving those atoms which experience the greatest change in electron density between the ground and excited charge-transfer state. A recent report of SERS for benzene on platinum,² strongly suggests charge-transfer enhancement because the electromagnetic-field-enhancing plasmon resonances are strongly damped in this metal.The complete paper will be published in the December 1, 1982 issue of the Journal of Chemical Physics.     

Resonant Raman scattering in CdSxSe1−x nanocrystals: effects of phonon confinement,composition, and elastic strain

Optical phonon modes, confined in CdS_xSe_1−x nanocrystal (NC) quantum dots (≈2 nm in radius) grown in a glass matrix by the melting‐nucleation method, were studied by resonant Raman scattering (RRS) spectroscopy and theoretical modeling. The formation of nanocrystalline quantum dots (QDs) is evidenced by the observation of absorption peaks and theoretically expected resonance bands in the RRS excitation spectra. This system, a ternary alloy, offers the possibility to investigate the interplay between the effects of phonon localization by disorder and phonon confinement by the NC/matrix interface. Based on the concept of propagating optical phonons, which is accepted for two‐mode pseudo‐binary alloys in their bulk form, we extended the continuous lattice dynamics model, which has successfully been used for nearly spherical NCs of binary materials, to the present case. After determining the alloy composition for NCs (that was evaluated with only 2–3% uncertainty using the bulk longitudinal optical phonon wavenumbers) and the NC size (using atomic force microscopy and optical absorption data), the experimental RRS spectra were described rather well by this theory, including the line shape and polarization dependence of the scattering intensity. Even though the presence of a compressive strain in the NCs (introduced by the matrix) masks the expected downward shift owing to the phonons' spatial quantization, the asymmetric broadening of both Raman peaks is similar to that characteristic of NCs of pure binary materials. Although with some caution, we suggest that both CdSe‐like and CdS‐like optical phonon modes indeed are propagating within the NC size unless the alloy is considerably heterogeneous. Copyright © 2011 John Wiley & Sons, Ltd.     

Theoretical study on SERRS of rhodamine 6G adsorbed on Ag2 cluster: chemical mechanism via intermolecular or intramolecular charge transfer

The problem of the chemical enhancement of rhodamine 6G (R6G) adsorbed on silver cluster has been theoretically investigated by charge difference densities (CDDs) to show the direct charge transfer (CT) evidence. For surface‐enhanced resonance Raman scattering (SERRS) of R6G excited at 514.5 nm, the enhancements of v(151) and v(154) result from weak intermolecular (from Ag to R6G) CT and the strong intramolecular CT [similar to that of resonance Raman scattering (RRS) of R6G], respectively. The possibility of the SERRS of R6G contributed from pure intermolecular CT is also discussed, when the incident light is close to the new metal–R6G CT excited state at 1571.4 nm. Meanwhile compared with the absorption process the fluorescence yield of R6G is investigated by transition densities and CCDs. Copyright © 2008 John Wiley & Sons, Ltd.     

Resonance Raman scattering at the saddle points of semiconductors

An approximate theory is formulated to describe resonance Raman scattering near the critical points of semiconductors using a model density of states. Large resonance enhancements and absolute scattering cross sections are predicted near the saddle points.     

Spin-dependent phonon Raman scattering in CdCr2Se4

Influences of ferromagnetic ordering on the phonon Raman scattering are studied for CdCr₂Se₄ through the intensity measurements of Raman spectra between 25 and 300 K with various wavelengths of excitation light (488.0–676.4 nm). Spin-dependent enhancements of Raman cross section are observed for optical phonon lines D(168 cm^?1) and F(238 cm^?1) with excitation wavelengths of about 630 and 550 nm, respectively. This kind of phenomenon in spinel-type chalcogen chromites seems to originate in spin-dependent intermediate interactions in the excited states of specific electronic transitions with which the incident or scattered light is resonant.     

Vibronic scheme of the franck-condon state of F centers that consistently elucidates MCD and resonance raman scattering

Abstract

The resonance Raman scattering (RRS) of F centers, particularly the photon-energy dependence of linear polarization of the RRS, has been studied on the basis of a vibronic viewpoint. With combinination of previous results that have explained magnetic circular dichroism (MCD) spectra, a vibronic scheme of the Franck-Condon state of F centers for KCl, KBr and KI crystals is established.     

Surface enhanced Raman scattering of light by ZnO nanostructures

Raman scattering (including nonresonant, resonant, and surface enhanced scattering) of light by optical and surface phonons of ZnO nanocrystals and nanorods has been investigated. It has been found that the nonresonant and resonant Raman scattering spectra of the nanostructures exhibit typical vibrational modes, E ₂(high) and A ₁(LO), respectively, which are allowed by the selection rules. The deposition of silver nanoclusters on the surface of nanostructures leads either to an abrupt increase in the intensity (by a factor of 10³) of Raman scattering of light by surface optical phonons or to the appearance of new surface modes, which indicates the observation of the phenomenon of surface enhanced Raman light scattering. It has been demonstrated that the frequencies of surface optical phonon modes of the studied nanostructures are in good agreement with the theoretical values obtained from calculations performed within the effective dielectric function model.     

Wave vector conservation in the first order resonant Raman scattering

The dependence of the shape and the intensity of the first order resonant Raman line 1LO on the direction and magnitude of phonon wave vector has been investigated in CdS crystals. Comparison of RRS in different orientations shows that in the most pure samples the phonon wave vector is determined, to a great extent, by the momentum conservation law. In Ni doped crystals one can observe violation of momentum conservation, resulting in a sharp increase of 1 LO intensity. The shape of the 1 LO line in such sample does not depend on the experimental orientation. For the first time the dependence of the Raman intensity on the scattering angle has been observed by the comparison of forward and backward scattering spectra. Observation of this dependence shows that the free excitons are the dominating intermediate states in the resonant Raman scattering in A₂B₆ compounds.