Excited Raman Spectra Research Articles

Optical, Structural, and Synchrotron X-ray Absorption Studies for GaN Thin Films Grown on Si by Molecular Beam Epitaxy.

GaN on Si plays an important role in the integration and promotion of GaN-based wide-gap materials with Si-based integrated circuits (IC) technology. A series of GaN film materials were grown on Si (111) substrate using a unique plasma assistant molecular beam epitaxy (PA-MBE) technology and investigated using multiple characterization techniques of Nomarski microscopy (NM), high-resolution X-ray diffraction (HR-XRD), variable angular spectroscopic ellipsometry (VASE), Raman scattering, photoluminescence (PL), and synchrotron radiation (SR) near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. NM confirmed crack-free wurtzite (w-) GaN thin films in a large range of 180-1500 nm. XRD identified the w- single crystalline structure for these GaN films with the orientation along the c-axis in the normal growth direction. An optimized 700 °C growth temperature, plus other corresponding parameters, was obtained for the PA-MBE growth of GaN on Si, exhibiting strong PL emission, narrow/strong Raman phonon modes, XRD w-GaN peaks, and high crystalline perfection. VASE studies identified this set of MBE-grown GaN/Si as having very low Urbach energy of about 18 meV. UV (325 nm)-excited Raman spectra of GaN/Si samples exhibited the GaN E2(low) and E2(high) phonon modes clearly without Raman features from the Si substrate, overcoming the difficulties from visible (532 nm) Raman measurements with strong Si Raman features overwhelming the GaN signals. The combined UV excitation Raman-PL spectra revealed multiple LO phonons spread over the GaN fundamental band edge emission PL band due to the outgoing resonance effect. Calculation of the UV Raman spectra determined the carrier concentrations with excellent values. Angular-dependent NEXAFS on Ga K-edge revealed the significant anisotropy of the conduction band of w-GaN and identified the NEXAFS resonances corresponding to different final states in the hexagonal GaN films on Si. Comparative GaN material properties are investigated in depth.

Raman spectroscopy of bimagnon and trimagnon excitations and rotonlike points in a distorted triangular lattice antiferromagnet

We investigate the experimental signatures of Raman spectroscopy of bi- and tri-magnon excitations in the distorted triangular lattice antiferromagnets alpha-LCr2O4 (L=Sr, Ca). We utilize spin wave theory to analyze the nearly 120 degree spin-3/2 spiral ordered antiferromagnetic ground state to compute the single-magnon density of states, single-magnon dispersion, and bimagnon and trimagnon Raman spectra (polarized and unpolarized). It is found that Raman scattering is capable of capturing the effect of the rotonlike M and M' points on the bimagnon Raman spectrum. Our calculation confirms the connection between single-magnon rotonlike excitation energy and bimagnon Raman excitation spectrum observed experimentally. The roton energy minimum in momentum space is half of the energy of a bimagnon excitation signal. The experimental magnetic Raman scattering result displays two peaks which have a Raman shift of 15 meV and 40 meV, respectively. Theoretical modeling and analysis of the experimental spectrum of alpha-SrCr2O4 within our distorted Heisenberg Hamiltonian lattice suggests that the low-energy peak at 15 meV is associated with the bimagnon excitation, whereas the high-energy peak around 40 meV is primarily a trimagnon excitation. Based on our fitting procedure we propose a new set of magnetic interaction parameters for alpha-SrCr2O4. These parameters reproduce not only the experimental Raman spectrum, but also the inelastic neutron scattering response (including capturing high energy magnon branches). We also compute the unpolarized bimagnon and trimagnon Raman spectra for alpha-CaCr2O4. Furhtermore, we found that the polarization sensitivity of Raman spectrum can be utilized to distinguish the bi- and tri-magnon excitation channels.

Broadband Full-Spectrum Raman Excitation Mapping Reveals Intricate Optoelectronic-Vibrational Resonance Structure of Chirality-Pure Single-Walled Carbon Nanotubes.

The Raman excitation spectra of chirality-pure (6,5), (7,5), and (8,3) single-walled carbon nanotubes (SWCNTs) are explored for homogeneous solid film samples over broad excitation energy and scattering energy ranges using a rapid and relatively simple full spectrum Raman excitation mapping technique. Identification of variation in scattering intensity with sample type and phonon energy related to different vibrational bands is clearly realized. Excitation profiles are found to vary strongly for different phonon modes. Some modes' Raman excitation profiles are extracted, with the G band profile compared to earlier work. Other modes, such as the M and iTOLA modes, have quite sharp resonance profiles and strong resonances. Conventional fixed wavelength Raman spectroscopy can miss these effects on the scattering intensities entirely due to the significant intensity changes observed for small variations in excitation wavelength. Peak intensities for phonon modes traceable to a pristine carbon lattice forming a SWCNT sidewall were greater for high-crystallinity materials. In the case of highly defective SWCNTs, the scattering intensities of the G band and the defect-related D band are demonstrated to be affected both in absolute intensities and in relative ratio, with the ratio that would be measured by single wavelength Raman scattering dependent on the excitation wavelength due to differences in the resonance energy profiles of the two bands. Lastly it is shown that the approach of this contribution yields a clear path toward increasing the rigor and quantification of resonance Raman scattering intensity measurements through tractable corrections of excitation and emission side variations in efficiency with excitation wavelength.

Opto-electric flash Raman method for in situ measuring temperature variation of power device with a high temporal resolution

This paper develops an in-situ high temporal resolution opto-electric flash Raman method to accurately measure the temperature fluctuation of power devices caused by modulated driving voltage. By synchronous modulation, the pulsed laser can maintain the same frequency as the driving voltage of the power device, and the working temperature of the device during the laser pulse can be obtained from the excited Raman spectrum. By adjusting the time delay between the pulsed laser and the electric signal with 100 ps resolution, the temperature variation in a cycle can be accurately determined. This method measures the temperature changes of GaN high electron mobility transistors device versus a square wave driving signal with different frequencies. The experimental results show that, in amplitude modulation mode with 100 Hz, the maximum temperature change through a driving cycle can be more than 20 K. This illustrates that high temporal resolution measurement is significant in determining the peak temperature of hot spots in the power devices. Two samples fixed using different methods had considerably different transient temperature fluctuations under the same driving frequency, indicating that the transient temperature variation is a promising way to gauge how well the devices dissipate heat. The temperature variations caused by a complex driving signal were also determined in this work. As a transient method, the opto-electric flash Raman method is promising to be used in multi-type power devices to in situ detect temperature fluctuation and provide a reference for the evaluation and optimization of the device.

Vibrationally Induced Photophysical Response of Sr2NaMg2V3O12:Eu3+ for Dual‐Mode Temperature Sensing and Safety Signs

In the dual‐emitting Eu3+‐activated Sr2NaMg2V3O12 garnet, vibrationally induced thermometric response and thermochromic luminescence are investigated for the first time. Based on the diverse thermal quenching of VO43− and Eu3+ along with the advantage of variation in the fluorescence intensity ratio, a potential phosphor for sensitive dual‐mode ratiometric and colorimetric temperature sensors is proposed in which maximum absolute and relative sensitivity of 0.0135 K−1 and 1.61% K−1 are obtained at 420 K with a temperature resolution <0.2 K. Efficient thermochromic luminescence in which colorific shift from white (300 K) to red (500 K) is observed such that the requirement of larger number of phonons weakens the nonradiative relaxation of Eu3+, resulting in slow quenching, substantiated by estimating radiative and nonradiative decay rates by the 4f–4f intensity method. In contrast, a strong vibrational coupling of excited electrons of the VO43− complex is identified and verified by means of temperature‐dependent Raman and photoluminescence excitation spectra for the first time. Consequently, an increased thermal population of vibrational levels favors rapid thermal quenching of luminescence of VO43− via crossover mechanism. Hence dual‐centered Sr2NaMg2V3O12:Eu is an efficient thermometric and thermochromic luminescent material for optical thermometry and safety sign applications in a high‐temperature environment.

Dual-wavelength excitation combined Raman spectroscopy for detection of highly fluorescent samples.

As fluorescence is the major limitation in Raman scattering, near-infrared excitation wavelength (>780nm) is preferred for fluorescence suppression in Raman spectroscopy. To reduce the risk of fluorescence interference, we developed a dual-wavelength excitation combined Raman spectroscopy (DWECRS) system at 785 and 830 nm. By a common optical path, each laser beam was focused on the same region of the sample by a single objective lens, and the dual-wavelength excitation Raman spectra were detected by a single CCD detector; in addition, 785 and 830 nm excitation Raman spectra can be directly constructed as combined Raman spectrum in the DWECRS system. The results of pure peanut oil and glycerol indicate that the combined Raman spectrum cannot only reduce fluorescence interference but also keep a high signal-to-noise ratio in the high-wavenumber region. The results of dye-ethanol solutions with different concentrations show that the handheld DWECRS system can be used as a smart method to dodge strong fluorescence. Furthermore, we developed a peak intensity ratio method with the DWECRS system to distinguish different types of edible oils. The peak intensity ratio distribution chart of edible oils showed each oil normalized center was relatively independent and nonoverlapped, which can be used as the basis of edible oil classification analysis. In the future, the DWECRS system has potential to be used as a tool for more complex applications.

Direct Tracking Excited-State Intramolecular Charge Redistribution of Acceptor-Donor-Acceptor Molecule by Means of Femtosecond Stimulated Raman Spectroscopy.

Symmetric quadrupolar molecules generally exhibit apolar ground states and dipolar excited states in a polar environment, which is explained by the excited state evolution from initial charge delocalization over all molecules to localization on one branch of the molecules after a femtosecond pulse excitation. However, direct observation of excited-state charge redistribution (delocalization/localization) is hardly accessible. Here, the intramolecular charge delocalization/localization character of a newly synthesized acceptor-donor-acceptor molecule (ADA) has been intensively investigated by femtosecond stimulated Raman scattering (FSRS) together with femtosecond transient absorption (fs-TA) spectroscopy. By tracking the excited state Raman spectra of the specific alkynyl (-C≡C-) bonds at each branch of ADA, we found that the nature of the relaxed S1 state is strongly governed by solvent polarity: symmetric delocalized intramolecular charge transfer (ICT) characters occurred in apolar solvent, whereas the asymmetric localized ICT characters appeared in polar solvent because of solvation. The solvation dynamics of ADA extracted from fs-TA is consistent with the time constants obtained by FSRS, but the FSRS clearly tracks the excited state intramolecular charge transfer delocalization/localization.

Fresco Paintings: Development of an Aging Model from 1064 nm Excited Raman Spectra

In this study, we proposed a preliminary kinetic model applied to the carbonation process of fresh lime with the intention to realize a diagnostic tool for aged fresco paintings. The model can be useful, in particular, in the fields of conservation and restoration of ancient lime wall paintings. The dating procedure was achieved through the analysis of 1064 nm excited Raman spectra collected on artificially aged lime samples in addition to ancient samples taken from literature and covering a period of two thousand years. The kinetic model was developed monitoring the concentration of emitting defective centers related to the intensity of 780 cm−1 calcium hydroxide band as a function of the time and depth. This preliminary model shows how Raman spectroscopy, especially NIR micro-Raman, is advantageous for diagnostics and conservation in the cultural heritage field.

Investigation of the structural and photoluminescence properties of Eu3+ doped Na6CaP2O9 phosphors for solid state lighting

A series of Eu3+ doped Na6CaP2O9 phosphors were synthesized via conventional solid state reaction method and characterized through XRD, FTIR, diffused reflectance, photoluminescence excitation and emission spectra and Raman spectra. The XRD analyses confirm the successful synthesis of hexagonal structured Na6CaP2O9 matrix. The luminescent spectra reveal that the samples can be well excited under near UV light to get an efficient orange red emission. To get a deeper insight into the usefulness of the present material, the phonon sideband analysis and Judd- Ofelt analysis were also performed. The energy transfer interaction between Eu3+ ions was dipole-dipole in nature, as evident from the Dexter theory. The thermal stability analysis and quantum yield measurements were also made. The CIE coordinates of the phosphors were observed to lie in the orange–red region. The present investigation proves the Eu3+ doped Na6CaP2O9 to be a potential orange-red phosphors in near-UV based LEDs.

Thermal Silicidation of Ni/SiGe and Characterization of Resulting Silicide Films Using Raman Spectroscopy and X-ray Diffraction

For advanced application specific devices, combinations of Si/Ge, Ge/Si, Si1-xGex/Si are frequently introduced in the device fabrication process. Epitaxy, condensation and annealing processes are commonly used for controlling the Ge content to a desired level. Strain and crystallinity can be affected by a small variation in composition or Ge content, which can result in device performance deterioration or failure. Thus, the composition, strain and crystallinity must be carefully monitored and controlled throughout the manufacturing process. The electrode formation process is also very critical for successful device fabrication. Any spikes and/or electrically active defects near junctions can be fatal to the device yield. Silicidation processes and resulting silicides must be investigated as much as possible using various non-invasive material characterization techniques.In this study, we report the thermal silicidation characteristics of Ni/Si1-xGex with various Ge content under different annealing temperatures in the range of 225oC ~ 400oC in N2 ambient. Thermal silicidation was performed in a stacked hotplate-based SAO-302LP system designed for 300mm wafers. For resulting silicide characterization, measurements of sheet resistance, Raman spectra, X-ray diffraction curves as well as scanning electron microscopy (SEM) observations were performed. We have studied Ge content and annealing temperature dependence on the resulting electrical and crystallographic silicide characteristics.Figure 1 shows 647nm excited Raman spectra and X-ray diffraction (XRD) curves from reference Si, and resulting silicide from Ni/Si0.75Ge0.25 before and after annealing under at 235oC, 310oC and 400oC.Raman spectra and sheet resistance measurements showed silicide formation and silicide layer thickening with increasing annealing temperature. XRD curves clearly indicated the change of crystalline phase of resulting silicide with annealing temperature increase. Various aspects of thermal silicidation and its characterization will be discussed at the conference. Figure 1

Twisted Intramolecular Charge Transfer State of a "Push-Pull" Emitter.

The excited state Raman spectra of 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) in the locally-excited (LE) and the intramolecular charge transfer (ICT) states have been separately measured by time-resolved stimulated Raman spectroscopy. In a polar dimethylsulfoxide solution, the ultrafast ICT of DCM with a time constant of 1.0 ps was observed in addition to the vibrational relaxation in the ICT state of 4–7 ps. On the other hand, the energy of the ICT state of DCM becomes higher than that of the LE state in a less polar chloroform solution, where the initially-photoexcited ICT state with the LE state shows the ultrafast internal conversion to the LE state with a time constant of 300 fs. The excited-state Raman spectra of the LE and ICT state of DCM showed several major vibrational modes of DCM in the LE and ICT conformer states coexisting in the excited state. Comparing to the time-dependent density functional theory simulations and the experimental results of similar push-pull type molecules, a twisted geometry of the dimethylamino group is suggested for the structure of DCM in the S1/ICT state.

Controlling the Resonance Raman Effect in Tip-Enhanced Raman Spectroscopy Using a Thin Insulating Film.

Both surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS) are widely used for the investigation of nanoscale materials. One of the most critical aspects of both SERS and TERS is the control of both the plasmon and molecular resonance precisely. Here, we demonstrate single-molecule TERS under molecular resonance conditions using a scanning tunneling microscope. This was achieved by placing the molecule on a sodium chloride (NaCl) film in order to directly compare the absorption with Raman excitation spectra. Varying the NaCl film thickness changes the degree of screening effect from the metal surface, which leads to a variation of the molecular resonance phenomena. Although it is generally accepted that the target molecule should be directly attached to the metal surface in SERS, our observation using TERS suggests that this is not always optimal, especially under molecular resonance Raman conditions. Our work demonstrates the possibility of controlling molecular resonance by carefully modifying the local environment. This will be useful for future investigation of isolated single molecules or even two-dimensional molecular assemblies.

Influence analysis of the detection accuracy of atmospheric water vapor using the solar-blind ultraviolet Raman lidar

Solar-blind ultraviolet Raman lidar can realize the daytime detection of atmospheric water vapor, as the transmitting wavelength of 266.0 nm and its excited vibrational Raman spectra of N2, O2 and H2O are within the solar-blind region. However, the spectra of the O3, NO2, SO2 absorptions and fluorescence are within the solar-blind region as well, and Raman channel of H2O still has a small amount of residual solar background noise, which will influence the detection accuracy and detection capability of the solar-blind ultraviolet Raman lidar. Moreover, although a high efficiency polychromator is required to extract the vibrational Raman spectra of N2, O2 and H2O, the suppression of aerosol Mie scattering and molecular Rayleigh scattering, and optical cross-talks are still required to discuss carefully in detail. Simulation results show that the retrieval accuracy of water vapor mixing ratio using the solar-blind Raman lidar are mainly influenced by the O3 absorption and the optical cross-talk of aerosol Mie scattering and molecular Rayleigh scattering. The rejection ratio with more than 5 orders of magnitude to elastic scattering signal is required in the design of polychromator to avoid the optical cross-talk between each extracted spectrum. The influences of NO2, SO2 absorptions, solar background noise and fluorescence on the retrieval of water vapor mixing ratio can be neglected. The theoretical analysis of the solar-blind ultraviolet Raman lidar on the retrieval of water vapor mixing ratio can further enhance the performance of the system detection accuracy and detection capability.

Structural and optical characteristics investigations in oxygen ion implanted GaN epitaxial layers

This paper presents the lattice disorder-induced effect by oxygen ion implantation in GaN epitaxial layers. Oxygen ion implantation in GaN epitaxial layers is done with fluencies 5 × 1014 cm−2 and 5 × 1015 cm−2 at 120 keV energy on two different pieces of a GaN sample. Unimplanted and implanted GaN layers are investigated by High-resolution X-ray diffraction (HRXRD), Optical absorption and Raman spectroscopy. The in-plane and out of plane lattice parameters (i.e. a and c) of the distorted and undistorted region in the GaN samples are determined from the respective XRD peak positions. Due to the incorporation of oxygen ions in GaN layers up to implantation depth, lattice parameters are extended, as a result, the samples are under hydrostatic strain. Raman spectroscopic studies on the unimplanted and oxygen ion-implanted GaN samples are done by green and ultra-violet (UV) lasers. Raman spectroscopy results indicate that the broadening of the E2 (High) peak and intensity of A1 (LO) peak increases with increasing fluence. A doublet in A1 (LO) peak is found in UV excited Raman spectra in unimplanted and implanted GaN samples. The occurrence of the A1 (LO) doublet is due to surface defects and phonon-plasmon coupled-mode generated due to nonequilibrium photoexcited carriers. In this article, the origin of doublet has been studied and reported.

Study of redox and protonation processes of polyaniline by the differential multiwavelength Raman spectroelectrochemistry.

Polyaniline layer has been deposited at a gold electrode and subjected to differential multiwavelength Raman spectroelectrochemical study. A broad set of laser line excitation wavelengths was used, including UV (325 nm), blue (442 nm), green (532 nm), red (633 nm), and far red (785 nm). From measurements performed, potential-difference Raman spectra, related to small-step changes of electrode potential were derived, and specific spectral and structural features were obtained and analysed. Similarly, pH-difference spectra for solution pH changes were obtained. A strong resonance enhancement of Raman spectra for reduced form of polyaniline at UV and blue line excitations, and for oxidized forms at red and far red excitations was observed and analysed. The 442-nm excited potential-difference resonance Raman spectra revealed presence of intermediate oxidation state compound formed during the electrooxidation of leucoemeraldine with characteristic vibrational bands at 1622, 1187, 881, and 817 cm-1.

Tunable emission and energy transfer in TeO2-GeO2-ZnO and TeO2-GeO2-MgCl2 glasses activated with Eu3+/Dy3+ for solid state lighting applications

The results presented here refer to the tunability of global emission characteristics of Eu3+, Dy3+ and Eu3+/Dy3+ ions, varying the composition glasses; TeO2-GeO2-X (X = ZnO, MgCl2). Also, the influence of exchanging the modifier compound on the global luminescent response of the glasses was analyzed by Raman spectroscopy, excitation and emission spectra, and emission decay profiles. Changes in the Te-O-Te network structure, when MgCl2 substitutes ZnO, were identified from Raman spectrum deconvolution analysis. The energy transfer between Eu3+ and Dy3+ ions, and tunable emission characteristics, were studied under UV excitations that correspond with the emission of InGaN (370–420 nm) based LEDs. The energy transfer process between Eu3+ and Dy3+ ions was studied based on the emission spectra with different excitation wavelengths and time decay curves of the 5D0→7F2 level of Eu3+ at 612 nm. In TGZED and TGMED glasses and upon 351 nm, the time shortening of Dy3+ emission decay in presence of Eu3+ was attributed to an Dy3+→Eu3+ non-radiative energy transfer process. The energy transfer probabilities PD→E and energy transfer efficiency ηD→E were calculated for TGZ and TGM glasses. According to the Inokuti-Hirayama model it might be dominated through an electric dipole-dipole interaction, with efficiency of 5.0% and 1.9% and the obtained γ6 energy transfer parameter values γ6 = 0.082 ± 0.005 and 0.026 ± 0.005 respectively, for TGZED and TGMED glasses. The non-radiative Eu3+→Dy3+ energy transfer was observed too for both glasses TGZED and TGMED, so that transfer of energy is more favored in the oxide vitreous matrix than in the oxide-halide one. The dominated are an electric dipole-dipole interaction with γ6 energy transfer parameter values are 0.072 ± 0.005 (TGZED) and 0.036 ± 0.005 (TGMED), with efficiency 6.9 and 4.1% respectively. In TGM glasses is very low efficiency of non-radiative Dy3+→Eu3+ and Eu3+ →Dy3+ energy transfer that TGZ matrix. Neutral white emissions of 4135, 4567 K were observed in the Dy3+ and 3914 and 242 K, Eu3+/Dy3+ doped TGZ glasses excited at 351 and 388 nm, respectively. Similarly, global emissions of Dy3+ single doped were 4028 and 4123 K, but in Eu3+/Dy3+ double doped TGM glasses are neutral white light of 3929 and 3979 K, respectively. Upon 394 nm excitation, the Eu3+ doped TGZ and TGM glasses displayed reddish-orange global emissions of 1979 and 1964 K, respectively. For excitations at 382 and 394 nm the Eu3+/Dy3+ doped TGZ and TGM glasses emit warm white light of 3414 and 3160 K (382 nm excitation) and reddish-orange of 2123 and 2030 K (394 nm excitation), respectively, depending mostly on the Eu3+ and Dy3+ relative excitation intensity.

Raman spectroelectrochemical study of polyaniline at UV, blue, and green laser line excitation in solutions of different pH

A detailed study on Raman spectroelectrochemistry of polyaniline layer deposited at a gold electrode was performed. Raman spectra were excited by three laser wavelengths: UV line at 325 nm, a blue line at 442 nm, and a green line at 532 nm in solutions of different pH ranging from 1 to 9, and at different electrode potentials ranging from −0.5 V to 0.8 V. UV excitation results in a strong resonance with the reduced leucoemeraldine form of polyaniline that absorbs visible light at a maximum around 315 nm, revealing features characteristic for this form, thus nearly avoiding the possibility to observe the oxidised form and the corresponding electrochemical redox transformations. Both redox forms and their redox interconversions depending on electrode potential and solution acidity were well observed and analysed for green laser line excited Raman spectra. Blue laser line probably appears in resonance with the intermediate polyaniline form that absorbs visible light at a maximum of 420 nm.

Surface determination of 3D confocal Raman microscopy imaging of the skin

A surface determination method for the application of 3D confocal Raman microscopy on inhomogeneous skin sections has been presented, which is based on depth profiles of the keratin contribution of the acquired Raman spectra. The method was compared to two similar auto-focusing methods that are based on the intensity of the reflected excitation light and Raman spectra, respectively.The measurements were performed on hair follicles containing skin sections of porcine ears ex vivo. The surface determination on such samples is especially challenging due to their different molecular composition and surface inhomogeneity.An advantage of this method is molecular sensitivity, whereby only the surface of the sample will be detected and not the substrate of the microscope slide, in the case of disruptions during the processing of samples. A disadvantage of the method is the increased overall acquisition time if only the surface spectra are to be applied for 2D mapping.

Effect of helium nanoclusters on the spectroscopic properties of embedded SF6: Ionization, excitation and vibration

Ionization and excitation energies, IR and Raman spectra of sulfur hexafluoride (SF6), located inside helium (He) nanoclusters with different sizes (SF6@Hen; n=20, 40, 60), were calculated. The effect of the cluster size on the spectroscopic properties of the SF6 was investigated and found that the Hen-SF6 interaction in the He clusters with large number of atoms is small so that the ionization and absorption energies of SF6 are not affected while for small He nanoclusters the Hen-SF6 interaction is more important. The effect of Hen-SF6 interaction and deformation of the fragments on the photoelectron and absorption spectra of SF6@Hen were separated theoretically and discussed in details. It was deduced that the effect of the cluster size on the IR and Raman vibrational frequencies of the SF6 is negligible for the cluster size range considered in this work. Density functional theory (DFT) employing M06-2X functional and 6-31+G(df) basis set were used for optimizing the structures of SF6@Hen. Symmetry adapted cluster-configuration interaction (SAC-CI) methodology, with the same basis set, were used to calculate the ionization and excitation energies of the SF6@Hen structures. Using the calculated ionization and absorption energies and their intensities, the photoelectron and absorption spectra of the considered SF6@Hen structures were simulated and compared with the experiment.

Quantitative analysis of sugar composition in honey using 532‐nm excitation Raman and Raman optical activity spectra

Raman spectroscopy based on the 1064‐nm laser excitation was suggested as a handy non‐invasive technique allowing to quickly determine sugar content in honey and similar food products. In the present study, the green 532‐nm laser radiation is explored instead as it provides higher‐quality spectra in a shorter time. The sample fluorescence was quenched by purification with activated carbon. For control mixture decomposition of Raman spectra to standard subspectra led to a typical error of the sugar content of 3%. Raman optical activity (ROA) spectra that could be measured at the shorter excitation wavelength as well provided a lower accuracy (~8%) than the Raman spectra because of instrumental sensitivity and noise limitations. The results show that Raman spectroscopy provides elegant and reliable means for fast analyses of sugar‐based food products. Copyright © 2016 John Wiley & Sons, Ltd.