Temperature Effects in the Raman Spectrum of Solid Orthocarborane

Abstract

Variable temperature studies of the laser Raman spectrum of solid orthocarborane indicate a change in the line widths of the peaks in the observed frequency region from 745 cm^?1 to 815 cm^?1. A marked change in the line width of the 807 cm^?1 peak around 4°C confirms recently observed anomalies in the NMR spectrum at this temperature.     

Investigation of L(+)-Ascorbic acid with Raman spectroscopy in visible and UV light

Abstract: Raman spectroscopy investigations of l(+)-ascorbic acid and its mono- and di-deprotonated anions (AH^? and A^2?) are reviewed and new measurements reported with several wavelengths, 229, 244, 266, 488, and 532 nm. Results are interpreted, assisted by new DFT/B3LYP quantum chemical calculations with 6-311++G(d,p) basis sets for several conformations of ascorbic acid and the anions. Raman spectra were measured during titration with NaOH base in an oxygen-poor environment to avoid fluorescence when solutions were alkaline. The ultraviolet (UV) absorption band for ascorbic acid in aqueous solution at ～247 nm was found to cause strong resonance enhancement for the ring C?C stretching mode (called B) at ～1692 cm^?1. The ascorbate mono-anion absorbs at ～264.8 nm giving Raman resonance enhancement for the same ring C–C bond stretching, downshifted to ～1591 cm^?1. Finally, for the ascorbate di-anion, absorption was found at ～298.4 nm with molar absorptivity of ～7,000 L mol^?1 cm^?1 and below ～220 nm. With UV light (244 and 266 nm), strongly basic solutions gave pronounced Raman resonance enhancement at ～1556 cm^?1. Relatively weak preresonance enhancement was seen for A^2? when excitation was done with 229 nm UV light, allowing water bands to become observable as for normal visible light Raman spectra.     

Laser-induced Raman scattering in calcium titanate

The Raman spectrum of polycrystalline calcium titanate prepared by a liquid mix technique and heated to 800°C has been recorded at room temperature using an argon-ion laser as exciter. The observed spectrum was interpreted on the basis of factor-group C_2V. Not all of the Raman active modes predicted by factor group analysis were observed and this could be due to: over-lapping of bands, or very low polarizabilities of some of the modes or masking of the weak bands by intense bands. The band at 639 cm^?1 is tentatively assigned to the TiO symmetric stretching vibration (γ₁) and the bands at 495 and 471 cm^?1 to torsional modes. The bands in the region 180–340 cm^?1 are assigned to the OTiO bending modes and the 155 cm^?1 band to the Ca(TiO₃) lattice mode. The observed Raman bands are compared with the available infrared absorption data and, as expected, some coincidences in frequencies are seen for this compound with a noncentrosymmetric structure.     

Synthesis of Ge-Sn at high pressure and high temperature in a laser-heated diamond anvil cell

Ge–Sn compound is predicted to be a direct band gap semiconductor with a tunable band gap. However, the bulk synthesis of this material by conventional methods at ambient pressure is unsuccessful due to the poor solubility of Sn in Ge. We report the successful synthesis of Ge–Sn in a laser-heated diamond anvil cell (LHDAC) at ~7.6 GPa &; ~2000 K. In situ Raman spectroscopy of the sample showed, apart from the characteristic Raman modes of Ge TO (Г) and β-Sn TO (Г), two additional Raman modes at ~225 cm^?1 (named Ge–Sn₁) and ~133 cm^?1 (named Ge–Sn₂). When the sample was quenched, the Ge–Sn₁ mode remained stable at ~215 cm^?1, whereas the Ge–Sn₂ mode had diminished in intensity. Comparing the Ge–Sn Raman mode at ~225 cm^?1 with the one observed in thin film studies, we interpret that the observed phonon mode may be formed due to Sn-rich Ge–Sn system. The additional Raman mode seen at ~133 cm^?1 suggested the formation of low symmetry phase under high P–T conditions. The results are compared with Ge–Si binary system.     

Calibration of berlinite (AlPO4) as Raman spectroscopic pressure sensor for diamond‐anvil cell experiments at elevated temperatures

Changes in the band position of the 462 and the 1111 cm^–1 A₁ modes of berlinite (AlPO₄) with temperature and pressure were determined in situ to 500°C and to 10 GPa using Raman spectroscopy and diamond‐anvil cells. These bands shift in opposite directions with pressure and, likewise, with temperature. At a known temperature, the relative difference of both band positions (Δν)_P,T can therefore be used as a pressure gauge that does not require calibration of the spectrometer. At ambient pressure, the observed temperature dependence of this relative difference of the line positions is very close to linear and can be described by (Δν)_{T, 0.1 MPa} (cm^–1) = 0.0181 T – 0.46 where 23 ≤ T (°C) ≤ 500. Along the 23°C isotherm to 10 GPa, pressure and relative wavenumber difference (Δν)_{P, 23°C} are related by the equation P (GPa) = 0.00083 [(Δν)_{P, 23°C}]² – 0.062 (Δν)_{P, 23°C}. Both equations can be combined to determine pressures at higher temperatures under the assumption that the change in (Δν)_P,T with pressure is insensitive to temperature. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman identification of lonsdaleite in Popigai impactites

Micro‐Raman spectroscopy and X‐ray diffraction method (XRD) were used to characterize impact carbonaceous rocks excavated from the Popigai crater (Siberia). The deconvolution of the first‐order Raman spectra of the rocks containing different amounts of carbon phases (diamond, lonsdaleite and graphite) allowed the identification of lonsdaleite spectrum. The most intensive band at 1292–1303 cm⁻¹ was ascribed to A_1g vibration mode of lonsdaleite, whereas the less intense band at 1219–1244 cm⁻¹ was attributed, in agreement with previously reported ab initio calculations, to E_2g vibration mode. The established correlation between the intensities of Raman and XRD peaks permits a rough estimation of lonsdaleite/diamond phase ratio in the impact rocks using micro‐Raman measurements. The second‐order Raman spectra of lonsdaleite–diamond rocks were recorded. Copyright © 2014 John Wiley & Sons, Ltd.     

Low Frequency Raman Spectra of Some Lactams

Abstract

Low frequency Raman spectra from 20 to 200 cm^?1 of δ-valerolactam and ε-caprolactam in CCl₄ solution have been measured at different temperatures (25–80°C). Experimental data were transformed to the R(v) representation and the assignments of some bands are discussed based on measurements of depolarization ratio. The spectral features indicate that C₂ symmetry dimers are predominant. Previous assignments of some bands are also revised.     

Effect of pressure on the Raman spectra of synthetic diamonds with boron impurity

The raman scattering technique is used for studying diamonds with a 0.04–0.1 at % boron impurity under a pressure up to 3 GPa in a chamber with sapphire anvils. The Raman frequency increases linearly with pressure for all samples with pressure coefficients of 2.947 cm^?1/GPa for pure diamond and 3.01 cm^?1/GPa for boron-doped samples. The Raman linewidths remain unchanged for pure diamond and for diamond with a boron concentration of about 0.04 at % and decrease linearly upon an increase in pressure for samples with a boron concentration of about 0.1 at %. The Raman spectra with a line profile corresponding to the Fano resonance do not change qualitatively up to a pressure of 3 GPa. In diamond samples with a boron impurity exceeding 0.1 at %, the boron concentration in the surface layer can be substantially higher than at the center of the sample.     

Raman Spectroscopy Investigation of Nano Hydroxyapatite Doped with Yttrium and Fluoride Ions

In this study, nano hydroxyapatite doped with yttrium (2.5, 5, and 7.5 mol%) and fluoride (2.5 mol%) ions were synthesized by precipitation method and sintered at 900°C, 1100°C, and 1300°C. Raman spectroscopy was applied to track the structural modifications in pure and doped hydroxyapatites. The results showed that the main characteristic band of pure hydroxyapatite at 963 cm^?1 was not affected significantly by ion doping but exhibited higher intensity with increasing sintering temperature. Due to fluoride substitution, the 1048 and 1034 cm^?1 bands of pure hydroxyapatites appeared with a wavenumber shift in the spectra of ion-doped hydroxyapatites. The 333 cm^?1 band of pure hydroxyapatite disappeared and an additional calcium–fluor bond at 322 cm^?1 was observable in ion-doped hydroxyapatites. Two fluorescence bands at 770 and 697 cm^?1, which were also observed in the spectra of pure hydroxyapatites, shifted to higher wavenumbers in the spectra of ion-doped hydroxyapatites. This was considered to result from the perturbation in the hexagonal structure of hydroxyapatite due to yttrium and fluoride codoping.     

Raman spectrum of strontium titanate

The Raman spectrum of strontium titanate has been recorded using λ 4358 of mercury as exciter. The observed spectrum consists of 7 Raman lines, one of which is of low frequency, as expected from the recent theory of Cochran. 6 of these Raman lines have been interpreted as the first order spectrum arising from a small deviation of the cubic strontium titanate from its idealized symmetry. It has been shown that one normal mode of SrTiO₃ neglected by J.T.Last, will be really active in infrared absorption in the region of 440 cm^?1 and that it has to be taken into account in the interpretation of the infrared spectra of titanates. The four vibrational modes of the unit cell of SrTiO₃ correspond to frequencies of 90, 335, 441 and 620 cm^?1 observed in Raman effect. The large width of the Raman lines and the additional lines at 256 cm^?1 and 726 cm^?1 have been attributed to a splitting of the longitudinal and transverse optical modes. With the observed frequencies it has been found possible to account for in a satisfactory manner the specific heat of SrTiO₃ in the range 54·84° K to 1800° K.     

Raman scattering of high-temperature phase transition in KH2PO4

Raman scattering was applied to study the high-temperature phase transition (near 175°C) in KH₂PO₄. Drastic temperature-dependent changes were observed to take place in the normal modes of B₁ symmetry between 1000–3400 cm^?1. The disintegration of the dominant broad feature near 2500 cm^?1 when temperature rises beyond 150°C suggests that the alteration of the hydrogen-bond network is closely connected with this high-temperature phase transition.     

High‐order Stokes and anti‐Stokes Raman generation in monoisotopic CVD 12C‐diamond

We determined, for the first time, the room temperature phonon energy related to the F_2g vibration mode (ω_SRS(12C) ～ 1333.2 cm^–1) in a mono‐crystalline single‐isotope CVD ¹²C‐diamond crystal by means of stimulated Raman scattering (SRS) spectroscopy. Picosecond one‐micron excitation using a Nd³⁺:Y₃Al₅O₁₂‐laser generates a nearly two‐octave spanning SRS frequency comb (～12000 cm^–1) consisting of higher‐order Stokes and anti‐Stokes components. The spacing of the spectral lines was found to differ by Δω_SRS ～ 0.9 cm^–1 from the comb spacing (ω_SRS(natC) ～ 1332.3 cm^–1) when pumping a conventional CVD diamond crystal with a natural composition of the two stable carbon isotopes ¹²C (98.93%) and ¹³C (1.07%). (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Thermo‐Raman spectroscopy of synthetic nesquehonite — implication for the geosequestration of greenhouse gases

Pure nesquehonite (MgCO₃·3H₂O)/Mg(HCO₃)(OH)·2H₂O was synthesised and characterised by a combination of thermo‐Raman spectroscopy and thermogravimetry with evolved gas analysis. Thermo‐Raman spectroscopy shows an intense band at 1098 cm⁻¹, which shifts to 1105 cm⁻¹ at 450 °C, assigned to the ν₁CO₃²⁻ symmetric stretching mode. Two bands at 1419 and 1509 cm⁻¹ assigned to the ν₃ antisymmetric stretching mode shift to 1434 and 1504 cm⁻¹ at 175 °C. Two new peaks at 1385 and 1405 cm⁻¹ observed at temperatures higher than 175 °C are assigned to the antisymmetric stretching modes of the (HCO₃)⁻ units. Throughout all the thermo‐Raman spectra, a band at 3550 cm⁻¹ is attributed to the stretching vibration of OH units. Raman bands at 3124, 3295 and 3423 cm⁻¹ are assigned to water stretching vibrations. The intensity of these bands is lost by 175 °C. The Raman spectra were in harmony with the thermal analysis data. This research has defined the thermal stability of one of the hydrous carbonates, namely nesquehonite. Thermo‐Raman spectroscopy enables the thermal stability of the mineral nesquehonite to be defined, and, further, the changes in the formula of nesquehonite with temperature change can be defined. Indeed, Raman spectroscopy enables the formula of nesquehonite to be better defined as Mg(OH)(HCO₃)·2H₂O. Copyright © 2008 John Wiley & Sons, Ltd.     

Temperature dependence of the Raman spectra of Bi2Te3 and Bi0.5Sb1.5Te3 thermoelectric films

The temperature dependence of the Raman spectra of Bi₂Te₃ and Bi_0.5Sb_1.5Te₃ thermoelectric films was investigated. The temperature coefficients of the E_g(2) peak positions were determined as –0.0137 cm^–1/°C and –0.0156 cm^–1/°C, respectively. The thermal expansion of the crystal caused a linear shift of the Raman peak induced by the temperature change. Based on the linear relation, a reliable and noninvasive micro‐Raman scattering method was shown to measure the thermal conductivity of the thermoelectric films. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman spectra in doped cadmium oxide

Raman spectra of polycrystalline CdO-samples with electron-densities between 0.8 × 10¹⁹ and 13 × 10¹⁹ cm^?3 and mobilities between 80 and 250 cm²V^?1sec^?1 were observed at 300 and 2 K. Two first order Raman peaks are found at 404 and 345 cm^?1 while the second order spectrum is interpreted as due to the following processes: 2LO(L) near 970 cm^?1, 2LO(X) near 780 cm^?1, 2TO(X) or 2TO(L) at 480 cm^?1 and TA + TO(X) at 270 cm^?1. The 2LO(L)-peak shift to lower energiesand broadens with increasing electron density. This effect cannot be explained by existing theories.     

Raman Spectroscopic Study of the Molybdate Mineral Szenicsite and Comparison with Other Paragenetically Related Molybdate Minerals

Abstract

The molybdate‐bearing mineral szenicsite, Cu₃(MoO₄)(OH)₄, has been studied by Raman and infrared spectroscopy. A comparison of the Raman spectra is made with those of the closely related molybdate‐bearing minerals, wulfenite, powellite, lindgrenite, and iriginite, which show common paragenesis. The Raman spectrum of szenicsite displays an intense, sharp band at 898 cm^?1, attributed to the ν₁ symmetric stretching vibration of the MoO₄ units. The position of this particular band may be compared with the values of 871 cm^?1 for wulfenite and scheelite and 879 cm^?1 for powellite. Two Raman bands are observed at 827 and 801 cm^?1 for szenicsite, which are assigned to the ν₃(E _g ) vibrational mode of the molybdate anion. The two MO₄ ν₂ modes are observed at 349 (B _g ) and 308 cm^?1 (A _g ). The Raman band at 408 cm^?1 for szenicsite is assigned to the ν₄(E _g ) band. The Raman spectra are assigned according to a factor group analysis and are related to the structure of the minerals. The various minerals mentioned have characteristically different Raman spectra.     

High-pressure Raman and infrared spectroscopic studies of ZrP2O7

High-pressure Raman and mid-infrared spectroscopic studies were carried out on ZrP₂O₇ to 23.2 and 13 GPa respectively. In the pressure range 0.7–4.3 GPa the lattice mode at 248 cm^?1 disappears, new modes appear around 380 and 1111 cm^?1 and the strong symmetric stretching mode at 476 cm^?1 softens, possibly indicating a subtle phase transition. Above 8 GPa all the modes broaden, and all of the Raman modes disappear beyond 18 GPa. On decompression from the highest pressure, 23.2, to 0 GPa all of the modes reappear but with larger full width at half maximum. Lattice dynamics of the high temperature phase of ZrP₂O₇ were studied using first principles method and compared with experimental values.     

IR Absorption and Raman spectroscopic study of reentrant-nematic liquid crystalline N-[4-(4-Octyloxy-benzoyloxy) Benzylidene]-4-Cyanoaniline (OBBC)

Abstract

The IR absorption and Raman scattering of OBBC have been investigated in the solid, ReN, SmA and nematic phases. The intensity of the 2229 cm^?1 band assigned to the C[tbnd]N stretching mode decreases with increasing temperature in the reentrant nematic phase; this is attributed to a change in the overlap of the molecules. While the IR bands at 1728 and 841 cm^?1 also show a remarkable temperature dependence, Raman bands do not show significant temperature dependence in the liquid-crystal phases.