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1.
《Vibrational Spectroscopy》2002,28(2):209-221
Syngenite (K2Ca(SO4)2·H2O), formed during treatment of manure with sulphuric acid, was studied by infrared, near-infrared (NIR) and Raman spectroscopy. Cs site symmetry was determined for the two sulphate groups in syngenite (P21/m), so all bands are both infrared and Raman active. The split ν1 (two Raman+two infrared bands) was observed at 981 and 1000 cm−1. The split ν2 (four Raman+four infrared bands) was observed in the Raman spectrum at 424, 441, 471 and 491 cm−1. In the infrared spectrum, only one band was observed at 439 cm−1. From the split ν3 (six Raman+six infrared) bands three 298 K Raman bands were observed at 1117, 1138 and 1166 cm−1. Cooling to 77 K resulted in four bands at 1119, 1136, 1144 and 1167 cm−1. In the infrared spectrum, five bands were observed at 1110, 1125, 1136, 1148 and 1193 cm−1. From the split ν4 (six infrared+six Raman bands) four bands were observed in the infrared spectrum at 604, 617, 644 and 657 cm−1. The 298 K Raman spectrum showed one band at 641 cm−1, while at 77 K four bands were observed at 607, 621, 634 and 643 cm−1. Crystal water is observed in the infrared spectrum by the OH-liberation mode at 754 cm−1, OH-bending mode at 1631 cm−1, OH-stretching modes at 3248 (symmetric) and 3377 cm−1 (antisymmetric) and a combination band at 3510 cm−1 of the H-bonded OH-mode plus the OH-stretching mode. The near-infrared spectrum gave information about the crystal water resulting in overtone and combination bands of OH-liberation, OH-bending and OH-stretching modes.  相似文献   

2.
We calculated IR, nonresonance Raman spectra and vertical electronic transitions of the zigzag single-walled and double-walled boron nitride nanotubes ((0,n)-SWBNNTs and (0,n)@(0,2n)-DWBNNTs). In the low frequency range below 600 cm−1, the calculated Raman spectra of the nanotubes showed that RBMs (radial breathing modes) are strongly diameter-dependent, and in addition the RBMs of the DWBNNTs are blue-shifted reference to their corresponding one in the Raman spectra of the isolated (0,n)-SWBNNTs. In the high frequency range above ∼1200 cm−1, two proximate Raman features with symmetries of the A1g (∼1355 ± 10 cm−1) and E2g (∼1330 ± 25 cm−1) first increase in frequency then approach a constant value of ∼1365 and ∼1356 cm−1, respectively, with increasing tubes’ diameter, which is in excellent agreement with experimental observations. The calculated IR spectra exhibited IR features in the range of 1200–1550 cm−1 and in mid-frequency region are consistent with experiments. The calculated dipole allowed singlet–singlet and triplet–triplet electronic transitions suggesting a charge transfer process between the outer- and inner-shells of the DWBNNTs as well as, upon irradiation, the possibility of a system that can undergo internal conversion (IC) and intersystem crossing (ISC) processes, besides the photochemical and other photophysical processes.  相似文献   

3.
We investigate the nature of bonding and charge states in (U1−yCey)O2 (y = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) by Raman spectroscopy. Raman spectrum of UO2 exhibits two prominent bands below 1000 cm−1, a F2g mode at 446 cm−1 and a F1u LO mode at 578 cm−1. As y is increased from 0 to 0.6, the F1u exhibits a large blue shift of 90 cm−1, and from y = 0.6 to 1.0, a red shift of 54 cm−1. We show that our results can be interpreted as arising from anisotropic compression/relaxation of the lattice under Ce substitution and this can give an indication of its charge states. Alternate interpretations have been given in the literature on the effect of substituents and dopants to the Raman spectra of UO2 and CeO2. The present interpretation of chemical stress effects can be taken as another plausible explanation.  相似文献   

4.
The samples of dibarium magnesium orthoborate Ba2Mg(BO3)2 were synthesized by solid-state reaction. The X-ray diffraction (XRD) patterns and Raman spectra of the samples were collected. Electronic structure and vibrational spectroscopy of Ba2Mg(BO3)2 were systematically investigated by first principle calculation. A direct band gap of 4.4 eV was obtained from the calculated electronic structure results. The top valence band is constructed from O 2p states and the low conduction band mainly consists of Ba 5d states. Raman spectra for Ba2Mg(BO3)2 polycrystalline were obtained at ambient temperature. The factor group analysis results show the total lattice modes are 5Eu + 4A2u + 5Eg + 4A1g + 1A2g + 1A1u, of which 5Eg + 4A1g are Raman-active. Furthermore, we obtained the Raman active vibrational modes as well as their eigenfrequencies using first-principle calculation. With the assistance of the first-principle calculation and factor group analysis results, Raman bands of Ba2Mg(BO3)2 were assigned as Eg (42 cm−1), A1g (85 cm−1), Eg (156 cm−1), Eg (237 cm−1), A1g (286 cm−1), Eg (564 cm−1), A1g (761 cm−1), A1g (909 cm−1), Eg (1165 cm−1). The strongest band at 928 cm−1 in the experimental spectrum is assigned to totally symmetric stretching mode of the BO3 units.  相似文献   

5.
Spontaneous Raman spectra in the BaWO4 were measured in the temperature range from 4 K to 280 K, and the temperature dependence of the linewidth of the Ag (191 cm−1) Raman mode was analyzed using the lattice dynamical perturbative approach and one-phonon density of states (PDOS). The linewidth slope for the 191 cm−1 peak for an external mode is 7.2 times larger than that for the 926 cm−1 peak for a breathing mode. The different behaviors of these two modes in the case of temperature broadening could be attributed to the large energy band gap in the one-phonon density of states (PDOS) resulting in different anharmonic interactions. The origin may be that the ratio of up-conversion TDOS to down-conversion TDOS for Eg mode (191 cm−1) is more than that for Ag (926 cm−1). The peak of the Eg mode (191 cm−1) is attributed to the coupling mode both a rotation of the Barium and an out-of-phase rotation of the oxygen in xy plane as a librational mode.  相似文献   

6.
The mineral ettringite has been studied using a number of techniques, including XRD, SEM with EDX, thermogravimetry and vibrational spectroscopy. The mineral proved to be composed of 53% of ettringite and 47% of thaumasite in a solid solution. Thermogravimetry shows a mass loss of 46.2% up to 1000 °C. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1072 cm−1 attributed to a carbonate symmetric stretching mode, confirming the presence of thaumasite. The observation of multiple bands in the ν4 spectral region between 700 and 550 cm−1 offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3629 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3487 cm−1 to water stretching bands. Vibrational spectroscopy enables an assessment of the molecular structure of natural ettringite to be made.  相似文献   

7.
The phonon dispersions of SrMoO4 crystal are calculated using the lattice dynamical calculations approach. Spontaneous Raman spectra in the SrMoO4 were measured in the temperature range from 10 K to 295 K, and the temperature dependence of the linewidth of the Bg (95 cm−1) and Ag (888 cm−1) Raman modes was analyzed using the lattice dynamical perturbative approach. We found that different behaviors of these two modes in the case of temperature broadening could be attributed to the large energy band gap in the phonon spectrum resulting in different anharmonic interactions. The calculated temperature dependence of the linewidth of Ag (888 cm−1) mode was well accounted for the experimental one by including both down-conversion by the cubic term and the dephasing by quartic term. The dephasing processes are increased only at high temperatures and the effect of dephasing is related to the size of a large phonon band gap.  相似文献   

8.
Raman and infrared spectroscopy were applied for the vibrational characterization of lapachol and its pyran derivatives, α-lapachone and β-lapachone. Experimental spectra of solid state samples were acquired between 4000 and 100 cm−1 in Raman experiments, and between 4000 and 600 cm−1 (mid-infrared) and 600–100 cm−1 (far-infrared) with FTIR spectroscopy, respectively. Full structure optimization and theoretical vibrational wavenumbers were calculated at the B3LYP/6-31 + + G(d,p) level. Detailed assignments of vibrational modes in an experimental and theoretical spectra were based on potential energy distribution analyses, using Veda 4.1 software. Clear differentiation between the three compounds was verified in the region between 1725 and 1525 cm−1, in which the ν(CO) and ν(CC) modes of the quinone moiety were assigned.  相似文献   

9.
The paper presents the study of selected montmorillonite standards by Raman spectroscopy and microscopy supported by elemental analysis, X-ray powder diffraction analysis and thermal analysis. Dispersive Raman spectroscopy with excitation lasers of 532 nm and 780 nm, dispersive Raman microscopy with excitation laser of 532 nm and 100× magnifying lens, and Fourier Transform-Raman spectroscopy with excitation laser of 1064 nm were used for the analysis of four montmorillonites (Kunipia-F, SWy-2, STx-1b and SAz-2). These mineral standards differed mainly in the type of interlayer cation and substitution of octahedral aluminium by magnesium or iron. A comparison of measured Raman spectra of montmorillonite with regard to their level of fluorescence and the presence of characteristic spectral bands was carried out. Almost all measured spectra of montmorillonites were significantly affected by fluorescence and only one sample was influenced by fluorescence slightly or not at all. In the spectra of tested montmorillonites, several characteristic Raman bands were found. The most intensive band at 96 cm−1 belongs to deformation vibrations of interlayer cations. The band at 200 cm−1 corresponds to deformation vibrations of the AlO6 octahedron and at 710 cm−1 can be assigned to deformation vibrations of the SiO4 tetrahedron. The band at 3620 cm−1 corresponds to the stretching vibration of structural OH groups in montmorillonites.  相似文献   

10.
《Vibrational Spectroscopy》2007,43(2):284-287
Geometrically frustrated pyrochlore Y2Ru2O7, which shows a spin-glass-like transition at TG  80 K, were investigated by temperature-dependent Raman scattering. Three discernable phonons appear around 315, 410, and 510 cm−1 without any abrupt change in the number of Raman active modes within the temperature range of 10–300 K. Fitting each phonon with Lorentz oscillators, we analyzed the effects of temperature on the phonon frequencies and the linewidths. The temperature-dependence of the mode near 510 cm−1 shows abnormal behavior below TG, while the other two phonons follow the usual thermal effect of lattice vibration. This behavior can be understood in terms of spin–phonon coupling. Considering the atomic modulations of each phonon mode, it is conjectured that the 510 cm−1 phonon mode is isotropically coupled to the spin degree of freedom, while the other modes are not.  相似文献   

11.
The phosphate mineral series eosphorite–childrenite–(Mn,Fe)Al(PO4)(OH)2·(H2O) has been studied using a combination of electron probe analysis and vibrational spectroscopy. Eosphorite is the manganese rich mineral with lower iron content in comparison with the childrenite which has higher iron and lower manganese content. The determined formulae of the two studied minerals are: (Mn0.72,Fe0.13,Ca0.01)(Al)1.04(PO4, OHPO3)1.07(OH1.89,F0.02)·0.94(H2O) for SAA-090 and (Fe0.49,Mn0.35,Mg0.06,Ca0.04)(Al)1.03(PO4, OHPO3)1.05(OH)1.90·0.95(H2O) for SAA-072. Raman spectroscopy enabled the observation of bands at 970 cm−1 and 1011 cm−1 assigned to monohydrogen phosphate, phosphate and dihydrogen phosphate units. Differences are observed in the area of the peaks between the two eosphorite minerals. Raman bands at 562 cm−1, 595 cm−1, and 608 cm−1 are assigned to the ν4 bending modes of the PO4, HPO4 and H2PO4 units; Raman bands at 405 cm−1, 427 cm−1 and 466 cm−1 are attributed to the ν2 modes of these units. Raman bands of the hydroxyl and water stretching modes are observed. Vibrational spectroscopy enabled details of the molecular structure of the eosphorite mineral series to be determined.  相似文献   

12.
《Vibrational Spectroscopy》2007,43(2):353-356
We present results of Raman scattering studies on LaMn1−xCoxO3+δ over a wide range of doping content (x = 0.1–0.75) and temperature range of 20–300 K. Powder X-ray diffraction patterns show that there is a structural change from orthorhombic to rhombohedral at x = 0.5 as x increases. Raman spectra of all LaMn1−xCoxO3+δ samples show peaks near 260, 500, and 650 cm−1. However, the Raman spectra are not drastically different from each other across the structural phase transition at x = 0.5. On the other hand, the peak frequencies of the modes near 260 and 500 cm−1 as functions of Co content (x) show slope changes at x = 0.5. The full-width at the half-maximum (FWHM) of the mode near 650 cm−1 as a function of Co content (x) shows minimum at x = 0.5. Normally, larger values of FWHM are expected at near x = 0.5, if the mode were affected by the structural disorder at the phase boundary. Therefore, it is likely due to lowest charge concentration at x = 0.5, which results in lowest screening effect. This is consistent with the fact that the intensity of the phonons is strongest at x = 0.5. As the temperature decreases, the two peaks near 500 and 650 cm−1 of different Co contents, related with octahedral distortions, are found to shift to lower frequencies unlike the usual temperature behavior. However, no abrupt change in the peak frequencies and the FWHM is observed across measured temperature range, regardless of the Co content.  相似文献   

13.
We observed the Raman spectra of carriers, positive polarons and bipolarons, generated in a poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-C14) film by FeCl3 vapor doping. Electrical conductivity and Raman measurements indicate that the dominant carriers in the conducting state were bipolarons. We identified positive polarons and bipolarons generated in an ionic-liquid-gated transistor (ILGT) fabricated with PBTTT-C14 as an active semiconductor and an ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [BMIM][TFSI] as a gate dielectric using Raman spectroscopy. The relationship between the source−drain current (ID) at a constant source−drain voltage (VD) and the gate voltage (VG) was measured. ID increased above −VG = 1.1 V and showed a maximum at −VG = 2.0 V. Positive polarons were formed at the initial stage of electrochemical doping (−VG = 0.8 V). As ID increased, positive bipolarons were formed. Above VG = −2.0 V, bipolarons were dominant. The charge density (n), the doping level (x), and the mobility of the bipolarons were calculated from the electrochemical measurements. The highest mobility (μ) of bipolarons was 0.72 cm2 V−1 s−1 at x = 110 mol%/repeating unit (−VG = 2.0 V), whereas the highest μ of polarons was 4.6 × 10−4 cm2 V−1 s−1 at x = 10 mol%.  相似文献   

14.
Behavior of the regularity modes of isotactic polypropylene is analyzed in Raman spectra of a number of random propylene/olefin copolymers. The regularity modes at 809, 841, 973, 998, and 1220 cm−1 decrease in intensity with growth of the content of the incorporated monomer. For the lines at 809, 973, and 1220 cm−1 the rate of intensity damping varies depending on the structure of the incorporated monomer. The type of the incorporated monomer has inconsiderable effect on the evolution of intensity of the regularity bands at 841 and 998 cm−1. Anomalous behavior of the mode at 1220 cm−1 was observed for the propylene/1-butene copolymers.  相似文献   

15.
Infrared and Raman spectra of cubic magnesium caesium phosphate hexahydrate, MgCsPO4·6H2O (cF100), and its partially deuterated analogues were analyzed and compared to the previously studied spectra of the hexagonal analogue, MgCsPO4·6H2O (hP50). The vibrational spectra of the cubic and hexagonal dimorphic analogues are similar, especially in the regions of HOH stretching and bending vibrations. In the difference IR spectrum of the slightly deuterated analogue (<5% D), one distinctive band appears at 2260 cm−1 with a small shoulder at around 2170 cm−1, but only one band is expected in the region of the OD stretchings of isotopically isolated HDO molecules. The small weak band could possibly result from second-order transitions (a combination of HDO bending and some libration of the same species) rather than statistical disorder of the water molecules. By comparing the IR spectra in the region of external vibrations of water molecules of the protiated compound recorded at RT (room temperature) and at LNT (liquid nitrogen temperature) and those in the series of the partially deuterated analogues, it can be stated with certainty that the bands at 924 and 817 cm−1 result from librations of water molecules, rocking and wagging respectively. And the band at 429 cm−1 can be safely attributed to a stretching Mg–Ow mode. In the ν3(PO4) and ν4(PO4) region in the infrared spectra, one band in each is observed, at 995 and 559 cm−1, respectively. In the region of the ν1 modes, in the Raman spectrum of the protiated compound, one very intense band was observed at 930 cm−1 which is only insignificantly shifted to 929 cm−1 in the spectrum of the perdeuterated compound. The band at 379 cm−1 in the Raman spectrum could be assigned to the ν2(PO4) modes. With respect to the phosphate ion vibrations, the comparison between the two polymorphic forms of MgCsPO4·6H2O and their deuterated compounds shows that ν1(PO4) and ν3(PO4) appear at lower wavenumbers in the cubic phase than in the hexagonal phase. These data are in full agreement with the lower repulsion potential at the cubic lattice sites compared with that for the hexagonal lattice sites.  相似文献   

16.
Excess molar volumes VmE of binary mixtures of 2,2,2-trifluoroethanol with water, or acetone, or methanol, or ethanol, or 1-alcholos, or 1,4-difluorobenzene, or 4-fluorotoluene or α,α,α-trifluorotoluene were measured in a vibrating tube densimeter at temperature 298.15 K and pressure of 101 kPa. The VmE extrema are: 1.540 cm3 · mol−1 for (2,2,2-trifluoroethanol + 1-heptanol); 1.452 cm3 · mol−1 for (2,2,2-trifluoroethanol + 1-hexanol); 1.238 cm3 · mol−1 for (2,2,2-trifluoroethanol + 1-butanol); 0.821 cm3 · mol−1 for (2,2,2-trifluoroethanol + 4-fluorotoluene); 0.817 cm3 · mol−1 for (2,2,2-trifluoroethanol + ethanol); 0.647 cm3 · mol−1 for (2,2,2-trifluoroethanol + methanol); 0.618 cm3 · mol−1 for (2,2,2-trifluoroethanol + acetone); 0.605 cm3 · mol−1 for (2,2,2-trifluoroethanol + α,α,α-trifluorotoluene); 0.485 cm3 · mol−1 for (2,2,2-trifluoroethanol + 1,4-difluorobenzene); and −0.656 cm3 · mol−1 for (2,2,2-trifluoroethanol + water). The limiting excess partial molar volumes are estimated.  相似文献   

17.
We present a Raman study of liquid and polycrystalline dioxolane, together with data for a solid dioxolane/argon film. Observed bands are assigned to the bent conformer on the basis of ab initio calculated vibrations, accompanied with potential energy distribution. Two internal modes were calculated at 658 and 720 cm−1 for the bent form. These were observed at 665 and 722 cm−1 in liquid, and split into four bands (at 694, 697, 725, and 728 cm−1) in the crystal at 10 K. In the solid dioxolane/argon film an additional band appears at 705 cm−1 (between the bands at 675 and 726 cm−1). A search for an additional dioxolane conformer trapped in argon was undertaken by performing molecular dynamics simulations of dioxolane/argon solid film and averaging overall molecular conformations. The resulting conformation did not correspond to an energy minimum, but indicated that changes of only a few degrees in dihedral angles could shift ring deformation and OCO bending modes for more than 10 cm−1. Differential scanning calorimetric measurements gave evidence of solidification upon cooling at 146 K, and two phase changes on heating (one at 158.3 K, and a melting transition at 180.3 K). Further study is required on the hysteresis effect in the temperature behavior of dioxolane, and on the nature of the intermediate solid phase.  相似文献   

18.
Raman and infrared (IR) spectroscopy are complementary spectroscopic techniques. However, measurement of Raman and IR spectra are commonly carried out on separate instruments. A dispersive system that enables both Raman spectroscopy and NIR spectroscopy was designed, built, and tested. The prototype system measures spectral ranges of 2600–300 cm−1 and 752–987 nm for Raman and NIR channels, respectively. A wavelength accuracy better than 0.6 nm and spectral resolution better than 1 nm (14.4 cm−1 for Raman channel) could be achieved with our configuration. The linearity of spectral response was better than 99.8%. The intensity stability of the instrument was found to be 0.7% and 0.4% for Raman and NIR channels, respectively. The performance of the instrument was evaluated using binary aqueous solutions of ethanol and ovalbumin. It was found that ethanol concentrations (2–10%) could be predicted with a root mean squared error of prediction (RMSEP) of 0.45% using Raman peak height at 882.2 cm−1. Quantification of ovalbumin concentration (8–16 g/L) in aqueous solutions and in denatured states yielded RMSEP values of 1.05 g/L and 0.74 g/L, respectively. Using concentration as external perturbation in two-dimensional correlation spectroscopy (2DCOS), heterospectral correlation analysis revealed the relationship between NIR and Raman spectra.  相似文献   

19.
Raman analyses were performed on thin films prepared from B-doped Si nanoparticles with an average diameter of 15 nm using the spin-coating method. The resulting spectrum exhibited a broad band with a peak near 520 cm−1. The band was decomposed into three bands corresponding to the crystalline, grain boundary (GB), and amorphous regions by the least-squares band-fitting method based on the three Voigt bands. The fractions of the crystalline, GB, and amorphous regions were 37%, 35%, and 28%, respectively. A spherical particle exhibited an ordered crystalline core surrounded by a disordered shell in a transmission electron microscope (TEM) image. The crystalline fraction of the 15-nm B-doped Si nanoparticle film was much lower than that of the 19-nm P-doped Si nanoparticle film. This result suggested that the B-doping mechanism was different from that of P-doping. The temperature of the sample was estimated from the ratio of the peak intensities of anti-Stokes to Stokes Raman bands (IAS/IS) observed near 520 cm−1. The temperature of the B-doped Si nanoparticle film upon irradiation at a power density of 4.6 kW/cm2 was 298 °C, whereas the temperature of the P-doped Si nanoparticle film was 92 °C. The B-doped Si nanoparticle films were capable of producing light-induced heat.  相似文献   

20.
The efficiently hydrothermal route using sucrose without any catalysts is employed to prepare the uniform carbon spheres. The monodisperse 100–150 nm carbon spheres are obtained with the activation treatment in molten KOH. The carbon spheres are characterized by transmission electron microscope, X-ray diffraction, N2 adsorption, Raman spectroscopy and electrochemical techniques. The relationships of specific capacitance and surface properties of carbon spheres are investigated. A single electrode of carbon nanosphere materials performs excellent specific capacitance (328 F g−1), area capacitance (19.2 μF cm−2) and volumetric capacitance (383 F cm−3).  相似文献   

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