Electronic Absorption Spectra of Some Fluoroaminotoluenes

Abstract

The near ultraviolet absorption spectra of 2-fluoro-5-amino-; 3-fluoro-4-amino-, 3-fluoro-6-amino-and 4-fluoro-2-aminotoluene have been investigated in vapour phase. The strongest band appearing at 2887.5 Å (34621 cm^?1), 2966.1 Å (33704 cm^?1), 3026. 7 Å (33029 cm^?1) and 2891.4 Å (34575 cm^?1) in the respective molecules has been identified as the 0,0 band. All the bands have been analysed in terms of some ground and excited state fundamentals. The assignment of the fundamental frequencies to the probable modes of vibration have also been discussed.     

Vibrational Spectroscopy of the Borate Mineral Priceite—Implications for the Molecular Structure

ABSTRACT

Priceite is a calcium borate mineral and occurs as white crystals in the monoclinic pyramidal crystal system. We have used a combination of Raman spectroscopy with complimentary infrared spectroscopy and scanning electron microscopy with Energy-dispersive X-ray Spectroscopy (EDS) to study the mineral priceite. Chemical analysis shows a pure phase consisting of B and Ca only. Raman bands at 956, 974, 991, and 1019 cm^?1 are assigned to the BO stretching vibration of the B₁₀O₁₉ units. Raman bands at 1071, 1100, 1127, 1169, and 1211 cm^?1 are attributed to the BOH in-plane bending modes. The intense infrared band at 805 cm^?1 is assigned to the trigonal borate stretching modes. The Raman band at 674 cm^?1 together with bands at 689, 697, 736, and 602 cm^?1 are assigned to the trigonal and tetrahedral borate bending modes. Raman spectroscopy in the hydroxyl stretching region shows a series of bands with intense Raman band at 3555 cm^?1 with a distinct shoulder at 3568 cm^?1. Other bands in this spectral region are found at 3221, 3385, 3404, 3496, and 3510 cm^?1. All of these bands are assigned to water stretching vibrations. The observation of multiple bands supports the concept of water being in different molecular environments in the structure of priceite. The molecular structure of a natural priceite has been assessed using vibrational spectroscopy.     

Electronic Absorption Spectra of 2-Fluoro-4-bromo, 4-Fluoro-2-bromo and 2-Fluoro-5-bromo Toluenes

Abstract

Absorption spectra of 2-Fluoro-4-Bromo, 4-Fluoro-2-Bromo and 2-Fluoro-5-Bromo Toluenes have been investigated in the near ultraviolet region in vapour phase. The band systems correspond to allowed transitions with the most intense bands at 2742.09 Å (36458 cm^?1), 2745.96 Å (36406 cm^?1) and 2771.74 Å (36068 cm^?1) identified as 0,0 transitions in 2-Fluoro-4-Bromo, 4-Fluoro-2-Bromo and 2-Fluoro-5-Bromo Toluenes respectively. The bands in 4-Fluoro-2-Bromo Toluene have been analysed in terms of the ground state fundamental 208 cm^?1 and excited state fundamentals 244, 611, 855 and 1211 cm^?1 and the bands in 2-Fluoro-4-Bromo and 2-Fluoro-5-Bromo Toluenes are explained in terms of the upper state fundamentals 716, 987 and 1230 cm^?1 and 722, 886 and 2130 cm^?1 respectively.     

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.     

Raman Spectroscopic Analysis of Perovskite-Structured Alkali Metal Fluorides Containing Nickel and Copper Ions

ABSTRACT

The mixed metal fluorides containing alkali metals have a range of important applications in optical and electronic devices. Raman spectrums of two such fluorides were examined. Raman spectrum of KCuF₃ at 300 K exhibited bands at 261, 295, 363, 468, 519, and 549 cm^?1, indicating site symmetry (orthorhombic) lower than the tetragonal symmetry as observed from the powder X-ray diffraction pattern. Cubic KNiF₃ showed bands at 410, 468, and 657 cm^?1. The first two bands were attributed to the second-order phonon scattering, and the band at 657 cm^?1 was assigned to two-magnon peak.     

Anti-stokes emission in an additively colored KCl caused by excitation with a Nd: YAG laser

Abstract

We have observed the quadratic laser power dependence of two anti-Stokes emission bands at 15100cm^?1 and 14000cm^?1 in an additively colored KCl when excited with a Nd:YAG laser. The cross section of two photon absorption to cause the 14000cm^?1 band is estimated to be 4×10^?40cm⁴sec. We have observed that emission intensities are dependent on temperature in the range between 4. 2K and 130K. They are enhanced by means of optical bleaching and also with the increase of the F concentration. From a qualitative analysis of these observations, we propose that these emissions are correlated to the loose aggregation of the F centers.     

The Electronic and Infrared Absorption Spectra of Toluene-d

Abstract

The infrared and ultraviolet absorption spectra of toluene-d have been investigated for the first time in the regions 400 - 4000 cm^?1 and 2350 ?2750 A° respectively. The intense band at 2666.3 A°(37494 cm^?1) in the u.v. vapour absorption spectrum has been identified as the o,o band and others have been interpreted in terms of the three (519,632 and 785 cm^?1) ground state and the six (454,526,743,935,963 and 1180 cm^?1 excited state fundamentals. The correlation of the various frequencies of the ground and excited states of toluene and toluene-d has been done. The observed isotopic shift for toluene-d is 14 cm^?1.     

Comparative Fourier Transform Infrared Investigation of Oltu-Stone (Natural Carbon Black) and Jet

Fourier transform infrared (FT-IR) investigation of Oltu-stone (natural carbon black) and jet revealed several differences between these carbonaceous materials. The band peaking at about 1000 cm^?1 is the first important difference: while the band in the jet spectra appears as one sharp peak at about 1001 cm^?1, the similar band in the Oltu-stone spectra is shifted to about 1026 cm^?1 with a broad shoulder toward high frequency. Even though the assignment of the shifted band is at present controversial, it may be attributed to carbon-oxygen stretching mode. Second, the doublet bands at about 2912 and 2843 cm^?1 are much more intense in the jet spectra then in the Oltu-stone spectra. They are confidently attributed to aliphatic C-H stretching mode. Finally, the broad water band on setting at about 3750 cm^?1 is maturated in Oltu-stone, and it is much more evident than in that of jet.

Therefore, FT-IR appears as a favorable identification method for these kinds of carbonaceous materials.     

Changes in Dentin Collagen After Sample Grinding and Heating

ABSTRACT

Changes to the structure of the organic matrix of the dentin tissue were determined after sample grinding and heating. Powder dentin measuring 25–38 µm and slices with a thickness of about 50 µm were employed. Spectra acquisition was conducted with a Fourier-transform infrared spectrometer. The thermal treatment was performed between 100°C and 300°C, with steps of 25°C. After grinding, two bands (1283.5 ± 0.5 cm^?1 and 1240.7 ± 0.5 cm^?1) shifted to higher wavenumbers, while three bands (1339.5 ± 0.5 cm^?1, 1283.5 ± 0.5 cm^?1, and 1202.7 ± 0.5 cm^?1) shifted to lower wavenumbers after thermal treatment in the range 100–300°C; the band at 1283.5 ± 0.5 cm^?1 shifted only 2 cm^?1. Thermal treatment produced a wavenumber shift in the opposite direction compared with the shift produced after grinding. The observed changes in the vibration modes of the structure indicate that sample preparation or sterilization involving grinding and heating must be carefully evaluated in order to preserve the natural characteristic of the collagen structure.     

A Vibrational Spectroscopic Study of the So-Called Healing Mineral Papagoite CaCuAlSi2O6(OH)3

ABSTRACT

Papagoite is a silicate mineral named after an American Indian tribe and was used as a healing mineral. Papagoite CaCuAlSi₂O₆(OH)₃ is a hydroxy mixed anion compound with both silicate and hydroxyl anions in the formula. The structural characterization of the mineral papagoite remains incomplete. Papagoite is a four-membered ring silicate with Cu²⁺ in square planar coordination.

The intense sharp Raman band at 1053 cm^?1 is assigned to the ν₁ (A _1g) symmetric stretching vibration of the SiO₄ units. The splitting of the ν₃ vibrational mode offers support to the concept that the SiO₄ tetrahedron in papagoite is strongly distorted. A very intense Raman band observed at 630 cm^?1 with a shoulder at 644 cm^?1 is assigned to the ν₄ vibrational modes.

Intense Raman bands at 419 and 460 cm^?1 are attributed to the ν₂ bending modes.

Intense Raman bands at 3545 and 3573 cm^?1 are assigned to the stretching vibrations of the OH units. Low-intensity Raman bands at 3368 and 3453 cm^?1 are assigned to water stretching modes. It is suggested that the formula of papagoite is more likely to be CaCuAlSi₂O₆(OH)₃ · xH₂O. Hence, vibrational spectroscopy has been used to characterize the molecular structure of papagoite.     

Vibrational spectroscopic characterization of the magnesium borate-phosphate mineral lüneburgite

ABSTRACT

Lüneburgite, a rare magnesium borate-phosphate mineral from Mejillones, Chile, has been characterized using Raman and mid-infrared spectroscopy methods. Boron tetrahedra are characterized by sharp Raman band at 877?cm^?1, attributed to the ν₁[BO₄]^5? symmetric stretching mode. The phosphate anion is associated with a distinct band at 1032?cm^?1, attributed to the ν₃[PO₄]^3? antisymmetric stretching mode. The most intensive Raman band at 734?cm^?1 is ascribed to stretching vibrations of bridging oxygen atoms in boron–oxygen–phosphor bridges. Bonds associated with water bending mode and stretching vibration are observed at 1661?cm^?1 (infrared) and in the 3000–3500?cm^?1 region (Raman and infrared spectrum).     

Untersuchung von Raumladungsschichten an Zinkoxid-Oberflächen mit Hilfe der Elektroreflexion

Using the electroreflectance method space charge layers on crystals of different conductivities have been identified. The space charge layers were formed by adsorption of oxygen or atomic hydrogen. The limit of sensitivity required the irradiation with 5×10¹³ photons/cm²×sec of band gap energy. After exposure to atomic hydrogen all samples showed accumulation layers. With a partial pressure of oxygen above 350 mm Hg crystals of high conductivity (σ=47 ohm^?1 cm^?1) exhibit depletion layers, which change into accumulation layers, if the partial pressure is reduced below the limit. Crystals of a lower conductivity (σ=10^?3–10^?1 ohm^?1 cm^?1) show accumulation layers up to the highest applied oxygen pressure of 760 mm Hg. The phenomena are attributed to a dynamical equilibrium between adsorption and photo-desorption of oxygen. This equilibrium depends on oxygen pressure and free carrier concentration. By comparing a calculated curve with the experimental results the value of 3.31 ev is obtained for the energy gap, light polarized perpendicular to thec-acis.     

Irradiation and heating effects in amethyst crystals from brazil

Abstract

In this work we report optical absorption spectroscopy study of thermal and irradiation effects on samples of amethyst from Minas Gerais and Rio Grande do Sul, Brazil. Three bands were studied: 10500 cm^?1 (k), 18300 cm^?1 (θ) and 28000 cm^?1 (ζ). Thermal and irradiation effects shows that the θ and ζ bands belongs to a same center and the k band to another center. The isothermal decay and irradiation growth of these band reveal a complex kinetics. The optical absorption bands of amethyst from Minas Gerais do not recover the prmitive absorbance after being bleached at 470°C and irradiated. This sample heated at 470°C in highly reducing atmosphere gets a yellow-brown color. The amethyst from Rio Grande do Sul treated at 400°C gets, also, a yellow-brown color. We suggest this color is probalbly due to the formation of Fe₂O₃ submicroscopc segregate crystals due to the diffusion of Fe ions and oxygen vacancies.     

3-Naphthyl-4-Quinazolone Infrared and Nuclear Magnetic Resonance Band Assignments

Abstract

The ir and nmr spectra of 24 3-naphthyl-4-quinazolones were examined. There are three principal ir bands in the 1500 and 1705 cm^?1 region of the spectra. The first at 1685–1705 cm^?1 is assigned to the tertiary amide carbonyl (ArCONR₂), the second at 1593–1645 cm^?1 to the anil chromophore (ArN=C-N) and the third to the naphthalene ring at 1600 cm^?1. The nmr band assignments are straight forward.     

Indole in Argon Matrix: The Near UV Spectra.

Abstract

The near UV absorption, steady-state polarized fluorescence excitation and time–-resolved fluorescence emission spectra of indole in argon matrix are reported. The absorption maxima of the four lowest singlet transitions were identified at 35095 cm^?1(also the S_{1, 0} 0–0 band), 37650 cm^?1 (S_2,0), 47415 cm^?1 (S_3,0), and 51680 cm^?1 (S_4,0). No distinct 0–0 band of the second transition was identified but the linearly polarized, steady-state fluorescence excitation spectrum indicates an onset of weak S_2,0 bands on the blue side of the S_1,0 0–0 peak (35095 + 400 cm^?1). Only one fluorescence emission component, of 4.9±0.2 ns, was obtained by excitation over the S_{1, 0} 0–0 + 565 cm^?1 to S_1,0 0–0 - 245 cm^?1 domain. The reported data strongly suggest the ¹L_b ^?1A₁ and ¹L_a ^?1A₁assignment for the lowest and next lowest transitions, respectively.     

Chemisorption of carbon monoxide on platinum {111}: Reflection-absorption infrared spectroscopy

Reflection-adsorption infrared spectroscopy has been combined with thermal desorption and surface stoichiometry measurements to study the structure of CO chemisorbed on a {111}- oriented platinum ribbon under uhv conditions. Desorption spectra show a single peak at coverages > 10¹⁴ molecules cm^?2, with the desorption energy decreasing with increasing coverage up to 0.4 of a monolayer, and then remaining constant at ≈135 kJ mol^?1 until saturation. The “saturation” coverage at 300 K is 7 × 10¹⁴ molecules cm^?2, and no new low temperatures state is formed after adsorption at 120 K. Infrared spectra show a single very intense, sharp band over the spectral range investigated (1500 to 2100 cm^?1), which first appears at low coverages at 2065 cm^?1 and shifts continuously with increasing coverage to 2101 cm^?1 at 7 × 10¹⁴ molecules cm^?2. The halfwidth of the band at 2101 cm^?1 is 9.0 cm^?1, independent of temperature and only slightly dependent on coverage. The band intensity does not increase uniformly with increasing coverage, and hysteresis is observed between adsorption and desorption sequences in the variation of both the band intensity and frequency as a function of coverage. The frequency shift and the virtual invariance of the absorption band halfwidt with increasing coverage (Jespite recent LEED evidence for overlayer compression in this system) are attributed to strong dipole-dipole coupling in the overlayer.     

Absolute integrated intensity and individual line parameters for the 6·2μ band of NO2

The absolute integrated intensity of the 6·2μ band of NO₂ at 40°C was determined from quantitative spectra at ~ 10 cm^?1 resolution by the spectral band model technique. A value of 1430±300 cm^?2 atm^?1 was obtained. Individual line parameters, positions, intensities and ground state energies were derived, and line-by-line calculations were compared with the band model results and with the quantitative spectra obtained at ~ 0·5 cm^?1 resolution.     

The Electronic Absorption Spectrum of Hafnium Monochloride

Abstract

Intracavity laser spectroscopy has been applied for investigation of absorption spectrum of HfCl molecule. In the region 560–700 nm 59 bands have been obtained. Rotational structure analysis of 0–0 band indicated that Hund's case (c) of angular moment coupling applied to this molecule. The molecular constants (cm^?1) calculated for upper and ground electronic states are: ω′ = 353.05 cm^?1, ω″ = 379.65 cm^?1, B′=0.21486 cm^?1 B″ = 0.21801 cm^?1.     

Monitoring the Process of Crystallization and Determination of the Degree of Crystallinity of NaA Zeolites by Infrared Spectroscopy

Abstract

The course of crystallization and the degree of crystallinity of NaA zeolite, as well as its modified forms after treatment with HCl can be monitored by infrared cpectroscopy. As internal standard the band at 470cm^?1, due to vibrations in the SiO₄ tetrahedron may be used. During the crystallization process the amount of double fourfold rings (D4R) in the alumino-silicate gel increases which can be followed by the IR band at 560cm^?1. The ratio of intensity of this band and the one at 470cm^?1 increases in the course of crystallization.     

Raman Spectroscopic Study of the Copper Silicate Mineral Apachite Cu9Si10O29 · 11H2O

ABSTRACT

Apachite, Cu₉Si₁₀O₂₉ · 11H₂O, is a mineral named after the American Indian Apache tribe. Raman and infrared spectroscopy have been used to characterize the molecular structure of apachite. The structure of the mineral shows disorder, which is reflected in the difficulty in obtaining quality Raman spectra. Raman spectroscopy clearly shows the presence of OH units in the apachite structure, which attests the formula to be not correct. Both Raman and infrared spectroscopy show the presence of water in the apachite structure. Different water molecules are present with different hydrogen bonding strengths. A suggested formula might be Cu₉Si₁₀O₂₃(OH)₁₂ · 5H₂O.

The Raman band at 967 cm^?1 is assigned to the –SiO₃ symmetrical stretching vibration and the bands at 997 and 1096 cm^?1 are assigned to the ν₃ –SiO₃ antisymmetric stretching vibrations. An intense Raman band at 673 cm^?1 with a shoulder at 663 cm^?1 is assigned to the ν₄ Si-O-Si bending modes. Raman spectroscopy complemented with infrared spectroscopy enabled a better understanding of the molecular structure of apachite.