Vibrational spectra of 3,5-dimethylpyrazole and deuterated derivatives

The infrared (IR) and Raman spectra of 3,5-dimethylpyrazole have been recorded in the vapor, liquid (melt and solution) and solid states. Two deuterated derivatives, C5H7N-ND and C5D7N-NH, were also studied in solid state and in solutions. Instrumental resolution was relatively low, 2.0 cm(-1) in the IR and approximately 2.7 cm(-1) in the Raman spectra. The solids are made of cyclic hydrogen-bonded trimers. These trimers, present also in chloroform and acetone solutions, give rise to characteristic high absorption IR spectra in the 3200-2500 cm(-1) region, related to Fermi resonance involving nu(NH) vibrations. Bands from trimers are not present in water solutions but these solutions show spectral features similar in several ways to those of the trimer, attributable to solvent-bonded complexes. Evidence of H-bonding interactions with the other solvents is also visible in the high-frequency region. The two very intense bands in the Raman spectra of the solids appearing at 115 and 82 cm(-1) in the parent compound are also connected with a trimer formation. To interpret the experimental data, ab initio computations of the harmonic vibrational frequencies and IR and Raman intensities were carried out using the Gaussian 94 program package after full optimization at the RHF/6-31G* level for the three monomeric compounds as well as for three models of the trimer, with C3h, C3 and C1 symmetry. The combined use of experiments and computations allow a firm assignment of most of the observed bands for all the systems. In general, the agreement between theory and experiment is very good, with the exception of the IR and Raman intensities of some transitions. Particularly noticeable is the failure of the theoretical calculation in accounting for the high intensity of the Raman bands of the solid about 115 and 82 cm(-1).     

Schwingungsspektren von As4S4 und As4Se4

Vibrational Spectra of As₄S₄ and As₄Se₄ The vibrational spectra of solid α- and β-As₄S₄ and the Raman spectrum of molten As₄S₄ have been recorded. The assignments of the frequencies are proposed mainly based on polarization data. The Raman melt spectra suggest that As₄S₄ molecules (symmetry D_2d) are retained in the molten state. A partial decomposition of the melt by prolonged laser irradiation was observed. The Raman spectrum of solid As₄Se₄ is presented and the frequencies are tentatively assigned to an As₄Se₄ molecule of the cradle type, possessing D_2d symmetry.     

The dissociation of fluoroaluminates in FLiNaK and CsF-KF molten mixtures: a Raman spectroscopic and solubility study

By using a new furnace design, M(3)AlF(6) (M = Na, K, Cs) and mixtures of small amounts of AlF(3) in FLiNaK (46.5 mol % LiF, 11.5 mol % NaF, 42 mol % KF) and CsF-KF eutectic have been investigated over a wide temperature range (25-1050 degrees C) by Raman spectroscopy. The peak positions and their relative intensities have been measured as a function of temperature. In FLiNaK, up to 750 degrees C, the bands shift gradually to lower wavenumbers, and their halfwidths increase in agreement with published data. However, it is shown from solubility measurements and Raman data that, in these conditions, the mixture is not totally molten and the spectra correspond mainly to AlF(6)(3-) in the solid state. When the mixture is completely molten, a new band appears clearly on the high-frequency side of the main band of the spectrum, and its intensity grows up when the temperature is increased. The present results are a clear confirmation of the dissociation of AlF(6)(3-) into AlF(5)(2-) and AlF(4)(-) that our study of the Raman bands of the fully melted systems MF-AlF(3) (M = Na, K, Li) previously suggested. On these systems, it is then important to know if the spectra belong mainly to solid or liquid fluoroaluminates before drawing any conclusion concerning the liquid phase structure.     

The molecular structure of 4-piperidinemethanol in gas,solutions, and solid state: spectral and theoretical investigations

Structural Chemistry - FT-IR (4000–400 cm) spectra of gaseous, solid 4-piperidinemethanol, and its solutions in tetrachloromethane and dichloromethane and Raman spectrum...     

Vibrational assignments and resonance Raman spectra of N,N′-ethylenebis(salycilideneiminato)copper(II)

The i.r. spectrum of N,N′-ethylenebis(salycilideneiminato)Cu(II) has been recorded from 4000 to 200 cm⁻¹; polarized i.r. spectra of single crystals have also been obtained. The Raman spectra of polycrystalline samples and solutions have been measured and the resonance behaviour of several Raman bands has been investigated. A detailed assignment of most of the fundamentals is proposed on the basis of the i.r. dichroism and Raman spectra. The origin of the resonance enhancement of some Raman lines is also discussed.     

Raman spectra from very concentrated aqueous NaOH and from wet and dry, solid, and anhydrous molten, LiOH, NaOH, and KOH

High-temperature, high-pressure Raman spectra were obtained from aqueous NaOH solutions up to 2NaOHH2O, with X(NaOH)=0.667 at 480 K. The spectra corresponding to the highest compositions, X(NaOH)> or =0.5, are dominated by H3O2-. An IR xi-function dispersion curve for aqueous NaOH, at 473 K and 1 kbar, calculated from the data of Franck and Charuel indicates that the OH- ion forms H3O2- by preferential H bonding with nonhydrogen-bonded OH groups. Raman spectra from wet to anhydrous, solid LiOH, NaOH, and KOH yield sharp, symmetric OH- stretching peaks at 3664, 3633, and 3596 cm(-1), respectively, plus water-related, i.e., H3O2-, peaks near LiOH, 3562 cm(-1), NaOH, 3596 cm(-1), and, KOH, 3500 cm(-1). Absence of H3O2- peaks from the solid assures that the corresponding melt is anhydrous. Raman spectra from the anhydrous melts yield OH- stretching peak frequencies: LiOH, 3614+/-4 cm(-1), 873 K; NaOH, 3610+/-2 cm(-1), 975 K; and, KOH, 3607+/-2 cm(-1), 773 K, but low-frequency asymmetry due to ion-pair interactions is present which is centered near 3550 cm(-1). The ion-pair-related asymmetry corresponds to the sole IR maximum near 3550 cm(-1) from anhydrous molten NaOH, at 623 K. Bose-Einstein correction of published low-frequency Raman data from molten LiOH revealed an acoustic phonon, near 205 cm(-1), related to restricted translation of OH- versus Li+, and an optical phonon, at 625 cm(-1) and tau approximately 0.05 ps, due to protonic precession and/or pendular motion. Strong H bonding between water and the O atom of OH- forms H3O2-, but the proton of OH- does not bond with H significantly. Large Raman bandwidths (aqueous solutions) are explained in terms of inhomogeneous broadening due to proton transfer in a double well. Vibrational assignments are presented for H3O2-.     

Poly(β-amino acid)s. IV. Synthesis and conformational properties of poly(α-isobutyl-L-aspartate)

Poly(α-isobutyl-L -aspartate) was prepared by the polycondensation reaction of p-nitrophenyl ester of α-isobutyl-L -aspartate and the conformation of the poly(β-amino acid) was investigated by X-ray diffraction, polarized infrared, circular dichroism (CD), optical rotatory dispersion (ORD), and NMR spectroscopy. α-Isobutyl β-p-nitrophenyl-L -aspartate hydrochloride and hydrobromide were used as monomers and dimethylformamide, chloroform, and chlorobenzene, as solvents. A high-molecular-weight polymer with [η] 1.0 dl/g (dichloroacetic acid, 25°C) was formed in the polymerization of the hydrochloride in chloroform at 25°C. The X-ray diagram and polarized infrared spectrum of the stretched polymer film obtained from a chloroform solution suggested a cross-β-form as the most probable structure in the solid state. The CD spectra of the polymer in a 2,2,2-trifluoroethanol (TFE) solution and its film cast from the solution showed a peak at 205 nm and a trough at 190 nm which were assigned to a β-structure. The polymer was associated in chloroform. The NMR and ORD spectra in chloroform were similar to those in TFE, which suggests that the polymer also exists in the β-structure in chloroform. The addition of small amounts of dichloroacetic acid and sulfuric acid to chloroform and TFE solutions, respectively, destroyed the β-structure. A random copolymer of α-isobutyl-L -aspartate with β-alanine was also prepared by polycondensation reaction. The copolymer apparently did not form an ordered structure in the solid state or in solution.     

The conformations and vibrational spectra of 2,2,4,4,6,6,9,9-octamethyl-3,7-decadiyne

The IR spectra of the title compound as a solute in various solvents, as a melt and as a crystalline solid have been recorded. Raman spectra of the solutions, the melt and of the crystalline solid were obtained and semiquantitative polarization measurements carried out.The data have been interpreted in terms of one conformer (anti) present in the crystal. In the melt and in solutions an additional conformer (gauche) was present in low abundance, probably between 5 and 10%, and ΔH^o (gauche → anti) was estimated to be −7.9 ± 2 kJ mol⁻¹. Spectral correlations with the related molecule, 1,5-hexadiyne are pointed out.     

Raman spectra of complexes of HNO3 and NO3- with NO2 at surfaces and with N2O4 in solution

Raman spectra of HNO(3).NO(2) have been detected on liquid and solid surfaces in the presence of concentrated HNO(3) and NO(2) gas. The Raman spectrum of HNO(3) solutions containing N(2)O(4) has been partly reinterpreted in terms of contributions from HNO(3).N(2)O(4) and N(2)O(4).NO(3)(-) complexes.     

Conformational analysis,barriers to internal rotation and vibrational assignment for dimethylethylamine

The IR (50–3500 cm^?1) and Raman (20–3500 cm^?1) spectra have been recorded for gaseous and solid dimethylethylamine. Additionally, the Raman spectrum of the liquid has been recorded and qualitative depolarization values have been obtained. Due to the fact that three distinct Raman lines disappear on going from the fluid phases to the solid state, it is concluded that the molecule exists as a mixture of the gauche and trans conformers in the fluid phases with the gauche conformer being more stable and the only one present in the spectra of the unannealed solid. From the temperature study of the Raman spectrum of the liquid a rough estimate of 3.9 kcal mol^?1 has been obtained for ΔH. Relying mainly on group frequencies and relative intensities of the IR and Raman lines, a complete vibrational assignment is proposed for the gauche conformer. The potential functions for the three methyl rotors have been obtained, and the barriers to internal rotation for the two CH₃ rotors attached to the nitrogen atom have been calculated to be 3.51 and 3.43 kcal mol^?1, whereas the barrier for the CH₃ rotor of the ethyl group has been calculated to be 3.71 kcal mol^?1. The asymmetric torsional mode for the gauche conformer has been observed in both the IR and Raman spectra of the gas at 105 cm^?1 with at least one hot band at a lower frequency. Since the corresponding mode has not been observed for the trans conformer, it is not possible to obtain the potential function for the asymmetric rotation although estimates on the magnitudes of some of the terms have been made. Significant changes occur in the low-frequency IR and Raman spectra of the solid with repeated annealing; several possible reasons for these changes are discussed and one possible explanation is that a conformational change is taking place in the solid where the trans form is stabilized by crystal packing forces. These results are compared to the corresponding quantities for some similar amines.     

Matrix-isolated Al2OF6(2-) ion in molten and solid LiF/NaF/KF

A Raman spectrum consistent with that expected from an Al2OF6(2-) ion was observed when Na2O was dissolved in a eutectic LiF/NaF/KF (FLINAK) melt at 500 degrees C, which contained a low concentration of either AlF3 or Na3AlF6. Furthermore, it was possible to trap the Al2OF6(2-) ion in the frozen solid and to measure its Raman and IR spectra at 25 degrees C. A number of bands have been detected; among those, the two most characteristic bands of the Al2OF6(2-) ion at 494 (polarized) and 265 cm-1 in the FLINAK melt at 500 degrees C, and those at 509 and 268 (Raman) and approximately 780 to approximately 900 (IR) cm-1 for the compound matrix isolated in solid FLINAK at 25 degrees C. In the absence of added oxide, the dissolved aluminum fluoride was in the form of the octahedral AlF6(3-) ion, which has characteristic Raman bands at 542 and 325 cm-1 in the FLINAK melt at 500 degrees C. Whereas alumina, Al2O3, was found to be essentially insoluble in FLINAK melts, it was possible to dissolve sufficient amounts of Na2O to convert most of the AlF6(3-) to the oxyfluoroaluminate, Al2OF6(2-). These solutions appeared to be metastable with respect to formation of insoluble alumina at higher temperatures. The present results can be compared to previous measurements on alumina dissolved in pure molten cryolite at much higher temperatures, where alumina solubility is low and broad bands due to oxide species are difficult to detect due to overlap with bands from AlF6(3-) and AlF4-.     

Structural Properties of Glass-Forming Ethanol and Glycerol From O–H Vibrational Spectra

The O–H stretching vibrations of hydrogen-bonded glass formers (ethanol and glycerol) are studied by Raman scattering in a temperature range where the liquid state changes from low-viscous to solid. Several characteristic bands exhibiting different temperature behavior can be distinguished in the O–H vibrational spectrum of ethanol. The appearance of an additional band on cooling ethanol below 220 K is related to the appearance of locally favored structures. No notable manifestations of these features are detected in the spectra of glycerol.     

Vibrational spectra of molten and aqueous NaClO3 and KClO3

Raman spectra of molten NaClO₃ and KClO₃ and of aqueous solutions of these salts were measured over the frequency interval from 50 to 1200 cm⁻¹|. Infrared emission spectra of the molten chlorates and of chlorate-nitrate mixtures were recorded, and absorption spectra of aqueous sodium and potassium chlorate also were determined. The ν₃(e) and ν₄(e) modes of ClO⁻₃ were split in the molten salt and aqueous solution spectra, and a single, weak band was observed between ca. 80 and 200 cm⁻ in the Raman spectra of molten NaClO₃ and KClO₃.     

Resonance Raman intensity analysis of the A band short-time photochemical dynamics of 4,5-ethylenedithio-1,3-dithiole-2-thione

Resonance Raman spectra (RRs) for 4,5-ethylenedithio-1,3-dithiole-2-thione (EDDT) were obtained with 397.9 and 416 nm excitation wavelengths, and density functional calculations were performed to elucidate the electronic transitions and the RRs of EDDT in chloroform solvent. The RRs indicate that the Franck-Condon region photodynamics have multidimensional character with nuclear motion predominantly along the C(4)═C(5) stretch and the C(4)═C(5) twist out-of-plane. Resonance Raman cross-sections of A-band absorption have been obtained for the vibrational modes of EDDT with its excitation frequencies spanning the 408 nm. Resonance Raman intensity analysis of the resulting RRs excitation profiles and absorption spectrum using a time-dependent wave packet formalism yields mode-specific nuclear displacement and vibrational reorganizational energies. The intensity analysis results for EDDT were compared to previously reported results for dimethyl 1,3-dithiole-2-thione-4,5-dicarboxylate (DDTD), which shows that the additional six-member heterocycle of EDDT strongly affects the reorganizational energy and energy participation. The authors briefly discuss the differences and similarities of the spectra in terms of molecular symmetry and electron density.     

A study of DFT and surface enhanced Raman scattering in silver colloids for thymine

The vibrational spectrum of crystal thymine is calculated by density functional theory (DFT) at the B3LYP complex function. Considering the effect of intermolecular H-bonds, we add two water molecules that can form H-bonds with the CO and NH groups of thymine. The experimental spectra of normal Raman of thymine in solid state and surface enhanced Raman (SERS) of thymine adsorbed in silver colloids are presented in this study. The calculated Raman spectrum of thymine by DFT is in agreement with the experimental result of normal Raman spectrum. The appearance of new bands of thymine in SERS shows that molecules of thymine are adsorbed in the surface of silver nanoparticles with a perpendicular orientation through an oxygen atom (O7).     

Darstellung und spektroskopische Eigenschaften von Nitridophthalocyaninatorhenium(V)

Preparation and Spectroscopical Properties of Nitridophthalocyaninatorhenium(V) Nitridophthalocyaninatorhenium(V) ([ReNPc^2?]) is prepared by the reaction of dirheniumheptoxide with ammoniumiodide in molten 1,2-dicyano-benzene. The diamagnetic complex is chemically und thermically extremely stable. In the Uv-vis spectra the typical π-π*-transitions of the Pc^2? ligand are observed. Extra bands in the solid state spectrum are due to strong excitonic coupling of ca. 2.8 kK. In the resonance Raman spectra the intensity of the Re≡N stretching vibration (v(Re≡N)) at 969 cm^?1 is selectively enhanced by laser excitations above 19.0 kK. v(Re≡N) is a dominant m.i.r. absorption at 976 cm^?1.     

Polarized Raman Spectra VII Correlations and Assignments of Raman Lines in p-Polyphenyls

The Raman spectra of powdered biphenyl, p-terphenyl, and p-quaterphenyl are compared with each other and also with the Raman spectrum of benzene. Most Raman lines in polyphenyls can be considered as derived from normal vibrations in benzene. The intense lines are thus assigned and the correlations between them are established.     

Electronic, infrared, and Raman spectral studies of the reaction of iodine with 4-aminopyridine

The reaction of iodine as an electron acceptor with the base 4-aminopyridine (4APY) has been investigated spectrophotometrically in chloroform at room temperature. The electronic absorptions, infrared and Raman spectra, photometric titration as well as elemental analysis of the obtained iodine complex indicate the formation of the pentaiodide charge-transfer complex with the general formula [(4APY)(2)](+)I(5)(-). The characteristic strong absorptions of I(5)(-) are observed around 380 and 295 nm. Far infrared and Raman spectra of the solid complex show the vibrations of the linear I(5)(-) ion with D(infinityh) symmetry at 154, 104 and 89 cm(-1) assigned to nu(s)(I--I), outer bonds, nu(s)(I--I), inner bonds and nu(as)(I--I) inner bonds, respectively.     

Raman scattering study of polyaminopropylsiloxane and its compounds for characterization of 3-aminopropylsilane-modified silica gel. Utility of the CH2 rock and skeletal stretch modes

 The Raman scattering spectra for polyaminopropylsiloxane (poly-APS) samples in the solid state and in aqueous solution and for the related compounds, γ-aminobutyric acid (GABA) and its hydrochloride salt (GABA ⋅ HCl), have been examined in the CH₂ rock and skeletal stretch region. The Raman spectrum of the solid poly-APS sample may be accounted for by direct combination of the Raman spectra for GABA and GABA ⋅ HCl, whose crystal structures have been elucidated by a single-crystal X-ray diffraction study, suggesting that the APS segments of poly-APS in the solid state are in a conformationally ordered state. It has also been found that the Raman spectra of the solid and aqueous poly-APS samples in this region are useful for diagnosing the conformations of APS moieties bound onto the surface of silica gel. Received: 18 September 1996 Accepted: 2 December 1996     

Non-resonance micro-Raman spectroscopic studies on crystalline domoic acid and its aqueous solutions

Domoic acid (DA) is a neurotoxin naturally present in the marine ecosystem. Since DA's toxicity has been explained by its molecular structure and particularly because of its ethylenic double bond, spectroscopic investigation of this molecule is of importance. We carried out Raman spectroscopy on crystalline DA and on DA in aqueous solutions (28,000-25 ng DA/mL) and assigned Raman modes in comparison with the Raman spectra of its substructures. Noise-free, clear Raman signal from the solutions containing low concentrations of DA were obtained by applying the drop coating deposition Raman (DCDR) technique. Raman spectra reveal that crystalline DA exists in the zwitterionic form. The Raman spectra of the DA aqueous solutions were analysed in the light of their pH whereas the variation in the spectra was attributed to the hydration, the degree of protonation and crystallinity of the solid film. We show that DCDR can be applied for the rapid detection of domoic acid down to 25 ng DA/mL (0.025 ppm).