Nonequivalence of NH Bonds in the Amino Group of Aminotoluenes in Complexes of Various Compositions

The association of aminotoluenes with different proton acceptors in CCl₄ was studied in the temperature range 290–330 K on the basis of IR absorption spectra in the region of the amino group stretching vibrations. It is found that the location of the maximum, halfwidth, and integrated intensity of the absorption bands (NH) of monomers and H-bonded complexes depend almost linearly on temperature. It is shown that in the 1:1 complexes the hydrogen bonding is more stable than in the 1:2 complexes.     

A Spectroscopic Study of Thermodynamic Characteristics of Hydrogen-Bond Complexes of Dichloroanilines with Proton Acceptors

The association of dichloroanilines with different proton acceptors in CCl₄ in the temperature range 290–330 K is studied using the IR absorption spectra in the region of stretching vibrations of an amino group. It is found that the position of maximum, halfwidth, and integral intensity of the (NH) absorbtion bands of free and H-bond molecules change almost linearly within the temperature range studied. The temperature dependence of constants of the equilibrium monomer – complex is examined, and thermodynamic characteristics of the complexes are calculated.     

Quantitative Analysis by Derivative Electronic Spectroscopy

Abstract

Absorption and emission spectroscopy in the ultraviolet and visible regions, apart from being the earliest physical techniques of analysis, have great utility in solving a variety of structural and analytical problems [l-41. However, in many cases the quantitative determination of individual components in a mixture by UV-VIS spectroscopy becomes very difficult owing to the spectral similarities and overlapping of weak absorption bands of one component by strong absorption bands of other components. It was recently recognized that derivative spectrophotometry, introduced about three decades ago [5-81 and originally proposed by Rutherford [9], can be a very useful analytical tool for characterizing an analyte band that is overlapped by other absorption bands with different halfwidths. On differentiation, the intensity of the absorption band with a small halfwidth increases more than that of a band with a large halfwidth [10]. The central idea behind the development of the science of derivatized spectra rests upon the measurement of the first or the higher derivatives of the absorbance A or the luminescence intensity I with respect to the wavelength λ, e.g., dI/dλ, dA/dλ, d²I/dλ², etc. These derivatives, when plotted or scanned against wavelength, yield an array of derivative spectra.     

Modeling of IR Spectra of Selectively Substituted Glucopyranoside Nitrates

The frequencies of the normal vibrations of the molecules of 2,6- and 3,6-di-O-nitro-methyl--D-glucopyranosides and 2,3,6-tri-O-nitro-methyl--D-glucopyranoside have been calculated within the valence-force-field approximation in combination with calculation of the absolute intensities of the IR absorption bands of these molecules by the CNDO/2 method. The regularities in the structure of the complex IR absorption bands characteristic for nitro groups formed as a result of selective nitrosubstitution have been explained.     

Role of Intermolecular Interactions in Forming the Vibrational Spectra of Carbohydrate Nitrate Crystals in the Region 1600–1700 cm−1

To elucidate the role of intermolecular interactions in forming the vibrational spectra of the crystals of carbohydrate nitrates in the region 1600–1700 cm^–1, theoretical calculations are performed (in the approximation of an additive model of interatomic interactions with the use of the Green's functions) for the density of vibrational states and the intensity of absorption bands in the IR spectrum of a methyl--D-glucopyranoside tetranitrate molecule in a crystal. It is shown that the splitting of absorption bands in the IR spectral region under consideration relates to the crystal effect.     

Analysis of the Structure of the Bands in the IR Spectrum of β-D Glucose by the Regularized Method of Deconvolution

Deconvolution of the IR absorption spectrum of -D glucose in the spectral range 1500–450 cm^–1 has been carried out. The results of the deconvolution were compared with the IR and Raman spectra recorded at room and low temperatures and with the data obtained by theoretical calculations for the frequencies of the normal vibrations of the -D glucose molecule in the crystalline state. It is shown that deconvolution of the IR spectra recorded at room temperature makes it possible to separate the bands observed experimentally only at a very low temperature of the sample and a number of components that were not resolved earlier. The number of bands separated on deconvolution of the IR spectra of -D glucose in the spectral range 1500–450 cm^–1 is more than twice the number of visible absorption maxima in the usual spectrum. The results of deconvolution of the IR spectrum of -D glucose are in good agreement with the data of theoretical calculations for the frequencies of the normal vibrations of the -D glucose molecule in the crystalline state. The existence of the factor-group (Davydov) splitting of a number of frequencies of the nondegenerate fundamental vibrations of molecules in a crystal cell has been revealed in the IR spectrum of -D glucose. It was concluded that the model of an isolated molecule is insufficient for detailed theoretical interpretation of the vibrational spectra of carbohydrates.     

IR Spectra of Derivatives of Immunotropic 8-Azasteroids

By the method of IR Fourier spectroscopy with the use of numerical differentiation of spectral line profiles we have studied the spectra of some structural and functional derivatives of immunotropic 8-azasteroids in the region of C=O and C=C bonds (1800–1400 cm^–1). We have established the dependence of vibration frequencies of the C=O and C=C groups on the size of the ring D, the presence of heteroatoms (O, S) in the ring D, transformations in the -acyl--aminovinylcarbonyl fragment and in its adjacent positions of the heterosteroid skeleton, and the composite character of the absorption bands that are due to the vibrations of the C=O and C=C groups. The role of the structural and stereoelectronic factors in the observed group frequencies of 8-azasteroids is discussed.     

Spectra and structure of hydroxycoumarin and hydroxyfurocoumarin salts

The sodium salts of 4-hydroxycoumarin, 5-hydroxy[2, 37, 6-furo]coumarin (bergaptol), 6-dyroxycoumarin, 7-hydroxycoumarin (umbelliferone) and 8-hydroxy[2, 37, 6-furo]coumarin (santhotoxol) have been prepared and their IR and UV spectra determined. The position and intensity of the IR absorption bands of these salts (both in the crystalline state and in D₂O solution) show that the ions of 7-hydroxycoumarin, 5-hydroxyfurocoumarin, and 5-hydroxycoumarin exist in a form intermediate between quinoid and coumarin, and the ions of 6-hydroxycoumarin and 8-hydroxyfurocoumarin exist as coumarins.In conclusion we thank G. K. Nikonov and Zh. A. Manaeva for the kind gift of the hydroxycoumarins and hydroxyfurocoumarins.     

Absorption Spectra of Pentamers of Tetrapyrrole Compounds in Aqueous Solutions

Pentamers of two types have been obtained in aqueous solutions containing mixtures of two tetrapyrrole compounds, in whose molecules there are positively or negatively charged peripheral groups. The pentamers of one type include one molecule of mesotetra(4Nmethylpyridyl) porphin (TMPP) and four molecules of the complex of mesomono(nsulfophenyl)etioporphyrin II with palladium (PdSPhEP), and the pentamers of the other type include one molecule of sulfonated phthalocyanine (PCS) and four molecules of TMPP. The absorption bands of the pentamers are broadened and shifted toward longer wavelengths in comparison with the bands obtained as a result of the addition of the spectra of the monomers. It seems that the changes in the absorption spectra are first of all due to the change in the interaction of the molecules of the pigments with the molecules of the surrounding in formation of associates and due to the influence of the resonance dipoledipole interaction between the molecules in the associates. The influence of the intermolecular photoinduced charge transfer is also possible (it is most probable for the associates with PCS). We have revealed an effective quenching of the fluorescence of PCS and TMPP solutions upon heteroassociation.     

Effect of the Pyranose Ring Conformation on the Vibrational Spectra of Sugar Epoxides

Normal vibrations of two sugar epoxides — methyl 2,3-anhydro-4-deoxy--D-ribohexopyranoside and methyl 3,4-anhydro--D-talohexopyranoside — have been carried out by the molecular mechanics method. Parametrization of the force field used has been performed and the parameters of the oxirane ring for sugar epoxides have been determined. A good agreement between the experimentally observed and calculated frequencies has been obtained. The IR spectral absorption bands of the molecules under investigation in the 1500–400-cm^–1 range have been assigned on the basis of the potential energy distribution function of normal vibrations. The investigation of the potential energy surface of these molecules has shown that their pyranose ring can take conformations close to half-chair, boat, skew boat, and twist forms. Comparative analysis of the normal vibrations of various conformers has revealed that the form of the pyranose ring influences the vibrational spectra of sugar epoxides.     

Synthesis and Spectroscopic Studies of 3-(3 N-Arylidenehydrazino-1,2,4-triazol-5-yl)-coumarins and Their Biological Activities

The electronic absorption spectra of 3-(3 N-arylidenehydrazino-1,2,4-triazol-5-yl) coumarin III are investigated in organic solvents of varying polarities and buffer solutions of different PH. The behaviour of the latter is utilized in calculating pka values of these compounds. The important bands in the IR spectra and the main ¹H NMR signals are assigned and discussed in relation to molecular structure. The antimicrobial activity of these compound has been investigated.     

Diffuse Reflectance Spectra of Rare Earth Benzoylacetonates in Ultraviolet region

Rare earth β-diketonates are promising laser materials. Their solid state spectra is expected to give their spectral characteristics. The diffuse reflectance spectra of some rare earth β-diketonates and esters in ultraviolet region have been reported recently by the authors¹. The ultraviolet absorption spectra of transition metal chelates have also been reported^2,3 recently. The spectra of the non-transition metal ion chelates usually consist⁴ only of the metal charge transfer and ligand intramolecular transitions. The ligand transitions in all the cases are characteristic of the coordinated ligand. The spectrum of the ligand, however, helps in assigning the transitions of the co-ordinated ligand. A comparison of the spectrum of ligands and their rare earth complexes^1,5,6 shows that on complexation no new bands appear in ultraviolet suggesting that unlike transition metal β-diketonates^2,3, charge transfer bands do not appear in the present case. The ligand intramolecular transitions are expected mainly due to the carbonyl group.     

Spectra of complexes of Tb with aromatic monocarboxylic and dicarboxylic acids

Absorption and emission (⁵D₄⁷F₅) spectra are reported for these complexes in methanol at room temperature. The effects of substitutents on the bands are discussed.We are indebted to A. A. Petrov for direction and for valuable comments.     

Magnetic Circular Dichroism Spectra of p-Disubstituted Benzenes Possessing Both Electron-Donating and Accepting Groups

Abstract

The magnetic circular dichroism (MCD) and absorption spectra of some p-disubstituted benzenes possessing both electron-donating and accepting groups were measured. The electronic spectra of the above compounds are characterized by the appearance of two absorption bands, one of which appears at 25000–40000 cm^?1 region with large intensity, and another at 40000–50000 cm^?1 region with rather small intensity. These absorption bands, especially the latter one, have been investigated by means of the MCD spectra and molecular orbital calculations based on the Pariser-Parr-Pople method.     

Effect of pressure on the intensity of absorption bands in the IR spectra of compacted polyethylene powde

The investigation of the IR spectra of compacted reactor powders of ultra-high-molecular-weight polyethylene showed that the intensities of the absorption bands depend on the compaction pressure; namely, they decrease with increasing pressure. It is found that the ultimate pressure above which the absorption band intensity ceases to decrease depends on the spectral position of the band; the shorter the wavelength, the higher the ultimate pressure. This pressure is 5–10 MPa for bands in the long-wavelength spectral region (the band at 720 cm^?1) and 100 MPa for the short-wavelength region (the band at 5875 cm^?1). It is assumed that this phenomenon is related to a change in the size of pores d with pressing. Beams with wavelengths λ < d will undergo multiple diffuse reflections and reach a photodetector that is weaker than beams with λ > d. With increasing pressure, the size of pores decreases and the boundary between the two regions of the spectra shifts to short wavelengths.     

A spectroscopic investigation of the conformational equilibrium of methyl cyclohexane

The vibrational spectra of the axial and equatorial conformations of methyl cyclohexane were computed. The temperature variation of the relative intensity of the 607 (axial) and 547 (equatorial) cm^–1 IR absorption bands were were used to determine H for the liquid and vapor. The IR spectrum at the liquid-vapor transition was investigated.In conclusion, the authors express their sincere gratitude to Z. I. Kaganov for his assistance in the computations and to V. T. Alekxanyan for his useful comments.     

Charge-transfer bands in crystals of alkaline earth fluorides with Eu<Superscript>3+</Superscript> and Yb<Superscript>3 + 1</Superscript>

The absorption, luminescence, and excitation spectra of CaF₂, SrF₂, and BaF₂ crystals with EuF₃ or YbF₃ impurity have been investigated in the range 1–12 eV. In all cases, strong wide absorption bands (denoted as CT₁) were observed at energies below the 4f ⁿ -4f ^{n ? 1}5d absorption threshold of impurity ions. Weaker absorption bands (denoted as CT₂) with energies 1.5–2 eV lower than those of the CT₁ bands have been found in the spectra of CaF₂ and SrF₂ crystals with EuF₃ or YbF₃ impurities. The fine structure of the luminescence spectra of CaF₂ crystals with EuF₃ impurities has been investigated under excitation in the CT bands. Under excitation in the CT₁ band, several Eu centers were observed in the following luminescence spectra: C _4v , O _h , and R aggregates. Excitation in the CT₂ bands revealed luminescence of only C _4v defects.     

Optical Spectra of Residual Porous Silicon

The spectra of absorption (), reflection (R), ₂, and E ²₂ of residual silicon (r-Si) were calculated using the R spectra of porous silicon in the range from 0 to 20 eV and with ₂(E) in the range 2.5–5.0 eV of porous silicon specimens with P = 0.57, 0.66, and 0.77. The ₂ spectra of r-Si were decomposed into elemental components. We calculated their main parameters: the energies of maxima E _i and halfwidths H _i of bands, their areas S _i , and heights I _i , and oscillator strengths f _i . The two-phase Bruggeman model of effective dielectric function and Kramers–Kronig analysis were applied in the calculations. The essential differences between the optical spectra of the residual and cubic silicon were established. They are at least partially attributed to the quantum dimensional effects. The data obtained are compared with the known theoretical spectra of silicon clusters.     

Infrared spectroscopy of ICAO taggants

The IR absorption spectra of the ICAO taggants, ethylene glycol dinitrate (EGDN), o-mononitrotoluene (2-NT), p-mononitrotoluene (4-NT) and 2,3-dimethyl-2,3-dinitrobutane (DMDNB) in the vapor phase, are studied at room temperature over a wide frequency range (500–4000 cm^–1). The pre-assignment of the observed vibrational bands was performed. Modern quantum-chemical methods are applied to calculate the equilibrium geometries of these molecules and the frequencies of their fundamental vibrations. For the most intense bands of 2-NT and 4-NT, the absorption cross sections are estimated. Based on analysis of current laser technology, it has been concluded that their use in conjunction with the available spectroscopic data makes it possible to reliably perform local and remote detection and identification of ICAO taggants in an open atmosphere in real time.