Formation of Metallophthalocyanine Trimers in Liquid Solutions

For solutions of the complexes of phthalocyanine (PhC) with magnesium (Mg-PhC) and of tetrachloromethyl-PhC with zinc (Zn-PhCCh) in mixtures of glycerin with dimethyl formamide (DMF) and for Zn-PhCCh in toluene and DMF it has been found that the electron absorption spectra substantially depend on the substance concentration. It is shown that these changes are attributable to the association of the molecules of pigments. The number of molecules in the associates and the equilibrium constants for this association are determined. The formation of the trimers of Mg-PhC in binary solutions and the dimers of Zn-PhCCh in toluene, DNF, and binary solutions has been established. It has been found that on association the Q absorption bands of the pigments shift to shorter wavelengths as compared to the bands of the monomers. For the Mg-PhC trimers, the shift is = 1410 cm^–1, while for the Zn-PhCCh dimers it is 990 cm^–1 in toluene, 930 cm^–1 in DMF, and 925 cm^–1 in the mixture of DMF with glycerin. It is concluded that the structure of the trimers and dimers is of the type of a stack in which molecules are arranged in parallel one above the other at a distance of 3.5 to 4.0 Å between the planes of the molecules. In association, the fluorescence intensity of the pigments decreases substantially (the decrease corresponds to the decrease in the concentration of the monomer molecules of phthalocyanines), with the fluorescence spectra remaining unchanged. Consequently, the associates of the pigments do not display pronounced fluorescence.     

Infrared luminescence and vibronic coupling in ZnTe:Fe2+

Samples of crystalline ZnTe with different concentrations of iron were prepared by the vertical high-pressure Bridgman method. Absorption and emission spectra were recorded at liquid-helium temperature in the region of the⁵ T ₂(D)⁵ E(D) infrared transitions of substitutional Fe²⁺(d ⁶) ions. In the range between 2400 and 2520 cm^–1 a rich structure is observed showing more lines than predicted by plain crystal-field theory. The explanation of all these lines is found after introducing a vibronic Jahn-Teller term to the Hamiltonian. A linear coupling between the doubly degenerate vibrational mode to the electronic orbitals of the ionic multiplet⁵ D is added to the electronic and vibrational terms of the Hamiltonian. A diagonalization follows using just one free parameter: the Jahn-Teller energy representing the strength of the coupling. The corresponding value is 3 cm^–1, which is identical to the one already reported for CdTe Fe²⁺. The calculated spectrum is in good agreement with the one determined experimentally. Measurements of the absorption spectra support conclusions drawn earlier about a Jahn-Teller coupling also for the excited multiplet. Finally a prediction of how the far-infrared would look like is also given.     

Photophysical Processes in the Gas Phase at High Levels of Vibrational Excitation of Triplet Molecules of Benzophenone and Fluorenone

By the delayed fluorescence activated by direct multiphoton excitation of triplet molecules by CO₂–laser radiation we have studied the prevailing deactivation pathways of triplet molecules with a high store of vibrational energy E _vib. The dependences of the kinetic characteristics of delayed fluorescence on the presence of vapors and foreign gases have been used to estimate the rates and efficiencies of intermolecular vibrational relaxation in the vibrational quasi–continuum of the triplet state T ₁. By the changes in the intensities and decay rates over a wide range of vibrational energies we have established the E _vib dependences of reversible intercombination conversion between the states T ₁ and S ₁ and interconversion from T ₁ to the ground electronic state S ₀ for both the case of isolated excited molecules and at a steady vibrational temperature. It is shown that at high vibrational temperatures the radiationless transition from the T ₁ state to S ₀ has an activation character and is accomplished through the energy barrier. The conditions for going to an exponential dependence have been determined. It has been found that the obtained dependences are in good agreement with the known experimental results. The influence of molecular and environmental characteristics on the decay rate of triplet molecules is compared.     

Photoinduced Oxidation of Diphenylbisanthene and Its Spectral Manifestations

The absorption and fluorescence spectra of diphenylbisanthene (DPB) in n-octane and benzene at 300 and 77 K have been investigated. The appreciable Stokes shift of the fluorescence band (180 cm^–1 in n-octane and 440 cm^–1 in benzene) points to the nonplanar character of the aromatic skeleton of DPB, which has been confirmed by results of the optimization of the molecule geometry by the AMI quantum-mechanical method. It has been found that spectral manifestations of the products of photoinduced transformations of DPB molecules are observed in the UV region (200–350 nm), and it has been shown that the observed photochemical process is two orders of magnitude less effective than for diphenylhelianthrene. On the basis of the experimental data and the results of the quantum-chemical calculations of the electronic spectra of molecules of DPB and endoperoxides (ZINDO/S method), it has been concluded that the end products of DPB phototransformations are its endobiperoxides in which —O—O— groups are added to the phenyl-substituted benzene rings of the aromatic skeleton.     

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.     

Infrared absorption of silane,ammonia, acetylene and diborane in the range of the CO2 laser emission lines: Measurements and modelling

Absorption spectra of the gases SiH₄, NH₃, C₂H₂ and of SiH₄/Ar and SiH₄/B₂H₆ mixtures have been measured in the spectral range of the CO₂ laser from 9.2 to 10.8 µm. In agreement with literature, silane shows the highest absorption (absorption coefficient = 3.3 × 10^–2 Pa^–1 m^–1). The deviation of the measured absorption behaviour of silane from literature, as far as the pressure dependence is concerned, can be explained by the enhanced spectral energy density in our experiment. This is confirmed by a rate-equation model involving the basic mechanisms of V-V and V-T energy transfer between vibrationally excited silane molecules. In contrast to silane, the absorption coefficient of NH₃ at the 10P(20) laser line is 4.5 × 10^–4 Pa^–1 m^–1 atp = 20 kPa and has its maximum of 4.5 × 10^–3 Pa^–1 m^–1 at the 10R(6) laser line. For C₂H₂ and B₂H₆, is even less ( 2.1 Ò 10^–5 Pa^–1 m^–1 for C₂H₂).     

Influence of Vibrational Excitation of Triplet Molecules of Anthraquinone on the Photochemical Processes in Gas Mixtures with Amines

By the quenching of the delayed fluorescence (DF) of anthraquinone vapors by aliphatic amines (diethylamine, dibutylamine, cyclohexylamine) and pyridine the photoinduced processes proceeding with the participation of vibrationally excited triplet molecules of anthraquinone have been investigated. The DF quenchingrate constants K _q varying from 1·10⁶ sec^–1·torr^–1 in mixtures with diethylamine to 7·10³ sec^–1·torr^–1 in mixtures with pyridine have been estimated. A correlation between the values of K _q and the ionization potentials of foreign gases confirming the important role of interactions with charge transfer in the quenching of triplet molecules in the gas phase has been established. The influence of other relaxation processes on the DF quenching is considered. It is shown that the intermolecular vibrational relaxation in the T ₁ triplet state leading to the establishment of relaxation equilibrium at a vibrational temperature T _vib considerably increasing the medium temperature is the fastest process among the biomolecular processes (rate constants K _col ^V > 10⁶ sec^–1·torr^–1 > K _q). The values of T _vib and the vibrational energies E _vib of the triplet molecules after the energy exchange in the collisional complex have been estimated. It has been concluded that the photochemical reaction yield is determined by the intermolecular processes proceeding in the T ₁ state at a vibrational equilibrium characterized by high values of T _vib. The influence of E _vib of triplet molecules on the DF quenching rates at a photoinduced electron transfer is considered.     

Frequency Dependence of the Components of Dielectric Permeability and Characteristic Losses of Fluorite

The ₁(E), –Im^–1, and Re^–1 spectra of the fluorite crystal are calculated on the basis of the experimental (10–35 eV) and theoretical spectra ₂(E) (10–27 and 8–20 eV). They were employed to decompose the ₂(E) and –Im^–1 spectra into elementary components. The most intense transverse and longitudinal components of transitions and their parameters have been determined. The correlation between two types of components of transitions and their distinguishing features have been established.     

Population of the higher-lying vibrational levels of the nitrogen B3π state in a glow discharge

The absolute populations of the higher-lying vibrational levels of the B³ state of the nitrogen molecule in a glow discharge have been determined for pressures from 0.1 to 1.0 torr and current densities from 80 to 200 mA/cm². The absolute concentrations of molecules at levels v = 5, 6, ..., 12 under these conditions are of the order of 10⁹–10¹¹ cm^–3. The most probable processes leading to a population of the B³ state are thought to be direct electronic impact, cascade transitions, and collisions of normal molecules with molecules in the singlet state.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 2, pp. 57–63, February, 1971.     

Resonant Auger decay study of core-excited OCS

The present work aims at characterizing short-lived C1s⁽⁻¹⁾π^*(1) core-excited states of the OCS molecule based on the analysis of the vibrational fine structure and lineshape profiles of the high-resolution resonant Auger decay spectra recorded at the excitation energies along the C1s→π^* resonance in the binding energy region 15–19 eV. Very different behavior in terms of lineshape and resonant enhancement is observed for the , and final states. This is explained by (1) the variation in the C–O bond lengths for the states involved in the electronic relaxation and (2) different contributions in terms of Mulliken population to the molecular orbitals determining the electronic character of the corresponding states. Since the final-state geometries are known from a number of previous experiments and ab initio calculations, the geometry of the C1s⁽⁻¹⁾π^*(1) intermediate states can be predicted in analogy with e.g. the N₂, CO₂ and N₂O molecules.     

Frequency- and wavelength-modulation spectroscopies: Comparison of experimental methods using an AlGaAs diode laser

Low-wavelength modulation (1 kHz), high-wavelength modulation (100 MHz) and two-tone frequency modulation (390±5 MHz) spectroscopies are systematically compared by measuring the minimum detectable absorption achieved using an AlGaAs diode laser tuned on a third-overtone methane transition at 886 nm. From the S/N behavior has been extrapolated a minimum relative absorption (1 Hz of bandwidth) of 4.5(1)×10^–7 for the LMW, 9.7(3)×10^–8 for the HWM and 6.4(2)×10^–8 for the TTFM. In the LWM case the detection-limit value is represented by the laser amplitude 1/f excess noise, while for the high-frequency detection techniques this contribution is negligible with respect to other noise sources. These detection limits well agree with the calculated quantum limited values based on measured laser power, modulation index, noise figure of the electronic components, and other parameters of the apparatus.     

Estimation of the Optimum Concentration Interval of the Contents of Praseodymium, Neodymium, Europium, Holmium, and Erbium in a Solution

Based on the electronic absorption spectra of Pr³⁺, Nd³⁺, Eu³⁺, Ho³⁺, and Er³⁺ ions in 1 M aqueous solutions of chloric acid, calibration graphs have been constructed in a concentration of metals–optical density of a solution format for different frequencies. The band for praseodymium was used at 22,520 cm^–1, for neodymium at 17,380, 13,480, and 12,560 cm^–1, for europium at 25,380 cm^–1, for holmium at 18,580 and 15,580 cm^–1, and for erbium at 39,160, 26,480, and 19,160 cm^–1. The errors in determining the concentration of the indicated elements as a function of their content have been calculated. It is shown that for perchloric solutions of praseodymium it is possible to correctly determine its contents within the concentration range 0.1–1.5% at a frequency of 22,520 cm^–1; for neodymium the ranges are 0.4–1.0, 0.3–1.0, and 0.5–1.0% at 17,380, 13,480, and 12,560 cm^–1, respectively; for europium 0.4–1.5% at 25,380 cm^–1; for holmium — 0.2–1.5 and 0.4–1.5% at 15,580 and 18,580 cm^–1, and for erbium the range is 0.4–1.0% at frequencies of 39,160, 26,480, and 19,160 cm^–1.     

Optical studies on free-standing polypyrrole films by the photopyroelectric method

Optical spectra of free-standing polypyrrole films were investigated by a novel PhotoPyroElectric (PPE) method. The reflection and absorption spectra in the range 2000–25000 cm^–1 of TsO^–- and ClO ₄ ^su– -doped polypyrrole films were obtained with an experimental setup comprising two pyroelectric sensors. The absorption bands due to electronic transitions to the bonding and antibonding bipolaronic levels appear at 11 000 and 21 500 cm^–1, respectively. Some relevant details in the polypyrrole spectrum in the 2000–5000 cm^–1 range were observed. The absorption band located at 3400 cm^–1 is characteristic for NH stretching vibration. The bands in the 2300–2500 cm^–1 range are ascribed to the vibration of N⁺H groups containing positively charged nitrogen. The PPE spectra also reveal changes of the electronic and vibrational absorption bands after polymer reduction and HCl treatment.     

Calculation of the Spectroscopic Constants and Strength of the Electron Transition <Emphasis Type="Italic">A</Emphasis>0<Superscript>+</Superscript>-<Emphasis Type="Italic">X</Emphasis><Superscript>1</Superscript>Σ<Superscript>+</Superscript> of the AgAu Molecule

The vibrational, rotational, and centrifugal constants for the electronic states A and X ¹Σ⁺ of the AgAu molecule have been calculated. The calculation is based on the Morse potential functions that were used to approximate the real potential curves of the ground and excited states of AgAu. Using the experimental data on the lifetime of the vibrational levels of the excited electronic state, the strength of the A-X transition was calculated.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 176–180, March–April, 2005     

Structural phase transition and internal fields in rubidium thiocyanate probed through vibrational spectroscopy

A comprehensive vibrational study of Rubidium thiocyanate (RbNCS), in the 298–448°K range reveals that the orthorhombic to tetragonal transition atT _c440°K is of order-disorder type exhibiting purely second order characteristics. A consistent order-parameter exponent 0.45±0.04 has been obtained from both Raman and IR measurements. In the Raman spectra, the appearance of sidebands in both the C–N&C–S stretching modes and their temperature dependence indicate the existence and a gradual diminution of internal electric field asT approachesT _c. These results have been discussed in the context of an anharmonic oscillator model. An activation energy (U) for the reorientational motion of NCS^– ions,U0.29±0.02 eV, has been calculated from large changes in the bandwidth (_C-N) nearT _c.     

Analysis of the High-Resolution Infrared Spectrum of the PHD2 Molecule: ν1 and 2ν1 Bands

The results of investigation into the infrared spectra of the PHD₂ molecule including the ₁ fundamental band centered at 2324.005 cm^–1 (with a resolution of 4.2·10^–3 cm^–1) and the first 2₁ valence overtone centered at 4563.634 cm^–1 (with a resolution of 8.8·10^–3 cm^–1) are given in the present paper. Based on an analysis of the results obtained, 1340 and 1020 lines are referred to the ₁ and 2₁ bands, respectively. This data are used to calculate 316 and 248 vibrational-rotational energies of the (100000) and (200000) excited vibrational states, respectively. Since both bands can be considered as isolated, we take advantage of the Watson Hamiltonian (the reduction A in the I ^r representation) to describe their rotational structure. The calculated spectroscopic parameters of the examined states of the PHD₂ molecule correlate well with each other and with the corresponding parameters of the ground vibrational state.     

Electronic absorption in silicate mineral of copper

The electronic absorption spectrum of chrysocolla, a silicate mineral of copper, has been studied at room and liquid air temperatures. The observed bands were satisfactorily explained as belonging to Cu²⁺ ion subjected to tetragonal and spin-orbit fields. A good fit between the theoretical and observed band positions was obtained for the following crystal field parameters:Dq=–1400 cm^–1 Ds=–3000 cm^–1 Dt=–800 cm^–1 =–800 cm^–1     

Spectral‐Luminescent Properties of Oxazoles and Oxadiazoles in a Gas Phase on Excitation by Electrons

The energyloss spectra of electrons, fluorescence excitation functions, and the fluorescence spectra on excitation of the vapors of a number of oxazoles and oxadiazoles by monokinetic beams of electrons of various energies are determined. In contrast to optical absorption spectra, in the energyloss spectra of a number of studied substances a band associated with the S ₀–T ₁ singlettriplet transition is observed. The –^*type transitions are fixed up to S ₀–S ₅ on excitation of molecules by highenergy electrons, including the region of vacuum ultraviolet. The cross sections of elastic and inelastic collisions of electrons of different energies with POPOP molecules have been measured. The dependences obtained differ substantially from those calculated in the Born approximation. The cross section of elastic scattering is in a rather good correspondence with the geometric section of the molecule.     

IR Spectra and Structure of Immunoactive 8–Azasteroids in Model Compounds

The IR spectra of biologically active molecules of 8-azasteroids and model compounds in the region of C=O, C=C, C--N, and C--H vibrations (1800–1400 cm^–1) have been studied in detail. The structure of compounds containing isostructural and isoelectronic --acyl----aminovinylcarbonyl and --acyl----alkoxyvinylcarbonyl fragments have been analyzed. Interpretation of the structure of the IR spectra and of the specificity of the manifestation of the vibrational modes under consideration in the molecules of a particular class of 8-azasteroids is given. The electronic structure of the molecules under investigation complies with the model of mesomeric tautomerism of the aminovinyldicarbonyl fragment.     

An experimental study and computation of the infrared absorption spectrum of 3,5-dimethyl-4-phenylpyridine

The infrared absorption spectrum of 3,5-dimethyl-4-phenylpyridine in the 400–2000 cm^–1 range was obtained. A valence-force model was used to compute the fundamental frequencies and normal vibrational modes. The experimental and computed data were found to be in good agreement. The addition of two methyl groups in the 3,5-positions of the-phenylpyridine molecule reduces conjugation between the benzene and pyridine rings, rendering the molecule noncoplanar. The free rotation of the methyl groups about the C-C bond is retarded by the free electron pair in the nitrogen atom of the pyridine ring.