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.     

Spectrophotometric Determination of Sm(III) Content in Hydrochloric Acid Solution

On the basis of the electronic absorption spectra of Sm³⁺ ions in aqueous solutions of hydrochloric and perchloric acids (1M) calibration plots of samarium content against the optical density of the solutions have been constructed for frequencies 47,800, 31,460, 29,140, 27,760, 26,740, 24,940, 24,020, 21,580, and 20,900 cm^–1 corresponding to the optical density maxima. The results of the calculation of errors in determining the metal concentration are presented. It has been shown that for hydrochloric acid solutions of samarium correct determination of its content is possible at frequencies 24,940, 21,580, and 20,900 cm^–1 in the concentration ranges 1.0–3.5, 2.5–5.0, and 0.08–5.00%, respectively. For perchloric acid solutions of samarium, correct determination of its content is possible at the 24,940 cm^–1 frequency in the concentration range from 1.0 to 3.5%.     

Shift Coefficients and Self-Pressure Broadening of H2 16O Lines in the Range 1950–2750 cm−1

Experimental values of the shift coefficient and self-pressure broadening by the own pressure have been determined for some spectral lines of water vapor in the range 1950–2750 cm^–1. A comparison with the calculated data obtained on the basis of the Robert–Bonamy method has been performed. A satisfactory agreement between the theory and experiment has been obtained.     

Radical-Recombination Luminescence of the Uranyl Nitrate Complex in the Adsorbed State

We have investigated the luminescence of uranyl nitrate molecules on the surface of powdery SiO₂ upon excitation by UV light (PhL) and hydrogen atoms (radical-recombination luminescence (RRL)). It has been found that the PhL and RRL spectra have a clearly defined vibrational structure. The luminescence peaks of the adsorbed UO₂ ^2– ion are characterized by a systematic longwave shift from the same peaks of crystalline uranyl nitrate (by 230–430 cm^–1 at 130 K). Moreover, in the adsorption centers the vibration frequencies of UO₂ ^2– are 20–80 cm smaller than in crystalline salt and the RRL bands are 150–350 cm^–1 (130 K) wider than the corresponding PhL bands.     

Phosphorescence spectra of acenaphthene,diphenyl, and carbazole

These spectra are for liquid-nitrogen temperature, the solvents being n-pentane, n-hexane, n-heptane, and n-octane. Each has a vibrational structure, the vibrational frequencies being independent of the solvent. Acenaphthene in pentane and octane gives 12 peaks corresponding to vibrational frequencies of 414, 630, 1152, 1409, and 1604 cm^–1, the last two being the strongest. Diphenyl in pentane and heptane gives gives 21 peaks; the strongest vibrations are 1610 and 1275 cm^–1, others being 1003, 320, and 735 cm^–1. Carbazole in pentane and hexane gives 15 peaks that fit the frequencies 750, 852, 1141, 1305, 1477, and 1605 cm^–1, the first and last being the strongest.     

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.     

Instability of the molecular structure of monobenzoporphin to the alternation of the macrocycle bond lengths and its manifestation in the electronic spectra

Quantum-chemical calculations of the geometric structure of the molecules of monobenzoporphin (H₂ MBP) and monobenzoporphin with methyl and ethyl substituents in the five-member rings (H₂MBPm) have been carried out by the restricted and unrestricted Hartree-Fock methods with the AM1 Hamiltonian (AM1 RHF and AM1 UHF methods). The calculation of the above-indicated molecules by the AM1 RHF method without restrictions on their symmetry has given, for them, a planar structure with an alternation of the lengths of the bonds along the 18-member azacyclopolyene and the symmetry C _1h for their aromatic part. The calculation of the transitions to the excited electron Q states in such a structure by the CNDO/S method has shown that these states are characterized by large hypsochromic shifts (~3000–4000 cm^–1 ) relative to the Q levels of porphin (H₂P), which is in contradiction with the experimental data, according to which these shifts are bathochromic and comprise = –330 cm ^–1 and = –750 cm^–1. Optimization of the geometry of the H₂ MBP and H₂MBPm molecules by the AM1 UHF method gives, for them, a structure with equal lengths of the bonds along the 18-member azacyclopolyene with a symmetry differing insignificantly from the D _2h symmetry; elements of the structure with a lower symmetry and an alternation of the lengths of the bonds are retained in the condensed pyrrolenine and benzene rings. The calculation of the shifts of the Q levels in the H₂MBPm molecule of this geometry relative to the analogous levels in H₂P has shown that they are bathochromic and equal to = –520 cm^–1, and the RHF calculation with optimization of the geometry of the molecule and restrictions on the effective symmetry D _2h of the 18-member azacyclopolyene has given = –350 cm^–1 and = –430 cm^–1. The restrictions imposed on the C ₂ symmetry of the H₂MBP molecules by the RHF method are inadequate to equalize the lengths of the bonds along the 18-member azacyclopolyene. The calculations of the energy of the B levels of the monobenzoporphyrins considered also lend credence to their geometric structure with equal lengths of the bonds along the 18-member azacyclopolyene.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 712–721, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

High-resolution far-infrared spectroscopy of C-13 methanol

The high-resolution far-infrared (FIR) Fourier transform spectrum of¹³CH₃OH has been studied from 25–350 cm^–1, andb-type^rR-branches in the torsional ground state have been assigned. The branches have been fitted to phenomeno-logical expansion parameters, which reproduce the branch frequencies generally to well within ±0.001 cm^–1. An interesting and relatively novel K=4 perturbation, localized to levels around J=18, has been observed between (nK)=(019) and (125) states.     

Excited Even-Symmetry States of Metallocomplexes of Porphin and Its Derivatives

Based on calculations by the CNDO/S method, data on the excited molecular states of even parity of the magnesium complexes of porphin (P), tetraazaporphin (TAP), tetrabenzoporphin (TBP), and phthalocyanine (Phc) are obtained. It is only in MgP that the first excited g-state 1¹ B _2g (29,000 cm^–1) is located 300 cm^–1 higher than the B level (28,700 cm^–1). In MgTBP, the two states 1¹ B _1g (24,700 cm^–1) and 1¹ B _2g (25,500 cm^–1) are found to be near the B level (27,500 cm^–1), while the states 1¹ B _2g (25,500 cm^–1) in MgTAP and 1¹ B _2g (21,000 cm^–1) and 1¹ B _1g (23,100 cm^–1) in MgPhc are located much lower than the B level; the energy of the latter is 31,900 and 32,400 cm^–1 in MgTAP and MgPhc respectively. The results obtained are in good agreement with experimental data on two-photon absorption: in the zinc complex of tetraphenylporphin (TPhP), the g-state is detected in the region of the B level, while in ZnPhc, two bands at 20,400 and 21,700 cm^–1 show up.     

Assignments of optically pumped CD3OH laser lines

Six FIR laser lines from CD₃OH pumped by the 10R(36) and the 10R(18) CO₂ laser lines are assigned to specific rotational energy levels in the excited C–0 stretch state. It is found that their upper laser levels are shifted by a Fermi resonance between the C–0 stretch vibration and the third and forth harmonics of the torsional mode. The Fermi resonance shifts are +0.332 cm^–1 and +2.251 cm^–1 for the upper laser levels pumped by the 10R(36) and the 10R(18) CO₂ laser lines, respectively. Calculated frequencies of the pump and the laser transitions agree with those of the pump CO₂ laser lines and the observed FIR laser lines within estimated accuracy.     

FTIR and Raman spectroscopic study of Fenugreek (<Emphasis Type="Italic">Trigonella foenum graecum L.</Emphasis>) seeds

The composition of Fenugreek seeds in the form of powder, ash, and oil is investigated through FTIR and FT Raman spectra measurements. The results indicate that Fenugreek seeds (powder) are rich in proteins. Fats (lipids) and starch are present in small amounts in the seeds. The FTIR absorption bands of seed powder appeared at: 3365 cm^–1 assigned as N-H stretching vibrations (amide A of protein), 1657 cm^–1 (C=O, amide I), 1540 cm^–1 (N-H bending vibration, amide II), and 1240 cm^–1 (N-H bending, amide III). In the FT Raman spectra the band at 1661 cm^–1 is ascribed to amide I (C=O) of proteins while the band at 1080 cm^–1 indicates the starch. The fenugreek oil Fourier transform infrared absorbance ratios A(3009 cm^–1)/A(2924 cm^–1), A(3009 cm^–1)/A(2854 cm^–1), and A(3009 cm^–1)/A(1740 cm^–1) were considered for measuring the iodine values. These ratios (0.3609, 0.4916, and 0.4129) revealed that the iodine value of fenugreek oil is higher than that of other oils. On the other hand, the ash of fenugreek is very rich in phosphate compounds. The spectra showed absorption bands at frequencies 1082, 1000, 618, and 566 cm^–1, and the FT Raman spectrum showed a strong absorbance band at 793 cm^–1, which is due to phosphate compounds. It could be concluded that the inorganic part of fenugreek consists mainly of phosphate compounds. The Fenugreek seed contains proteins, fat, fiber, and ash, which is in complete harmony with AACC, 1980.__________Published in Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 106–110, January–February, 2005.     

Calculation and study of the IR absorption spectrum of hydantoin

The IR absorption spectrum of hydantoin has been obtained in the range 400–3500 cm^–1, and the normal-vibration frequencies are calculated on the basis of the mechanical model. The spectrum is interpreted.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, Vol. 12, No. 6, pp. 116–120, June, 1969.     

The IR absorption spectrum of 2 - aminothiazolid - 4 - one

A mechanical model has been used to calculate the frequencies in the vibrational spectrum of the imine and amine tautomeric structures for this compound; the IR spectrum for the crystalline state has been deduced for the range 80–3500 cm^–1, and a discussion is given for the effect of the tautomeric prototropic forms on the vibrational spectrum.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 9, pp. 76–82, September, 1971.     

A high-resolution high-speed data acquisition system based on an IBM-PC 486, for control of a Fourier transform spectrometer

The mini-computer and control electronics of a Bruker 113v Fourier Transform Spectrometer (FTS), capable of 0.03 cm^–1 resolution for frequencies up to 4000cm^–1, have been replaced by an inexpensive IBM-PC 486-based system. The original performance is exceeded. JCAMP-DX standard is used for data exchange. The system can be adapted to any FTS or similar instrument which requires time domain data acquisition.     

Infrared spectra of urine from cancerous bladders

The infrared spectra of organic constituents of urine from cancerous bladders of some patients were recorded. The spectra of the organic part of the samples were classified into five types according to the bulk constituents. Samples with type A spectra consisted mainly of proteins with only trace amounts of lipids. Their spectra were characterized mainly by the absorption bands of proteins at the frequencies 3330, 3075, 2960, 2850, 1650, 1530, 1450, 1400 and 1320 cm^–1, in addition to a weak band at 1720 cm^–1 due to the absorption of lipids. Samples with type B spectra were characterized by high amounts of proteins and low amounts of lipids and phosphate compounds. The presence of phosphate compounds was indicated by the absorption bands at the frequencies 1100 and 1030 cm^–1. Samples giving spectral type C were characterized by high urea contents as indicated by the presence of two strong bands at 1670 and 1630 cm^–1. Samples with the spectral type D consisted of urea and phosphate compounds whereas the last spectral type E consisted mainly of calcium oxalates, uric acids and phosphate compounds. The presence of calcium oxalates was indicated by the presence of its diagnostic bands at the frequencies 1630 and 1330 cm^–1, while the presence of uric acid was indicated by the bands at the frequencies 1360, 1130, 1020 and 880 cm^–1. On the other hand, the spectra of the organic part of urine from some normal bladders exhibited the characteristic bands of urea only.Careful examination of the spectra of the inorganic part of urine revealed that some samples consisted mainly of hydroxyapatite. The absorption bands of hydroxyapatite appeared at the frequencies 568, 603, 985, 1037 and 1128 cm^–1. The spectra of other samples showed that the bands of basic phosphates at the frequencies 568, 620, 727, 890, 1035 and 1140 cm^–1. The spectra of the inorganic part of urine from a number of normal bladders displayed the bands of basic phosphates. The relationship between urine constituents and pathological types of bladder tumor tissue was discussed.     

Laser annealing of GaAs dual implanted with Si and P ions

Laser annealing of SI(100) GaAs:Cr implanted either with Si⁺ ions (150 keV, 6×10¹³-1×10¹⁵cm^–2) or dual implanted with Si⁺ ions (150 keV, 6×10¹⁴–1×10¹⁵cm^–2) and P⁺ ions (160 keV, 1×10¹⁴–1×10¹⁵cm^–2) has been examined using backscatteringchannelling technique and via electrical measurement of Hall effect. It has been found that at laser energy densities 0·8 J cm^–2 a full recovery of the sample surface occurs. In dual implanted samples (1×10¹⁵ Si⁺ cm^–2+1×10¹⁵P⁺cm^–2) up to 46% of Si atoms become electrically active after the laser annealing. Resultant Hall mobility of carriers is, however,lower than that obtained after common thermal annealing.The authors are pleased to take the opportunity of thanking Professor M. Kubát for his encouragement and continuous support. Accelerator staff is gratefully acknowledged for its assistance in the course of experiments.     

Infrared vibrational spectra of -histidinium dihydrogen orthophosphate orthophosphoric acid (LHP)

The entire vibrational spectrum of a single crystal of -histidinium dihydrogen orthophosphate orthophosphoric acid (LHP) was studied by infrared (IR) spectroscopy from 10 up to 4000 cm⁻¹. The polarized infrared (IR) reflectivity spectra were measured between 7 and 250 K, in the frequency range 10–600 cm⁻¹. From the IR spectral analysis, the phonon modes were classified within their symmetry species, and their longitudinal (LO) and transversal (TO) optical frequencies were calculated. A tentative assignment of the various internal modes observed in the transmissivity spectrum of LHP, between 300 and 4000 cm⁻¹, is proposed. The present study did not reveal any low-temperature structural phase transition.     

Calculation and study of the infrared absorption spectrum of 2, 5-dimethyl-4-phenylpyridine

The infrared absorption spectrum of 2, 5-dimethyl-4-phenylpyridine has been recorded in the range 400–2000 cm^–1 and the valence-force scheme has been used to calculate the values of the fundamental frequencies and the forms of the normal vibrations.In conclusion the author thanks M. M. Kusakov for directing the work and L. A. Gribov for discussion of the results.     

Theoretical calculations and Raman spectrum of intercalation modes in LixInSe

By using an extended linear-chain model which includes the interlayer forces, we have calculated the new vibrational modes, of Li intercalated InSe. The dispersion curves along thek _z wavevector perpendicular to the layers for the -polytype are determined in the first Brillouin zone. Assuming that the interlayer interaction is not modified upon intercalation and the interaction between lithium atom and adjacent layers in the van der Waals plane has the same value than the interlayer one, the new modes are determined with the force constant given by the rigid layer mode of the, -polytype at 18 cm^–1. This model gives the variation of the acoustic branches and the appearance of two optical intercalation modes at higher frequencies. The Brillouin zone boundary modes of the acoustic branches at 18 and 41 cm^–1 in the pure material are calculated to be 22 and 50 cm^–1 respectively forx=1/2. The dispersion of the new optical branches is flat along thez-direction and frequencies are obtained at 96 cm^–1 for the Li mode perpendicular tok _z and at 218 cm^–1 for the Li mode parallel tok _z. We compare also our results with the Li mode frequencies obtained in a total energy calculation. Raman scattering experiments have been performed in intercalated sample in order to verify the proposed model.