Quantum-mechanical calculation of the intensity distribution in the resonance Raman spectrum of benzonitrile

A direct quantum-mechanical calculation of the resonance Raman spectrum of a benzonitrile molecule upon excitation with laser radiation at a wavelength of 228.7 nm is performed in the Herzberg-Teller approximation with allowance made for the Duschinsky effect. The results of the calculation are in reasonable agreement with the available experimental data. The intensity distribution in the calculated resonance Raman spectrum of the benzonitrile molecule is compared with the intensity distributions in the spectra of benzene, methyl-substituted benzenes, and halogenated benzenes. It is revealed that the intensity distributions in the resonance Raman spectra of these compounds are characterized by a number of common features.     

Mechanism for quenching of the luminescence of 9,10-anthraquinone vapor by oxygen

The fluorescence of 9,10-anthraquinone, 1-aminoanthraquinone, 1,4-diaminoanthraquinone, and 1,5-diaminoanthraquinone is not quenched by oxygen because the singlet-triplet energy difference in these compounds is less than the energy needed for excitation of the triplet state of oxygen to the singlet state. Luminescence of 9,10-anthraquinone is quenched because it is mainly phosphorescence, for which the singlet-triplet difference is sufficient for quenching by a mechanism involving singlet oxygen formation. The weak fluorescence of 9,10-anthraquinone is not quenched. The resistance of the fluorescence of 9,10-anthraquinone vapor to quenching by oxygen and the quenching of its phosphorescence explain the different effects of oxygen on the luminescence of α-substituted and β-substituted anthraquinones known from the literature, and indicate that their singlet excited state cannot convert triplet oxygen to singlet oxygen. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 79–4, January–February, 2008.     

Quantum-mechanical calculation of the intensity distribution in resonance Raman spectra of cytosine

A quantum-mechanical calculation of the relative intensities of lines in resonance Raman (RR) spectra of cytosine excited by laser radiation at 266, 218, and 200 nm was performed in different approximations of the vibronic theory. Both the Herzberg-Teller effect and the contribution from electronic states located close to the resonance state are shown to play a significant role in determining the relative intensities of lines. A satisfactory agreement between the calculated results and experimental data is obtained. The specific features of the intensity distribution in the RR spectra of cytosine are compared with those in the spectra of the previously studied thymine and uracil, which have a similar structure and also belong to the simplest nucleic acid bases.     

石墨烯在强激光作用下改性的拉曼研究

采用化学气相沉积法制备了不同层数的石墨烯样品.根据石墨烯透过率曲线分析石墨烯样品层数与550 nm处透过率关系的同时,利用拉曼光谱法分析了不同层数石墨烯样品在强激光辐照下的损伤特性.结果表明:单层石墨烯样品经强激光辐照后,G带和2D带均向高频移动;多层石墨烯样品经强激光辐照后只有G带发生了略微的频移;石墨烯样品拉曼光谱G带与2D带强度比值表征了石墨烯的层数,此比值随激光辐照时间的增加而减小,这表明强激光对石墨烯样品具有明显的剥离现象.     

Quantum-mechanical calculation of the intensity distribution in resonance Raman spectra of guanine-cytosine pair

The method of quantum-mechanical calculation of the relative line intensities in the resonance Raman (RR) spectra of polyatomic molecules, which was previously applied to the analysis of the spectra of individual cyclic molecules and makes it possible to take into account the Herzberg-Teller and Duschinsky effects, as well as the frequency effect, is applied for the first time to the calculation of the spectra of a pair guanine-cytosine. Satisfactory agreement between the calculated results and the available experimental data is obtained. The particular features of the intensity distribution in the RR spectra of the guanine-cytosine pair excited by laser radiation at 266, 240, 218, and 200 nm are analyzed. The RR spectra of the guanine-cytosine pair are compared with the spectra of the individual guanine and cytosine molecules excited by the laser radiation at the same wavelengths.     

液芯光纤方法研究溶剂对分子拉曼光谱强度的影响

液芯光纤可以大幅度提高拉曼光谱强度. 本文用液芯光纤方法测量了CCl4 在CS2 和C6H5Br中不同浓度下459 cm-1,314 cm-1和218 cm-1的拉曼光谱强度,验证了一些溶剂使某些分子拉曼光谱增强的溶剂效应.     

Quantum-mechanical calculation of the intensity distribution in resonance Raman spectra of thiosubstituted derivatives of uracil

A quantum-mechanical calculation of the intensity distribution in the resonance Raman (RR) spectra of 2-thiouracil and 4-thiouracil is carried out for exciting laser radiation at 300, 257, and 248 nm. It is shown that, for satisfactory agreement between the calculated results and the experimental data, it is necessary to take into account in the calculations of the relative intensities of lines the Herzberg-Teller effect and the contribution from excited electronic states adjacent to the resonance state. The general and specific features of the intensity distribution in the RR spectra of uracil and its thiosubstituted derivatives are compared and discussed.     

Electrocatalytic properties of glassy carbon electrodes modified with hydroxy derivatives of 9,10-anthraquinone for oxygen reduction reaction

The electrochemical and electrocatalytic behavior of glassy carbon electrodes modified by one mono and four dihydroxy derivatives of anthra-9,10-quinone compounds have been investigated by cyclic voltammetric technique. The stability of the modified electrodes was ascertained in acidic and neutral media. The surface morphology of modified electrode was characterized by scanning electron microscope. The influence of pH on the electrochemical and electrocatalytic behavior was studied and pH?6.0 or 7.0 was chosen as the optimum working pH by comparing the shift in oxygen reduction potential. The anthraquinone-adsorbed glassy carbon electrodes possess excellent electrocatalytic ability for oxygen reduction with overpotential ranging from 388 to 547?mV lower than that at a plain glassy carbon electrode. Hydrodynamic volatammetric studies were performed to determine the heterogeneous rate constants for the reduction of O₂ at the surface of the modified electrodes, mass specific activity of the anthraquinones used, and the apparent diffusion coefficient of O₂ in buffered aqueous O₂-saturated solutions.     

Temperature dependence of the fine structure of vibronic bands of fluorescence of 1,4,5,8-tetraoxy-9,10-anthraquinone in a polymer matrix

L. Ya. Karpov Physicochemical Research Institute, 10, Obukhov Str., Moscow, 103064, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 2, pp. 65–69, March–April, 1995.     

Raman spectrum of monobromoindigo

Monobromoindigo is a component of Tyrian purple, a purple–red natural colorant extracted from various species of sea snails, which was possibly first produced by the ancient Phoenicians and has been employed as a symbol of royalty and power by several civilizations over the centuries. Raman spectroscopy has proved to be an effective analytical technique to detect historical dyes, as it allows rapid and accurate identification of unknowns in a nondestructive way. Although other constituents of Tyrian purple have been comprehensively investigated by Raman spectroscopy, the Raman bands of 6‐bromoindigo, a molecule that has been correlated with a specific snail species, Hexaplex trunculus (also known as Murex trunculus), have been reported but not previously assigned. This paper includes a complete assignment of the Raman spectrum of the 6‐bromoindigo isomer, including experimental spectra recorded at 488 and 785 nm, which were compared with those collected from indigo under the same conditions. 1 1 This article was first published online 03 November 2011. Errors were subsequently identified. This notice is included in both print and online versions to indicate that both have been corrected 07 December 2011.
Theoretical Raman spectra for both molecules were obtained using density functional theory calculations. Copyright © 2011 John Wiley & Sons, Ltd.     

Near-forward Raman scattering intensity in ZnO

We have measured the Raman scattering intensities of the E₁ (TO) polariton mode in ZnO, a wurtzite type crystal, at room and liquid nitrogen temperatures. These results reveal a novel behavior in contrast to that observed for ZnSe. These results confirm earlier theoretical considerations.     

Quantum-mechanical analysis of the intensity distribution in spectra of resonant Raman scattering spectra of aqueous solutions of tyrosine

Quantum-mechanical calculations of the intensity distribution in the resonant Raman scattering spectra of aqueous solutions of tyrosine excited by laser radiation with wavelengths of 244, 229, 218, 200, and 193 nm, as well as in the nonresonant Raman scattering spectrum excited at a wavelength of 488 nm, are performed. Satisfactory agreement is achieved between the calculation results and the experimental data. It is shown that the changes in the intensity distribution observed in the spectra with a change in the excitation wavelength from 244 to 193 nm correlate with the determined changes in the contribution made by excited electronic states into the scattering tensor components. It is noted that it is necessary to take into account the Herzberg–Teller effect and that the number of excited electronic states taken into account considerably affects the calculated relative intensities of lines. The possibility of existence of several tyrosine conformers in aqueous solution at room temperature is shown.     

Rotational Raman spectrum of cyclopropane

The pure rotational Raman spectrum of cyclopropane was observed up to J = 43. We have taken into account the effects of the unresolved K structure of the lines by assigning an effective value of K to the center of each unresolved line. Methods are developed for calculating effective K values for each value of J that allow a simultaneous fit to the R-and S-branch lines. The rotational constants of cyclopropane derived from this research are, in wavenumber units (cm^?1); B₀ = 0.6702₈, D_J = 1.0 × 10^?6, and D_JK = ?1.3 × 10^?6. We have also tested the validity of the method by using it with recent Raman data for BF₃.     

Raman spectrum of sodium iodide

Raman spectrum of a single crystal of sodium iodide has been recorded for the first time using λ 2537 excitation. The general features of the spectrum are discussed in the light of the existing theories on the dynamics of the alkali halides.     

Raman spectrum of strontium titanate

The Raman spectrum of strontium titanate has been recorded using λ 4358 of mercury as exciter. The observed spectrum consists of 7 Raman lines, one of which is of low frequency, as expected from the recent theory of Cochran. 6 of these Raman lines have been interpreted as the first order spectrum arising from a small deviation of the cubic strontium titanate from its idealized symmetry. It has been shown that one normal mode of SrTiO₃ neglected by J.T.Last, will be really active in infrared absorption in the region of 440 cm^?1 and that it has to be taken into account in the interpretation of the infrared spectra of titanates. The four vibrational modes of the unit cell of SrTiO₃ correspond to frequencies of 90, 335, 441 and 620 cm^?1 observed in Raman effect. The large width of the Raman lines and the additional lines at 256 cm^?1 and 726 cm^?1 have been attributed to a splitting of the longitudinal and transverse optical modes. With the observed frequencies it has been found possible to account for in a satisfactory manner the specific heat of SrTiO₃ in the range 54·84° K to 1800° K.