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.     

Quantum mechanical analysis of resonance Raman spectra of thymine

A direct quantum mechanical calculation of the relative intensities of lines in resonance Raman (RR) spectra of thymine was performed. The method of calculation is based on the adiabatic model in the Herzberg-Teller approximation. It is shown that the basic features of the intensity distribution in the spectra can be explained only by taking into account the vibronic mixing of electronic states and the contribution to the components of the scattering tensor from excited electronic states located close to the resonance state. The calculated results agree satisfactorily with experimental RR spectra of thymine excited by laser radiation at 266, 240, 218, and 200 nm. A comparative analysis of the intensity distribution in the RR spectra of thymine and uracil is carried out.     

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.     

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.     

Modulation of optical pulses under electromagnetically induced transparency conditions: transfer of the Rabi oscillations manifestation from the radiofrequency to the optical range

The relative intensities of lines in resonance Raman scattering spectra of isolated skatole and skatole-water complex have been calculated quantum mechanically. The influence of the intermolecular interaction on these spectra has been considered. Particular features of the intensity distribution in the resonance Raman scattering spectra of indole and skatole have been compared.     

Quantum-mechanical analysis of resonance Raman scattering spectra of the uracil molecule

A direct quantum-mechanical calculation of the relative intensities of lines in the resonance Raman scattering (RRS) spectra of uracil is performed by a method developed earlier by the authors on the basis of the adiabatic model in the Herzberg-Teller approximation [1]. It is shown that the main regularities in the intensity distribution of spectra can be explained only by taking into account the vibronic mixing of electronic states and the contribution to the scattering tensor components from the excited electronic states adjacent to the resonance state. The calculated results are in satisfactory agreement with the results of experimental studies of the RRS spectra of uracil excited by laser radiation at 266, 240, 218, and 200 nm.     

X-ray spectra simulation of Li-like nickel L-shell Ions

The X-ray emission spectra of nickel plasma were simulated under the collisional radiative model (CRM) by using the flexible atomic code (FAC). The dynamical processes including collisional excitation (CE), radiative recombination (RR), dielectronic recombination (DR), collisional ionization (CI) and resonance excitation were considered in the model, and the rate coefficients of DR, RR as well as CI were consistent with previous results within 15%. It was found that the contributions to spectra from cascades and indirect processes could not be ignored. The intensities of spectral lines for lithium-like nickel L-shell ions are sensitive to the electron temperature. The good agreement between present spectral peaks and earlier observed results can be taken as a measure of the accuracy of the present work.     

Resonance modes of layered ferromagnets in a transverse magnetic field

Intensities and positions of resonance lines are calculated for the ferromagnetic resonance spectra of multilayer ferromagnetic films in a magnetic field oriented normally to the film surface. It is shown that the positions of spectral lines depend on the number of ferromagnetic layers, while the line intensities are determined by the phase shift between the oscillations of the magnetic moments of neighboring layers. A qualitative comparison is carried out between the results of calculations and the spectra observed in experiments.     

Quantum-mechanical description of the intensity distribution in two-photon absorption spectra of dihalogenated benzenes

Using molecules of dihalogenated benzenes as an example, the verification of an earlier proposed method of direct quantum-mechanical calculation of the relative intensities of lines in the two-photon absorption spectra of polyatomic molecules is continued. The method of calculation is based on the adiabatic model in the context of the Herzberg-Teller approximation. A comparative analysis of the intensity distribution in the two-photon absorption spectra of dihalogenated and monosubstituted benzenes is carried out, and the vibrational characteristics of these molecules in the lowest singlet excited electronic states are determined. A satisfactory agreement with experimental values, along with the analysis of the possibilities of the method, confirms the expediency of its use for gaining information about the intensity distribution in two-photon absorption spectra of polyatomic molecules.     

Radiospectroscopic and dielectric spectra of nanomaterials

The shape of lines in the radiospectroscopic (NMR and EPR) and dielectric spectra of materials formed by nanoparticles (hereafter, nanomaterials) is analyzed theoretically. The theory is developed in the framework of the core and shell model according to which a nanoparticle consists of two regions whose properties are affected and unaffected by the surface, respectively. The changes in the resonance frequency, the relaxation time, and the static permittivity due to the surface tension are taken into account, and the Gaussian and Lorentzian shapes of homogeneously broadened lines are considered. The inhomogeneous broadening of the spectral lines is examined for several types of nanoparticle size distributions. It is demonstrated that the splitting of the initial lines in the spectra of bulk systems into pairs of lines with a decrease in the particle size is a specific feature of the spectra of nanoparticles. The intensities and half-widths of the lines are investigated as functions of the parameters of the size distribution of nanoparticles. The results of theoretical calculations are compared with recent experimental data on the ¹⁷O and ²⁵Mg NMR spectra of nanocrystalline MgO. The theoretical dependences of the intensity, the resonance frequency, and the half-width of the spectral lines are in good agreement with the experimental data. The proposed theory offers a satisfactory explanation of the behavior of the static permittivity in BaTiO₃ ceramic materials with nanometer-sized grains.     

Optical spectrum of a closed cycle MHD generator plasma

The spectra of argon-cesium plasmas, used as working fluids of closed-cycle MHD generators, were investigated in the visible and near-i.r. regions by using a Hilger-Watts medium quartz spectrograph. A number of argon and cesium lines was observed, as well as some lines originating from the impurities present in the cesium capsule. The molecular bands of aluminum monoxide have also been detected. The population temperatures estimated from relative intensities of cesium lines lie below those obtained by using either the line-reversal method or recombination-radiation measurements. The intensities of some neutral cesium lines follow the Boltzmann population relation at the population temperature. The Zeeman effect and reversed profiles of cesium resonance lines were not observed because of low resolution of the spectrograph used and because of light scattering on the film.     

Zum Konzept der charakteristischen Intensitäten der Resonanz-Ramanlinien von Azofarbstoffen

The resonance Raman spectra of the solutions of some azobenzene and hydroxyazonaphthalene compounds were investigated. The relative corrected scattering coefficientsS of the lines have been measured. Assuming the existence of a characteristic intensity, the frequency dependence and the influence of data of the long-wavelength electronic absorption band has been discussed. Testing formulas for intensity dependence in this way it has been shown, that they cannot exactly describe resonance Raman intensities, because there is the problem of the “effective” electronic absorption band. This was studied by comparison of the intensities of several azonaphthalene lines, excited by the mercury lines 4358 and 5461 Å.     

Structural form of vibronic intensities in vibronic induced transitions

A general method for calculating the overall shape of the spectrum of vibronic induced transitions in transition-metal ion systems is developed. The vibronic structure is expressed in terms of a weighted sum of medium induced lorentzian lines located at the frequencies of the fundamental odd vibrations of the complex. Each of these lines is followed by a series of vibronic lines assigned to the combination frequencies with one or more even vibrations. The relative intensities of these combination lines are determined by the values of an intramolecular distribution which includes both the effects of geometry and frequency changes of the modes involved in the transition. Values of the linear and the quadratic parameter for the molecule can be estimated from a fit to the experimental spectra.     

Quantum-mechanical calculation of the intensity distributions in spectra of resonance hyper-Raman scattering and two-photon absorption of indole and skatole

We have performed a quantum-mechanical calculation of the relative intensities of lines in the spectra of resonance hyper-Raman scattering and two-photon absorption of isolated indole, indole in an aqueous solution, isolated skatole, and skatole-water complex. The effects of hydrogen bonds and intermolecular interaction on the spectra have been considered. Particular features of the intensity distributions in the spectra of indole and skatole have been compared.     

Peculiarities of the radiospectroscopy line shape in nanomaterials

The theory of the radiospectroscopy (nuclear magnetic resonance [NMR] and electron spin resonance [ESR]) line shape for nanomaterials is developed. The consideration was performed in the core and shell models which are, respectively, the nanoparticle regions unperturbed and perturbed by the surface influence. The shift of the resonance frequency by the surface tension was taken into account. The homogeneously broadened line shape was supposed to be Gaussian or Lorentzian. Inhomogeneous broadening of lines via the distribution of nanoparticle sizes was calculated for several forms of the size distribution function. The splitting of radiospectroscopy spectra into two lines decreases with particle sizes, which looks like that in the bulk and on the surface. It was shown to be the characteristic feature of nanomaterial spectra. The changing of these lines’ intensity and width with the change of the distribution function parameters and the particle size decrease was considered. The comparison of the theory with NMR spectra of¹⁷O and²⁵Mg observed recently in nanocrystalline MgO is performed. The calculations fit pretty good the observed size dependence of the line shape, intensity and width.     

调制对磁共振谱的线宽,线形及幅值的影响

用付里叶分析方法从理论上分析计算了磁场调制对谱线(单一或重迭的)的线宽、线形及幅值的影响,并将理论计算结果与激光磁共振谱的调制效应的实验结果作了比较,两者符合得很好。据此作者提出了对于采用调制相检技术的磁共振谱技术普遍适用的选择调制参数的方法、步骤和原则。     

Autowave instability in refractive crystals

The intensities of vibronic lines are experimentally measured in fluorescence and fluorescence excitation spectra of jet-cooled anthracene. An original method is developed for calculating geometrical parameters of benzene hydrocarbons in the ground and excited electronic states. Using these parameters, the intensities of vibronic lines in fluorescence and absorption spectra of anthracene are calculated in the Franck-Condon approximation taking into account the mixing of all the twelve normal coordinates of totally symmetric vibrational modes. After correction for the quantum yield of fluorescence, good agreement is obtained between the calculated line intensities in the absorption spectrum and the measured line intensities in the fluorescence excitation spectrum. Based on these data, a new assignment of the lines in the fluorescence excitation spectrum corresponding to totally symmetric modes 7 and 8 is suggested.     

X-ray spectra from highly ionized dense plasmas produced by ultrashort laser pulses

Hydrogen-like and helium-like X-ray spectra (between 7.1 and 8.2 , i.e., 1500 to 17.50 eV, respectively) from solid aluminium targets irradiated with high intensity (up to 10¹⁷ W/cm²) subpicosecond (0.7 ps) laser pulses have been measured. The spectra show that the resonance lines are very broad and very asymmetric. Evidence for a Doppler-shifted reabsorption of the resonance line emission has been found. The spectra have been simulated by a computer code for the calculation of spectral-line intensities and linewidths. Electron densities exceeding the critical density have been estimated for different laser intensities by comparing the observed and simulated intensity ratio of different dielectronic satellite lines. From the X-ray spectra generated byp- ands-polarized radiation fat different laser intensities, the thresholds for the formation of hydrogen-like and helium-like ions have been determined.