Calculation of MAS spectra influenced by slow molecular tumbling.

A numeric algorithm is proposed that is suitable to calculate spectral lineshapes influenced by isotropic and anisotropic tumbling under sample spinning conditions. It is based on the stochastic Liouville equation and a rotational diffusion process described by a stationary Markov operator. A corresponding FORTRAN program can be implemented on a regular personal computer. The calculations result in spectral lineshapes including a complete set of spinning sidebands. The sensitive time scale of the resulting lineshapes depends on the deviation of the sample spinning axis from the magic angle. An example is presented demonstrating the potential of off-magic-angle spinning as a tool to analyze slow tumbling motions.     

Ordering in nematic liquid crystals from NMR cross-polarization studies

The measurement of dipolar couplings between nuclei is a convenient way of obtatining directly liquid crystalline ordering through NMR since the coupling is dependent on the average orientation of the dipolar vector in the magnetic field which also aligns the liquid crystal. However, measurement of the dipolar coupling between a pair of selected nuclei is beset with problems that require special solutions. In this article the use of cross polarization for measuring dipolar couplings in liquid crystals is illustrated. Transient oscillations observed during cross polarization provide the dipolar couplings between essentially isolated nearest neighbour spins which can be extracted for several sites simultaneously by employing two-dimensional NMR techniques. The use of the method for obtaining heteronuclear dipolar couplings and hence the order parameters of liquid crystals is presented. Several modifications to the basic experiment are considered and their utility illustrated. A method for obtaining proton-proton dipolar couplings, by utilizing cross polarization from the dipolar reservoir, is also presented.     

A tunable infrared plasmonic polarization filter with asymmetrical cross resonator

A tunable infrared plasmonic polarization filter is proposed and investigated in this paper. The filter is based on the sandwich absorption structure which consists of three layers. The top layer is an array of asymmetrical cross resonator.The middle and bottom layers are dielectric spacer and metal film respectively. By absorbing specific wavelength of the incident light perfectly, the reflection spectrum of the structure shows filter performance. The calculated results show that the absorption wavelength is strongly dependent on the length of branch of the asymmetrical cross resonator which is parallel to the light polarization and independent of the length of the vertical one. Therefore, the asymmetrical cross resonator filter structure opens the way for freely tuning the filtering wavelength for a different light polarization. We can fix a resonant wavelength(absorption wavelength) corresponding to one polarization and change the resonant wavelength for the other polarization by adjusting the corresponding branch length of the asymmetrical cross resonator, or change the two resonant wavelengths of both two polarizations at the same time.     

Simulation of Magnetic Resonance Static Powder Lineshapes: A Quantitative Assessment of Spherical Codes

Simulation of magnetic resonance static powder spectra is performed by a (possibly weighted) summation of single-crystal spectra computed for different orientations of the external field with respect to the principal axes of the magnetic interactions. The many available methods differ in the choice of the integration points (i.e., orientations) and weights, the set of which is called spherical code. There is continuing interest in minimizing the number of integration points necessary to a good simulation. Neglecting the possible interpolation of transition frequencies and intensities between integration points, we turn our attention to the efficiency of spherical codes themselves. To this end, an unbiased quantitative procedure to assess their efficiency in simulating magnetic resonance static powder spectra is proposed. To achieve an impartial judgement, the procedure has been designed by carefully taking into consideration the following points: choice of exact reference spectra; accurate definition of the merit figures; extended range of number of integration points; orientation dependence of the efficiency. The proposed procedure has been applied to an inclusive set of 23 spherical codes. It was found that most codes perform rather similarly. SPIRAL is the most efficient code, whereas Monte Carlo and “repulsive” codes show the best rotational invariance of the simulated lineshape with respect to the orientation of the spherical code.     

Kinetics of H→P cross-polarization in human trabecular bone

Bloch-decay and cross-polarization (CP) ³¹P nuclear magnetic resonance (NMR) spectra of healthy human trabecular bone were acquired under magic-angle spinning (MAS) at 3 kHz. A single peak at 3.1 ppm was detected. Variable-contact time ¹H → ³¹P CP experiments revealed three signal components growing at various rates. The fast, moderate and slow components were assigned and assessed in P atom % to proton-rich (24%), hydroxyapatite (58%) and proton-deficient (18%) phosphate domains, respectively. Examination of CP kinetics is useful for the chemical characterization of bone tissue.     

Fluorescence spectra of uranium induced by a linearly polarized laser light in a magnetic field

In this paper we reported the fluorescence spectra of U~(238) induced by a linearly polarized laser field in a magnetic field and offered a theoretical analysis. The consistence between the theoretical prediction and experimental results was satisfactory.     

Calculation of electronic spectra for intermolecular complexes of 3-aminophthalimide by a modified Hückel molecular orbital method

Calculation of the spectra of intermolecular complexes of 3-aminophthalimide is used as an example to show that when hydrogen bonds are present, the resonance integrals for the proton donor and acceptor atoms are different from zero. Theoretical analysis of strained 3-aminophthalimide complexes allowed us to establish the determining role of hydrogen bonds in their formation. Using an intramolecular peptide hydrogen bond as an example, we studied the effect of the solvent on its parameters. In particular, we showed that hydrogen bond formation with a proton-acceptor group of the chelate ring leads to a decrease in the resonance integral, and consequently a decrease in the enthalpy of formation of the intramolecular hydrogen bond, to a significantly greater degree than formation of a hydrogen bond at a proton-donor group. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 735–740, November–December, 2006.     

Multiple-quantum magic-angle spinning NMR with cross-polarization: Spectral editing of high-resolution spectra of quadrupolar nuclei

An experiment is presented that combines the multiple-quantum magic-angle spinning (MQMAS) technique with cross-polarization (CP). As a preliminary test of this new method, we measured and compared the ²⁷Al 3QMAS and ¹⁹F → ²⁷A1 CP 3QMAS spectra of a fluorinated AlPO₄ aluminophosphate. Complete discrimination between the fluorinated and nonfluorinated Al sites was easily achieved, which demonstrates the usefulness of CP MQMAS for spectral editing. Future applications of this experiment will include other spin pairs and heteronuclear correlation NMR spectroscopy.     

Effect of initial-state target polarization on the single ionization of helium by l-keV electron impact

We report new results of triple differential cross sections for the single ionization of helium by 1-KeV electron impact at the ejection energy of 10 eV. Investigations have been made for both the perpendicular plane and the plane perpendicular to the momentum transfer geometries. The present calculation is based on the threewCoulomb wave function. Here we have also incorporated the effect of target polarization in the initial state. A comparison is made between the present calculation with the results of other theoretical methods and a recent experiment [Diirr M, Dimopoulou C, Najjari B, Dorn A, Bartschat K, Bray I, Fursa D V, Chen Z, Madison D H and Ullrich J 2008 Phys. Rev. A 77 032717]. At an impact energy of 1 KeV, the target polarization is found to induce a substantial change of the cross section for the ionization process. We observe that the effect of target polarization plays a dominant role in deciding the shape of triple differential cross sections.     

Linewidth Analysis of Spin Labels in Liquids: I. Theory and Data Analysis

We present a method of simulating the EPR spectra of spin labels in liquids using direct convolution of hyperfine splitting with Lorentzian linewidths. The aim is to simulate the experimental lineshape by considering all spectrometer characteristics as well as inhomogeneous and homogeneous linewidth effects. A major advance in this method is the correction for the broadening produced by Zeeman modulation commonly used to obtain EPR signals; this allows experimenters much more freedom to optimize their experimental conditions for the best signal-to-noise ratio. Microwave power broadening (saturation) effects on the EPR lines are significant even at very low observer levels. Successful simulation requires that all contributions from unresolved hyperfine splittings be explicitly included. Inhomogeneous broadening is dealt with by including all spins that interact with the electron (as a set of superhyperfine interactions); there is no "effective Gaussian" to substitute for the correct superhyperfine interactions. The effects of spin exchange on the linewidth and lineshape can be observed and must be taken into account in order to extract the fundamental linewidths.     

Effect of initial-state target polarization on the single ionization of helium by 1-keV electron impact

We report new results of triple differential cross sections for the single ionization of helium by 1-KeV electron impact at the ejection energy of 10 eV. Investigations have been made for both the perpendicular plane and the plane perpendicular to the momentum transfer geometries. The present calculation is based on the three-Coulomb wave function. Here we have also incorporated the effect of target polarization in the initial state. A comparison is made between the present calculation with the results of other theoretical methods and a recent experiment [Drr M, Dimopoulou C, Najjari B, Dorn A, Bartschat K, Bray I, Fursa D V, Chen Z, Madison D H and Ullrich J 2008 Phys. Rev. A 77 032717]. At an impact energy of 1 KeV, the target polarization is found to induce a substantial change of the cross section for the ionization process. We observe that the effect of target polarization plays a dominant role in deciding the shape of triple differential cross sections.     

Analysis and Implications of Transition-Band Signals in High-Resolution NMR

The problem of signals generated in and received from regions outside the active coil area is discussed in the context of using standard measurement techniques. Some of the conceptual and practical consequences of the existence of such transition-band signals are highlighted. Examples include radiation damping, pulse-width calibration, lineshape and radiofrequency homogeneity tests, improper saturation, and exchange- and relaxation-rate determinations. One interesting implication is that apparent sample-to-sample variations in the calibrated 90° pulse width values are a function not only of probe tuning and bulk susceptibility effects, but also of the linewidths involved. A semi-quantitative treatment of the phenomenon is also given.     

The fractal nature of molecular trajectories in fluids

The scaled lengths of molecular trajectories obtained by molecular dynamics simulation of a hard-sphere fluid are shown to have the same fractal dimensionD=2 as the random walk. Self-similarity first appears on length scales typically a factor of 25 greater than the mean free-path length, whereas for the simple random walk with constant step size the onset occurs after only six steps; the reason for the slow convergence is shown to be the near exponential distribution of intercollision path lengths of the fluid molecules. The influence of density on the scaled path lengths is also discussed.     

Calculation of soft x-ray emission spectra of aluminium by APW method

In this paper an ab initio calculation of the shapes of emission bandsK andL _{2, 3} of aluminium is described, which is based on the band structure recently determined by the APW method [1]. The expression for the transition probability is derived under the assumption that wave functions of valence electrons are linear combinations of APW functions, whereas wave functions of core electrons are approximated by Bloch sums of atomic functions. A method analogous to that of Gilat and Raubenheimer is used to determine the shapes of spectra. The influence of transition probability and Auger effect are discussed, and the results of calculations are compared with experimental data.     

Calculation of the intensity and dichroism of the IR absorption bands of oriented polymers

An algorithm for calculating the intensity and dichroism of polarized IR absorption bands of oriented polymers is proposed. The absorption curves in the IR spectrum of amorphous cis-1,4-polyisoprene and the dichroism of its absorption bands have been calculated. The polarization IR spectra of oriented amorphous cis-1,4-polyisoprene for a stretching ratio equal to 3 have been constructed. The calculated values of the absorption-band dichroism are in fairly good agreement with the experimental data.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 129–132, January–February, 2005.     

Calculation of self-sputtering spectra of thin films by the discrete flow method

Self-sputtering of plane-parallel layers is described theoretically on the basis of the invariant immersion method combined with the discrete flow technique. Differential equations are derived for forward and backward self-sputtering functions, and exact solutions to these equations are obtained. Energy distributions of self-sputtered ions are calculated; total self-sputtering coefficients are compared to the results of computer experiment. The dependences of the total self-sputtering coefficients on the film thickness and the initial energy of ions are analyzed.