Molecular mobility of nitroxide spin probes in glassy polymers. Quasi‐libration model

ESR spectra of three spin probes with different molecular volumes: 2,2,6,6‐tetramethyl‐4‐oxopiperidine‐1‐oxyl, di‐p‐anisylnitroxide, and nitroxide derivative of fullerene in glassy polystyrene, polyvinyl trimethylsilane, and Teflon AF‐2400 were calculated numerically within the model of quasi‐libration motions. Temperature ranges, where the model is capable to reproduce spectra within experimental errors, were defined. It was found that simulation of X‐band ESR spectra allows to determine quasi‐libration amplitudes around molecular axes X and Y with accuracy ～ 3° and around Z axis with accuracy ～ 15–20°. A shape of distribution of quasi‐libration amplitudes was also determined qualitatively by ESR spectra simulations. It was established that the average amplitude of quasi‐libration motion depends on the free volume of each polymer and geometrical molecular volume of a spin probe. Quasi‐libration amplitudes increase as the temperature increases, and reach the value of 40 degrees. We found that upon further temperature increase, quasi‐libration model becomes inapplicable for quantitative numerical spectra simulation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 107–120, 2009     

Optical properties of carbon nanotubes and BaTiO3 composite thin films

Multiwalled carbon nanotubes and BaTiO₃ composite films have been prepared by pulsed-laser deposition technique at room temperature and high temperature of 600℃, separately. The structures of the composite films are investigated by using scanning electron microscopy and x-ray diffraction. The optical behaviours of the samples produced at different temperatures are compared with Raman spectroscopy, and UV-visible absorption. And the observation by Z-scan technique reveals that the composite films have a larger optical nonlinearity, and the samples prepared at high temperatures have better transmittance and opposite sign imaginary part of optical third-order nonlinearity.     

Molecular mechanics (MM4) calculations on carbonyl compounds part I: aldehydes

Aliphatic aldehydes have been studied with the aid of the MM4 force field. The structures, moments of inertia, vibrational spectra, conformational energies, barriers to internal rotation, and dipole moments have been examined for six compounds (nine conformations). MM4 parameters have been developed to fit the indicated quantities to the wide variety of experimental data. Ab initio (MP2) and density functional theory (B3LYP) calculations have been used to augment and/or replace experimental data, as appropriate. Because more, and to some extent, better, data have become available since MM3 was developed, it was anticipated that the overall accuracy of the information calculated with MM4 would be better than with MM3. The best single measure of the overall accuracy of a force field is the accuracy to which the moments of inertia of a set of compounds (from microwave spectroscopy) can be reproduced. For all of the 20 moments (seven conformations) experimentally known for the aldehyde compounds, the MM4 rms error is 0.30%, while with MM3, the most accurate force field presently available, the rms error over the same set is 1.01%. The calculation of the vibrational spectra was also improved overall. For the four aldehydes that were fully analyzed (over a total of 78 frequencies), the rms errors with MM4 and MM3 are 18 and 38 cm^?1, respectively. These improvements came from several sources, but the major ones were separate parameters involving the carbonyl carbon for formaldehyde, the alkyl aldehydes and the ketones, and new crossterms featured in the MM4 force field that are not present in the MM3 version. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1396–1425, 2001     

Novel Coordination Polymers Constructed from 4,4'-Bipyridine and Phosphate

The synthesis of open-fiamework metal phosphates has been a subject of intense research owing to their interesting structural chemistry and potential applications as ionexchangers, catalysts and adsorbents. A large number of these materials are synthesized in the presence of organic amines as structure-directing agents. Recently, many research activities have focused on the synthesis of inorganic-organic hybrid frameworks. As compared with inorganic ligands, the advantage of using organic multidentate ligands is the efficacy of rational design of crystalline solids through their coordinating propensities and geometries.     

Intensities of infrared bands in molecular mechanics (MM3)

The MM3 molecular mechanics program calculates a fair representation of vibrational frequencies for molecules. To make this information more useful, a qualitative intensity calculation has been added, as is described herein. Because each bond in the molecule is assigned a dipole moment, and the vibrational amplitudes are known from the frequency calculation, the change in dipole moment corresponding to each normal mode is readily calculated. In some cases a charge flux has to be added empirically for bond stretchings. This relatively simple calculation has been applied to a number of different functional groups, and gives band intensities adequate for dividing the bands into very strong, strong, medium, weak, or very weak (forbidden) categories. © 1992 by John Wiley & Sons, Inc.     

An approximate maximum likelihood estimation for non-Gaussian non-minimum phase moving average processes

An approximate maximum likelihood procedure is proposed for the estimation of parameters in possibly nonminimum phase (noninvertible) moving average processes driven by independent and identically distributed non-Gaussian noise. Under appropriate conditions, parameter estimates that are solutions of likelihood-like equations are consistent and are asymptotically normal. A simulation study for MA(2) processes illustrates the estimation procedure.     

Estimation for a class of nonstationary processes

Random processes with almost periodic covariance function are considered from a spectral outlook. Given suitable conditions, spectral estimation problems are discussed for Gaussian processes of this type that are neither stationary nor locally stationary. Spectral mass is concentrated on lines parallel to the main diagonal in the spectral plane. A method of estimation of the support of spectral mass under appropriate restraints is considered. Some open questions are discussed. Extension of the methods for a class of nonGaussian nonstationary processes with mean value function a trigonometric regression is given. Consistent estimates for frequency, amplitude and phase of the regression are noted when the residual process is zero mean almost periodic. The resulting estimation of the spectral mass of the residual is also considered.