Непрерывное фармакологическое образование при подготовке врачебных кадров

ОБРАЗОВАНИЕ МЕДИЦИНСКОЕВУЗЫМЕДИЦИНСКИЕ УЧЕБНЫЕ ЗАВЕДЕНИЯОБРАЗОВАНИЕ ФАРМАЦЕВТИЧЕСКОЕ, ПОВЫШЕНИЕ КВАЛИФИКАЦИИ /МЕТОДЫНЕПРЕРЫВНОЕ ФАРМАКОЛОГИЧЕСКОЕ ОБРАЗОВАНИЕМЕДИЦИНСКИЕ КАДР

The vibrational spectra of methyl groups in methylthiolate and methoxy adsorbed on Cu(100)

We show that the difference in the infrared vibrational spectrum of C-H stretch modes arising from the methyl group of two surface intermediates, methylthiolate and methoxy, originates from the difference in the methyl deformation modes frequencies of the two intermediates. Importantly, while the vibrational fingerprint of the two methyl groups are not transferable between the intermediates, the Fermi resonance coupling constants of the methyl group are

Surface adsorbate vibrations explored by infrared spectroscopy and DFT cluster calculations at the anharmonic level: CO on Cu(100).

The vibrational properties of the CO/Cu(100) surface adsorbate system have been explored by infrared spectroscopy and DFT cluster calculations. We show that all four fundamental, FT(x,y), FR(x,y), FT(z) and ν(C-O), vibrational modes are very well reproduced with respect to experiments by the present calculations and they are at the highest level reported to date. Our work demonstrates that it is essential to include both anharmonicity and cluster relaxation when modeling the CO/Cu(100) system. The absence and presence of binary modes: 2 ×ν(C-O) and FT(z) + ν(C-O) in our experimental data are discussed as well

New scale factors for harmonic vibrational frequencies using the B3LYP density functional method with the triple-xi basis set 6-311+G(d,p)

We have calculated optimal frequency scaling factors for the B3LYP/ 6-311+G(d,p) method for fundamental vibrational frequencies on the basis of a set of 125 molecules. Using the new scaling factor, the vibrational frequencies calculated with the triple-zeta basis set 6-311+G(d,p) give significantly better accuracy than those calculated with the double-zeta 6-31G(d) basis set. Scale factors were also determined for low-frequency vibrations using the molecular set of 125 molecules and for zero-point energies using a smaller set of 40 molecules. We have studied the effect on the calculated vibrational frequencies for various combinations of diffuse and polarization functions added to the triple-zeta 6-311G basis set. The 6-311+G(d,p) basis set is found to give almost converged frequencies for most molecules, and we conclude that our optimum scaling factors are valid for the basis sets 6-311 G(d,p) to 6-311++G(3df,3pd). The new scale factors are 0.9679 for vibrational frequencies, 1.0100 for low-frequency vibrations, and 0.9877 for zero-point vibrational energies

Complex Formation of Small Molecules during Isolation in Low Temperature Matrices: Water Dimers in p-H-2 and Ne Matrices

The concentrations of water dimer are compared in Ne and p-H-2 matrices at low temperatures, using infrared spectroscopy. Additional data are given for o-D-2 and Ar matrices. For a given monomer concentration, the dimer concentration is significantly higher in solid Ne (or Ar) than in solid p-H-2. In p-H-2, the dimer concentration is only slightly higher than expected for a random distribution of water in the matrix. The dimer concentration in o-D-2 matrices is intermediate between p-H-2 and noble gas matrices. This strongly suggests that most dimers form on the surface of the growing matrix, and not as the result of diffusion in the bulk of the matrix

Rotation of Water in Solid Parahydrogen and Orthodeuterium.

The far-infrared spectra of solid orthodeuterium and solid normal deuterium are presented and compared to the corresponding spectra of solid parahydrogen and solid normal hydrogen. Spectra of water in orthodeuterium are compared to spectra of water in parahydrogen. The water rotation constants in orthodeuterium are approximately 80% of the rotation constants of water in parahydrogen. The S(0)(0) band of orthodeuterium gets a strong satellite in the presence of water. The position and width of the satellite depends on the isotopic composition of the water present. If there is a corresponding satellite in parahydrogen it is weak and closer to the S(0)(0) band of the matrix. The conclusion of the paper is that interaction between guest rotation and the rotation of matrix molecules must be taken into account to explain the reduction of the rotation constants in orthodeuterium

First-Principle Calculations of the Experimental Vibrational Spectrum of a Surface Adsorbate: Anharmonic Resonance Coupling between Fundamental and Binary Modes.

By including relevant physical properties in our modeling of a surface adsorbate system we can, from first principles, correctly calculate all experimentally observed features in the vibrational spectrum of CH3CH2O– and CD3CH2O– adsorbed on Cu(100). That is, we reproduce the number of observed modes, the vibrational frequencies, and intensities of the modes including the presence/absence of binary overtone and combination modes. No scaling was performed. Our calculations show that the anharmonic terms of the potential energy surface of free ethanol are transferrable to the corresponding surface adsorbate, ethoxy, while the harmonic terms are not. ©2003 The American Physical Societ