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  • Wiley-Blackwell  (33)
  • 1
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quantum-chemical calculation of the energies of the electronic transitions and the electronic structures of the neutral and ionic species of the nucleic acids components in their ground and lower excited singlet and triplet ππ* and nπ* states has been carried out in the all-valence-electron approximation CNDO/S. The results of the calculation allow one to identify the most photoreactive sites of the molecules and to consider the dependence of the location of these sites on the ionic state of the molecules. The calculated data are compared with our previous results obtained in a π-electron approximation. The individual absorption spectra of various ionic and tautomeric species of the nucleic acids components obtained by us earlier have been decomposed into bands corresponding to separate electronic transitions. As a rule, there is a good agreement between the calculated data in the two approximations and the experimental results.
    Additional Material: 1 Ill.
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  • 2
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The individual absorption spectra of various ionic and tautomeric species of some derivatives of nucleic-acid components have been determined by computer handling of the summary spectra of these compounds measured at different pH values. These individual spectra have been decomposed into separate bands represented by log-normal curves and corresponding to different electronic transitions. Using the parameter system calculated earlier for the molecules of the vitamin B6 family, the calculation of the electronic spectra and electronic structure of various ionic and tautomeric species of the molecules studied have been carried out in the π-electron approximation. These properties have also been calculated by the all-valence electronic method CNDOS. The calculated results correlate well with both approximations and with our experimental spectral data. The localization of the molecular electronic excitation studied on the transition to the S1 and T1 states is considered in connection with the reactivity in these states.
    Additional Material: 2 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 34 (1988), S. 59-69 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Correlation energies are divided into two parts. One contribution is given by a configuration interaction calculation in the space of the natural orbitals with occupation numbers larger than an arbitrary threshold v. The remaining part is obtained from a v-dependent functional of the electronic density. Representative examples (for which the existing spin-density functionals fail) are (1) the correlation energies in the He and Be series and (2) the contribution of the correlation energy to the dissociation energy of the first-row dimers. It is shown that even for large values of v the errors remain on the order of 0.01 hartree.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 327-332 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Short-range nonclassical electron-electron interaction is described by a density functional in a scheme that allows multideterminant wave functions. The parameter that determines the coupling with the configuration-interaction-type calculations can be chosen in a controlled manner. Results are presented for the He and the Be series using a Yukawa-type interaction. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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  • 5
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a spectrokinetic approach the absorption spectra of the short-lived transient products in the enzymatic reaction of the glutamate decarboxylase with natural substrate are determined for the first time. The quantum-chemical calculations of the electronic structure and spectra of various ionic species of numerous vitamin B6 derivatives allowed a hypothesis on the nature of the intermediate products detected to be suggested. A model of the enzyme functioning taking into account the charge equilibria and some electronic-conformational relations is proposed.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 18 (1997), S. 1431-1439 
    ISSN: 0192-8651
    Keywords: electron localization function ; core-valence separation ; d electrons ; valence density ; Pauh kinetic energy density ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: The electron localization function (ELF) shows too-high values when computed from valence densities only (instead of using the total density). This effect is mainly found when d electrons are present in the outermost shell of the core. Although no pronounced qualitative differences could be noticed in the examples studied up to now, it is found that the quantitative differences between the values of ELF obtained from the valence densities only or from the total densities can be large. We also show, for the first time, an example (the Be atom) where ELF is obtained directly from the density. This exemplifies the possibility of computing ELF from highly accurate calculations (or from experimental data).   © 1997 John Wiley & Sons, Inc.   J Comput Chem 18: 1431-1439, 1997
    Additional Material: 14 Ill.
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  • 7
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Based on a dynamical lifetime concept a method for calculating the force and energy parameters of degradation of stressed polymer chains was developed. By this approach the failure is considered to be caused by vibration instabilities, the frequency of self-consistent phonons aquiring complex values at a critical stress. By various approximations the anharmonic effects are stepwise taken into account with respect to interatomic interactions as well as thermal atomic vibrations. The separation of anharmonic effects into force and temperature effects is suggested to be correct in quasiharmonic approximation only. The consideration of phonon damping results, without changing the qualitative features of the formation of instabilities, in decreasing critical stress and activation energy of chain degradation as compared with the pseudoharmonic approximation in which the degradation process of phonon excitation is not considered. The phonon damping, fluctuation volume of elementar failure and stress concentration coefficient are calculated. Satisfying agreement with the experimental results was achieved.
    Notes: Auf der Grundlage von dynamischen Betrachtungen zur Beständigkeit wurde eine Methode zur Berechnung der Kraft- und Energieparameter des Zerfalls von gespannten Polymerketten vorgeschlagen. Bedingung für den Bruch ist bei dieser Herangehensweise die Entstehung einer Schwingungsinstailität, wobei die Frequenz der „self-consistent“- Phononen bei einer kritischen Spannung komplex wird. In verschiedenen Näherungen werden schrittweise die anharmonischen Effekte berücksichtigt, sowohl in bezug auf die interatomaren Wechselwirkungskräfte als auch in bezug auf die thermischen Atomschwingungen. Es wird festgestellt, daß die Unterteilung der Anharmonie in eine Kraft-und eine Temperaturanharmonie nur in quasiharmonischer Näherung richtig ist. Die Berücksichtigung der Phononendämpfung führt, ohne das qualitative Bild der Entstehung einer Instabilität zu ändern, zu einer Verringerung der kritischen Spannung und der Aktivierungsenergie für den Zerfall der Polymerkette im Vergleich zu der die Zerfallsprozesse der Phononenanregungen nicht berücksichtigenden pseudoharmonischen Näherung. Die Phononendämpfung, das Fluktuationsvolumen des elementaren Bruchaktes und der Spannungskonzentrationskoeffizient werden berechnet. Der Vergleich mit experimentellen Resultaten ergibt eine gute Übereinstimmung.
    Additional Material: 4 Tab.
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  • 8
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The PMR spectrum recorded during the reaction of tert-butylmagnesium chloride with p-chlorophenyl diazonium tetrafluoborate shows the CIDNP effect in the spectra of the the reaction products. Enhanced absorption and emission (the multiplet effect) has been observed for the protons of the vinyl group of isobutylene and the methyl protons of isobutane. The reaction of these diazonium salts with benzylmagnesium chloride results in only one polarised product, chlorobenzene. Such a polarisation proves the radical mechanism of the reaction which started with one-electron transfer from the Grignard reagent to the diazonium salt.
    Additional Material: 2 Ill.
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  • 9
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 109 (1997), S. 2168-2170 
    ISSN: 0044-8249
    Keywords: Ab-initio-Rechnungen ; Elektronenlokalisierung ; Elektronenstruktur ; Hypervalente Verbindungen ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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