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  • 1995-1999  (1)
  • 1990-1994  (2)
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  • 1
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 1607-1613 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Dielectric relaxation studies have been made on a series of dialkyl esters of phthalic acid over a frequency range of 20 Hz to 1 MHz and over a temperature range of 77 to 573 K. Studies have also been made above room temperature (up to 363 K) at microwave frequencies of 5.3, 10, and 32 GHz. All the samples in their supercooled liquid state reveal yet another process in addition to the primary or α process. Careful measurements have been made to resolve the secondary or β process from the α process at temperatures above Tg. The activation energy of the β process decreases from 39 KJ/mole to 20 KJ/mole with increase in the size of the alkyl group. It is also noted that the bifurcation of liquid relaxation into α and β processes occurs at much higher temperature with increase in the alkyl group. A sharp increase with temperature in the magnitude of the β process in the vicinity of the glass transition Tg temperature, is noted. The relevance of these observations to glass formation in liquids is discussed.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 5362-5368 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The nature of the glass transition process in six monohydroxy alcohols, viz., the isomers of butanol, 2-propanol, and 3-methyl–1-butanol had been studied in detail using dielectric spectroscopy (frequency range 10+6–10−3 Hz) and differential scanning calorimetry (DSC). Measurements were made down to a temperature of 77 K in dielectric experiments and a temperature of 95 K in DSC. These results together with the published microwave data on these liquids reveal the existence of two glass transition processes—one due to the hydrogen bonded network which is very dominant and the other one due to the nonhydrogen bonded molecules, which is much weaker. Associated with the latter process, there is a secondary (or β-) relaxation process whose activation energy varies from 4.8 to 6.7 kcal/mol which is dependent on the shape and size of the liquid molecules. In addition to the β process, all the alcohols revealed yet another sub-Tg (γ) process whose activation energy varies from 2.1 to 2.6 kcal/mol and is found to be little dependent on the molecular shape. These results perhaps indicate that the β process is somehow connected to the relaxation of the free monomeric molecule and the γ process to that of hydroxyl group rotation, respectively.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 1245-1250 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Using molecular orbital approach and the generalized gradient approximation in the density functional theory, we have calculated the equilibrium geometries, binding energies, ionization potentials, and vertical and adiabatic electron affinities of SinOm clusters (n≤6,m≤12). The calculations were carried out using both Gaussian and numerical form for the atomic basis functions. Both procedures yield very similar results. The bonding in SinOm clusters is characterized by a significant charge transfer between the Si and O atoms and is stronger than in conventional semiconductor clusters. The bond distances are much less sensitive to cluster size than seen for metallic clusters. Similarly, calculated energy gaps between the highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) of (SiO2)n clusters increase with size while the reverse is the norm in most clusters. The HOMO-LUMO gap decreases as the oxygen content of a SinOm cluster is lowered eventually approaching the visible range. The photoluminescence and strong size dependence of optical properties of small silica clusters could thus be attributed to oxygen defects. © 1998 American Institute of Physics.
    Materialart: Digitale Medien
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