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  • 11
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 4827-4835 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photoisomerization of cis-stilbene in liquid solution was studied by time-resolved excited-state absorption spectroscopy using 306 nm pump and 612 nm probe pulses of 100 fs width. Transient absorption signals were found to decrease exponentially with time. Decay rate constants were determined over the pressure range 1–4000 bars at temperatures of 295 and 390 K in a series of alkane solvents as well as in methanol, acetonitrile, and in polymethylmethacrylate (PMMA). The viscosity dependence confirms the existence of two pathways of the reaction, one leading to ground-state cis- and trans-stilbene (C/TS), the other to dihydrophenanthrene (DHP). Whereas the DHP component shows only little viscosity dependence up to 4 kbar, the C/TS component is characterized by rate constants which are inversely proportional to the solvent viscosity. This is in contrast to earlier conclusions from studies with solvents at 1 bar. The C/TS process shows practically no temperature dependence apart from that of the viscosity, whereas the DHP process has an apparent activation energy of 8.5 kJ mol−1. The results are interpreted in terms of a Kramers–Smoluchowski equation for low-barrier processes as well as by solvent modifications of the low-barrier potential. Alternative interpretations by rate theory for barrierless processes are considered as well.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 4805-4816 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photoisomerization of diphenylbutadiene was studied by picosecond absorption spectroscopy over wide pressure and temperature ranges in liquid and supercritical alkanes, CO2, SF6, and He. The reaction shows typical features of a thermal unimolecular reaction on the S1 potential energy surface. The rate can be expressed by a combination of standard unimolecular rate theory and Kramers–Smoluchowski theory. However, multidimensional behavior manifests itself in the transition to the gas phase low pressure range as well as to the high density Kramers–Smoluchowski range: in the former case, the low pressure limit of a unimolecular reaction of the polyatomic molecule is approached; in the latter case, the effective imaginary barrier frequency shows a marked apparent temperature dependence. The experiments also suggest contributions of reactant–solvent cluster interactions, which modify the barrier height even in nonpolar solvents.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 3283-3291 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rayleigh–Brillouin spectra of aqueous solutions of hydroxyl ammonium nitrate (HAN) and triethanol ammonium nitrate (TEAN) were studied at atmospheric pressure over a temperature range from 205 to 298 K. The hypersonic velocity and absorption coefficient of the phonons were calculated from the spectra as a function of temperature. The absorption due to viscosity and internal energy exchange through the relaxation mechanisms were considered. We find that both mechanisms are responsible for the absorption, but at the lower temperature, the one related to internal energy dominates. The free volume model was used to estimate the activation energy. This value is quite consistent with values calculated from the relaxation time. The effects of relaxation and the water concentration on mixtures of aqueous solutions of HAN and TEAN are also discussed.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 2393-2404 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The pressure and temperature dependence of the photoisomerization rate coefficient of trans-stilbene in the S1 state have been measured in the solvents C2H6, C3H8, C4H10, Xe, Co2, SF6, and CHF3. At constant temperature, the pressure dependences up to 6 kbar can be well represented by the Kramers–Smoluchowski model. The comparison of results in different solvents clearly indicates the importance of reactant–solvent cluster formation modifying the height and imaginary frequency of the barrier. The change of the temperature dependence with pressure points towards a multidimensional barrier of nonseparable character. Multidimensional barrier effects manifest themselves most clearly via the temperature dependence of the rate coefficient in the Kramers–Smoluchowski limit.
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 91 (2002), S. 3205-3212 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Dielectric potting materials (encapsulants) are used to prevent air breakdown in high-voltage electrical devices. We report breakdown strengths in void-filled encapsulants, stressed with unipolar voltage pulses of the order of 10 μs duration. High strengths, on the order of 100 kV mm−1, are measured under these test conditions. The materials studied include low-density open celled gel-derived foams with cell sizes of 4 μm or less, closed celled CO2-blown polystyrene and urethane foams, and epoxies containing 48 vol % of hollow glass microballoon (GMB) fillers. These last specimens varied the void gas (N2 or SO2) and also the void diameters (tens to hundreds of μm). Our measurements are thought to be directly sensitive to the rate of field-induced ionization events in the void gas; however, the breakdown strengths of the materials tested appeared to vary in direct proportion with the conventional Paschen-law gas-discharge inception threshold, the electric stress at which gas-ionization avalanches become possible. The GMB-epoxy specimens displayed this type of dependence of breakdown strength on the void-gas density and void size, but the measurements were an order of magnitude above the conventional predictions. Small-celled foams also showed increased breakdown strengths with decreased cell size, although their irregular void geometry prevented a direct comparison with the more uniformly structured microballoon-filled encapsulants. The experimental observations are consistent with a breakdown mechanism in which the discharge of a few voids can launch a full breakdown in the composite material. © 2002 American Institute of Physics.
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  • 16
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 91 (2002), S. 5962-5971 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: We report breakdown strengths in a void-filled dielectric material, epoxy containing 48 vol % hollow glass microballoon filler, which is stressed with unipolar voltage pulses of the order of 10 μs duration. The microballoon voids had mean diameters of approximately 40 μm and contained SO2 gas at roughly 30% atmospheric pressure. This void-filled material displays good dielectric strength (of the order of 100 kV mm−1) under these short-pulse test conditions. Results from a variety of electrode geometries are reported, including arrangements in which the electric stress is highly nonuniform. Conventional breakdown criteria based on mean or peak electric stress do not account for these data. A statistics-based predictive breakdown model is developed, in which the dielectric is divided into independent, microballoon-sized "discharge cells" and the spontaneous discharge of a single cell is presumed to launch full breakdown of the composite. We obtain two empirical parameters, the mean and standard deviation of the spontaneous discharge field, by fitting breakdown data from two electrode geometries having roughly uniform fields but with greatly differing volumes of electrically stressed material. This model accounts for many aspects of our data, including the inherent statistical scatter and the dependence on the stressed volume, and it provides informative predictions with electrode geometries giving highly nonuniform fields. Issues related to computational spatial resolution and cutoff distance are also discussed. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Science Ltd
    Journal of neurochemistry 82 (2002), S. 0 
    ISSN: 1471-4159
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Medicine
    Notes: The motor signs of Parkinson's disease have been partly attributed to an overinhibition of the external globus pallidus (GP) that results from hyperactivity of striatopallidal GABA/enkephalinergic neurons. The goals of this study were to measure basal levels of extracellular fluid GABA in the GP of normal cats, 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP)-treated parkinsonian cats and cats spontaneously recovered from MPTP-induced parkinsonism, and to examine the effects of opioid receptor activation on potassium (K+)-evoked GABA release in the GP in these animals. Basal GP GABA levels were increased 75% from normal in parkinsonian animals 1 week after MPTP administration and returned to control levels in recovered animals 6 weeks afterMPTP administration. No significant differences were observed in K+-evoked GABA release across conditions. The opioid receptor agonist [D-Ala2]-Met-Enkephalinamide (DALA) significantly attenuated K+-evoked GABA release in the GP of MPTP-treated symptomatic and recovered cats, but had no significant effect on GABA release in normal animals. These data show that basal GP GABA levels are elevated coincident with expression of parkinsonian signs and return to normal in animals that have functionally compensated for a nigrostriatal lesion. DALA-induced inhibition of pallidal GABA release after a dopamine-depleting lesion, suggests that enkephalin may attenuate GABA release in the GP specifically after striatal dopamine loss.
    Type of Medium: Electronic Resource
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  • 18
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of agricultural and food chemistry 17 (1969), S. 791-795 
    ISSN: 1520-5118
    Source: ACS Legacy Archives
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 19
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of agricultural and food chemistry 17 (1969), S. 796-798 
    ISSN: 1520-5118
    Source: ACS Legacy Archives
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 86 (1964), S. 5235-5239 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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