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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 4077-4092 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ultraviolet photoelectron spectroscopy (UPS) has been applied to the investigation of the electronic structure of oligothiophenes with 4–8 thiophene rings. In a series of α-linked oligomers (αn with n being the number of rings), a systematic evolution of the π band is observed. Several peaks which correspond to the π band are observed in the region of 0.7–3 eV below the Fermi level (EF), and the bandwidth becomes broader with increasing n. The nonbonding π band is observed at 3.5 eV below EF and its energy is almost independent of the number of thiophene units. UPS spectra of α7 and α8 are fairly similar to the spectra of polythiophene, showing that these oligomers are good model compounds of the polymer. The ionization threshold energy of α7 and polythiophene was observed to be 5.3 eV. The effect of irregularity on the π-electron system was also studied by using oligomers which contain a β linkage or a vinylene group at the middle of the molecule. The UPS spectra showed that the β linkages significantly affect the electronic structure of polythiophene, while the vinylene group does not. In order to analyze the UPS spectra and to investigate the electronic structures of oligomers, the orbital energies and the geometries of these oligomers are calculated by the semiempirical MNDO-SCF-MO (modified neglect of diatomic overlap self-consistent-field molecular orbital) method. Theoretically simulated spectra of these oligothiophenes derived from the obtained orbital energies by Gaussian broadening are compared with the observed ones. The agreement between the observed and calculated spectra is very good, particularly in the π region. It is shown from the optimized geometry that (1) αn 's have planar structure and π electrons are delocalized, (2) the oligomer with β linkages has nonplanar structure leading to limited delocalization of π electrons, and (3) the oligomers with a vinylene group are almost planar and the disturbance by the vinylene group on the delocalization is small.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 1198-1199 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Oxford, UK; Malden, USA : Blackwell Science Ltd
    European journal of soil science 56 (2005), S. 0 
    ISSN: 1365-2389
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Natural wetlands are a significant source of atmospheric methane, an important greenhouse gas. Compared with numerous papers on measurements of methane emission from natural wetland surfaces, there are few reports on methane configuration and distribution within wetland soil profiles. By using a newly designed gas sampler, we succeeded in collecting free-phase gas from beneath the water table down to 120 cm in a peat. The volumetric percentage of methane in the gas phase increased with depth and was generally more than 50% beneath the zone within which the water table fluctuates. The volume of the gas phase in the peat beneath the water table was estimated to be from 0 to 19% with significant variation with depth, suggesting uneven distribution of gas bubbles. Using the volume ratio of the gas and liquid phases and methane concentration data in the gas phase, as well as assuming that methane was in equilibrium (based on Henry's Law between the two phases), we calculated that ∼60% of the methane accumulates in the form of bubbles. These results suggest the importance of ebullition in methane emission, which might be a major cause for the reportedly large variation of methane emission in both space and time. Most importantly, our results show the need to consider gaseous-phase methane for understanding the production, transport and emission mechanisms of methane in wetlands, which has been overlooked to date.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Electronic structures of 5, 10, 15, 20-zinctetraphenylporphyrin (ZnTPP)/metal (Au, Ag, Al, Mg) interfaces prepared in ultrahigh vacuum were investigated by ultraviolet photoelectron spectroscopy (UPS). We found that the electronic energy levels of ZnTPP align to the vacuum level of substrate metal, with a constant energy shift of vacuum levels across the interface. These findings cannot be explained by the simple models assuming vacuum level alignment at the interface. We also found that sample exposure to oxygen induces energy level shift in close relation with change of substrate work function at oxygen exposure. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 69 (1996), S. 1059-1061 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: In order to clarify electronic structures of molecular semiconductor/metal interfaces, a Schottky–Mott rule is examined for vacuum-sublimed films of two kinds of porphyrins, which have similar chemical structures, but opposite conductance types. The result shows that Schottky barrier heights are simply determined by the difference in work function between the porphyrin solids and metals irrespective of the conductance types of the porphyrin semiconductors, indicative of negligible influence of surface states on the Schottky barrier formation. Measurements of photocurrent generation efficiencies at these Schottky junctions indicate that a surface recombination process is not a major deactivation route for electron-hole pairs generated in the molecular semiconductors by light. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 1332-1337 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 2849-2862 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: For electron transfer (ET) reactions in liquid media, it is not uncommon to find that the stereoselectivity, mutual orientations, conformational fluctuations, spin multiplicity restrictions of the reacting system may kinetically limit its reactivity. We assume that the system in question can stochastically interconvert between reactive (open gate) and nonreactive (closed gate) states at rates competitive with diffusion-influenced ET, and refer to this kind of reaction as stochastically gated diffusion-influenced ET reactions. We utilize the Zhou and Szabo model of stochastically gated diffusion-influenced reactions in order to study the effect of such stochastic fluctuations of reactivity on the transient kinetics of fluorescence quenching in through-solvent photoinduced ET reaction. Different types of transient kinetics, fluorophore gated vis-a-vis quencher gated, are demonstrated in terms of survival probability of the fluorophore, which shows that the analysis of experimental results ignoring such phenomena can be dramatically in error. Approximate analytical solutions of the theory based on projection operator formalism are presented. The exact numerical results including the role of liquid structure and the hydrodynamic hindrance of fluorophore-quencher diffusion rates are found to compare extremely well with the results obtained from a molecular dynamics simulation of the same reaction system. The simulations are based on the rate equations obtained from the first principle. Illustrative calculations and comparisons are presented to demonstrate the competitive interplay between the reaction sink strength, diffusion, and gating rates on the reaction kinetics. A simple method, based on the distribution of ET distance and quantum yield of ET of gateless reactions, is proposed to help delineate the features of such competitive interplay on the asymmetry of the reaction kinetics. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 117 (2002), S. 1377-1384 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report a Brownian dynamics (BD) simulation study of the Förster energy transfer in a dye-labeled Rouse polymer chain. The simulation method is based on the normal mode BD propagation and numerical path integration of the survival probability. It is shown that a properly constructed truncated normal-mode approximation (TNMA) can speed up the simulations considerably, without essential loss of accuracy. In particular, an effective-sink TNMA scheme is found to be quite efficient. The idea is based on a standard time scale separation ansatz, where all the normal modes are separated into slow and fast, in terms of the corresponding relaxation times. The fast normal modes are assumed to be equilibrated in the course of reaction and thus can be integrated out. Their effect is to modify the reaction sink for the slow modes. The first-order approximation can be handled most easily, without a simulation. Even this simple approximation can be preferable to the well-known Wilemski–Fixman approximation, if the reaction sink is wide, i.e., when the Förster radius exceeds the polymer mean bond length, the condition often chosen in experiments on polymer folding. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Analytical Biochemistry 214 (1993), S. 468-473 
    ISSN: 0003-2697
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Biology , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0301-0104
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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