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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    The European physical journal 95 (1994), S. 101-111 
    ISSN: 1434-6036
    Keywords: 05.40.+j ; 02.50.+s
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Starting from the deformed commutation relationsa q (t) a † q (s)−q a † q (s) a q (t)=Γ(t−s)1, −1≦q≦1 with a covariance Γ(t−s) and a parameterq varying between −1 and 1, a stochastic process is constructed which continuously deforms the classical Gaussian and classical compound Poisson process. The moments of these distinguished stochastic processes are identified with the Hilbert space vacuum expectation values of products of $$\hat \omega _q (t) = \gamma (a_q (t) + a_q^\dag (t)) + \xi a_q^\dag (t)a_q (t)$$ with fixed parametersq, γ and ξ. Thereby we can interpolate between dichotomic, random matrix and classical Gaussian and compound Poisson processes. The spectra of Hamiltonians with single-site dynamical disorder are calculated for an exponential covariance (coloured noise) by means of the time convolution generalized master equation formalism (TC-GME) and the partial cumulants technique. The final result for the spectral function is given as aq-dependent infinite continued fraction. In the case of the random matrix processes the infinite continued fraction can be summed up yielding a self-consistent equation for the one-particle Green function.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    The European physical journal 92 (1993), S. 399-407 
    ISSN: 1434-6036
    Keywords: 05.40.+j ; 02.50.+s
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Generalized master equations correspond to different kinds of cumulants. Here, we discuss the recently introduced non-crossing cumulants from a physical point of view and propose the corresponding integro-differential master equation as a new type of equation for a self-consistent treatment of memory effects. We prove the cluster property of the non-crossing cumulants, and show that the Gaussian approximation of our equation is given by a random matrix process. As an instructive example for our expansion formula we treat the random frequency-modulated oscillator.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Fresenius' Zeitschrift für analytische Chemie 292 (1978), S. 97-107 
    ISSN: 1618-2650
    Keywords: Best. von Biphenylen, polychlorierte, Pesticide, chlorhaltig in Fisch ; Chromatographie, Gas ; Capillar, Persistenz
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Summary Besides 83 structurally defined trichloro- to octachloro-biphenyls (PCB), the following chlorinated pesticides have been identified in fish liver oil (DAB 6) and fish liver extracts: HCB;α-HCH;γ-HCH; 2,4′-DDE; 4,4′-DDE; 2,4′-DDT; 4,4′-DDT; 2,4′-DDD; 4,4′-DDD; dieldrin; endrin. By analysing constant relative amounts of PCB-components present only in defined technical PCB-mixtures, the original PCB-pattern in environmental samples could be calculated. A mixture of Clophen A 60/Clophen A50 or of Aroclor 1260/Aroclor 1254 of 2.2∶1 gives the best fit. The constant ratio of four octachloro-biphenyls in technical mixtures and environmental samples as well requires the assumption of complete environmental stability of these compounds despite of any thinkable differences in environmental pathways. This assumption of environmental persistency is supported by a degree of degradation up to 80% of the calculated input observed for some higher chlorinated PCB-components, e.g. 2,2′,3,4,5′,6-hexachloro-biphenyl. Correlating the amount of each identified PCB-component to the octachloro-biphenyl as the internal standard, a correlation of the degradation with the PCB-substitution pattern is possible. Persistency is observed, if vicinal hydrogens are missing or a 4-position is chlorinated. A 4,4′-disubstitution favours persistency most.
    Notes: Zusammenfassung Neben 83 strukturell definierten Trichlor- bis Octachlor-biphenylen (PCB) wurden folgende chlorierte Biocide in Lebertran (DAB6) und Fischleberextrakten identifiziert: HCB;α-HCH;γ- HCH; 2,4′-DDE; 4,4′-DDE; 2,4′-DDT; 4,4′-DDT; 2,4′-DDD; 4,4′-DDD; Dieldrin; Endrin. Aus den Verhältnissen von nur in PCB-Produkten mit bestimmtem Chlorierungsgrad vorkommenden, schwer abbaubaren PCB-Komponenten konnte die ursprünglich in die Umwelt gelangte Zusammensetzung der PCB berechnet werden: eine Mischung aus Aroclor 1260/Aroclor 1254 (Monsanto, USA) oder Clophen A 60/Chlophen A 50 (Bayer, Deutschland) im Verhältnis 2,2∶1 ergibt die beste Näherung. Aus dem in technischen Produkten und den Umweltproben gleichen relativen Vorkommen von vier Octachlor-biphenylen muß auf deren völlige Stabilität unter Umweltbedingungen geschlossen werden. Diese Annahme wird durch den Abbau von bis zu 80% des ursprünglichen Gehalts anderer hochchlorierter Biphenyle, wie des 2,2′,3,4,5′,6-Hexachlor-biphenyls, gestützt. Wird das Vorkommen der identifizierten Chlorbiphenyle, auf die als persistent angenommenen Octachlor-biphenyle als internen Standard bezogen, ergibt sich eine klare Persistenz-Abbau-Beziehung zu dem PCB-Substitutionsmuster. Persistenz ist gegeben bei fehlenden vicinalen Wasserstoffatomen oder 4-Chlorsubstitution, wobei die 4,4′-Di-Substitution die Persistenz am stärksten fördert.
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  • 4
    ISSN: 1618-2650
    Keywords: Analyse von Umweltmaterial, Pesticiden ; Chromatographie, Gas ; Capillar-, Ident. von Einzelkomponenten in komplexen Gemischen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Der Vergleich von präzise bestimmten Retentionsindices von Probe- und Referenzsubstanzen in der hochauflösenden Capillar-Gas-Chromatographie stellt eine aussagekräftige Methode der Identifizierung von Einzelkomponenten in komplexen Gemischen dar. Neben der Konstanz der GC-Parameter erfordert die präzise Bestimmung von Retentionsindices eine sehr genaue Bestimmung der Netto-Retentionszeiten. Insbesondere ist bei Anwendung einer Totzeitberechnung auf der Basis einer erzwungenen Linearisierung der log t s/Homologenzahl-Beziehung auf eine sehr genaue Retentionszeitmessung zu achten. Die Reproduzierbarkeit von präzise bestimmten Retentionsindices hängt von der Konstanz der Polarität und von der Adsorptivität der Capillarsäule ab. An ausreichend desaktivierten und konditionierten Hochleistungs-Capillarsäulen (TZ≥40) können unter der Voraussetzung einer Retentionszeit-Meßgenauigkeit von besser als 0,05% Retentionsindices über einen Zeitraum von mehreren Wochen innerhalb ±0,15 Indexeinheiten reproduziert werden. Eine Übertragung des n-Alkan bezogenen Retentionsindex-Konzeptes auf die homologe Reihe der n-Allkyl-trichloracetate (ATA) ermöglicht die Verwendung des Elektroneneinfang-Detektors (ECD) zur präzisen RetentionsindexBestimmung als Methode einer zuverlässigen Identifizierung von Substanzen im Picogrammbereich.
    Notes: Summary High resolution glass-capillary gas chromatography can be used as a powerful identification tool for single components in complex mixtures, when the matching of retention indices of reference compounds with those found in the sample is based on precise measurements. Besides the constancy of the GC-parameters high precision measurements of retention indices require an accurate determination of net retention times. Special care has to be taken for an accurate measurement of retention times when using a dead-time calculation on the basis of an enforced linearisation of the log t s/homologues-number relationship. The reproducibility of precise retention-index determinations strongly depends on the constancy of the polarity and on the adsorptivity of the capillary column. Provided a sufficiently deactivated and conditioned high performance capillary column (separation number ≥40) and an accuracy of retention-time measurement of better than 0,05 % retention indices can be reproduced within ±0.15 i.u. over a period of several weeks. A conversion of the n-alkane based retention-index concept to the use of the homologous series of n-alkyl-trichloro-acetates (ATA) allows the use of the electron-capture detector (ECD) for precise retention-index determinations for a reliable identification of compounds in the picogram range.
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