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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    European biophysics journal 26 (1997), S. 477-483 
    ISSN: 1432-1017
    Keywords: Key words Photosynthesis ; Electron transfer ; Fission ; Double excited states
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract A new mechanism for the primary photoinduced charge separation in photosynthesis is proposed. It involves as a real intermediate between the excited special pair state P* and the primary charge separated state P+ HL – a trip-trip-singlet BT BL T, which consists of a triplet on the dimer P and a further triplet on the monomer BL. Both combine to a singlet. The electron transfer is caused by spin exchange couplings. The transient spectrum of the short lived intermediate, formerly taken as evidence for the charge transfer state P+ BL –, is reinterpreted as a transient excitation of this trip-trip singlet.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1432-1017
    Keywords: Key words Carbonmonoxy-Myoglobin ; Recombination kinetics ; Mössbauer spectroscopy ; Scaling law ; Activated tunneling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract We have studied the recombination kinetics of carboxymyoglobin (after photodissociation of the CO ligand) by Mössbauer spectroscopy for temperatures in the range 4.2 – 60 K. The observed kinetics display non-exponential behaviour which was monitored over periods of a few days. It is shown that the time dependence of the kinetics can be reduced to a single universal function of the temperature-dependent variable (t/τ 1/2(T)) β(T) . The half-decay time τ 1/2(T) and the scaling parameter β(T) are analysed for the presence of tunneling effects. The non-Arrhenius temperature dependence of the half-decay time below 60 K is interpreted as activated tunneling in models with an Eckart barrier or a fluctuating barrier.
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. ; Stafa-Zurich, Switzerland
    Materials science forum Vol. 79-82 (Jan. 1991), p. 153-158 
    ISSN: 1662-9752
    Source: Scientific.Net: Materials Science & Technology / Trans Tech Publications Archiv 1984-2008
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1662-9752
    Source: Scientific.Net: Materials Science & Technology / Trans Tech Publications Archiv 1984-2008
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 4094-4101 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The cooling of vibrationally hot azulene is studied in different solvents by picosecond spectroscopy. Excitation to the electronic S1 state generates molecules with a vibrationally hot ground state by rapid internal conversion. The subsequent cooling is monitored by the temperature-dependent change of the S0–S1 absorption edge and occurs via interaction with the solvent on a time scale of several tens of picoseconds. A theoretical model of intermolecular energy transfer in the liquid phase is developed. The vibrational excess energy of azulene is transferred to the solvent molecules by isolated binary collisions, where the multimode vibrational system of the molecules is considered explicitly. The dissipation of energy within the solvent is simulated by the macroscopic conduction of heat. The temporal development of the vibrational temperature of the azulene molecules and the concommitant changes of absorption are calculated taking into account the properties of the specific solvent. The results of the theory show quantitative agreement with our data.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 3394-3395 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    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 87 (1987), S. 249-259 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Intramolecular vibrational energy redistribution (IVR) is treated. Nearly isoenergetic rigid-rotor harmonic-oscillator states are rovibronically coupled by the interplay of anharmonic and Coriolis forces. The theory predicts linewidth distributions of rovibronic states and explains the selective supression of rotational spectral lines. Applications to sub-Doppler spectra of the 1410120 band of benzene allow to extract values for effective intramolecular interactions. These results are supported by direct calculations based on the force field.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 354-365 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A description of electron transfer processes is presented which makes use of the concept of solitary states for the construction of the initial and the final state wave functions. Even though this concept is closely related to an adiabatic description in the sense that it provides partial delocalization of these states it also assures localization for a symmetric donor–acceptor system. The theory can be applied to arbitrary values of the internal parameters characterizing the system, that is the electronic donor–acceptor coupling V, the free energy change ΔE, and the coupling of the electron to nuclear motions represented by a Stokes shift S. This way the theory of nonadiabatic electron transfer processes is put on equal footing with the theory of adiabatic transitions and even more interestingly the same concept unifies the common electron transfer theory and the theory of internal conversion processes if ||ΔE|| and (or) ||V|| exceed S. It is shown analytically how the results of the conventional treatments for adiabatic, nonadiabatic, and internal conversion processes fall out of this theory as special cases. It is further examplified how the system develops from the so-called normal regime with ||ΔE||〈S into the inverted regime with ||ΔE||〉S as function of ΔE for fixed parameters of V and S and as function of V for fixed parameters of ΔE and S.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 3880-3887 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The electron transfer process from cytochrome c to the special pair is revisited. In the present model the transfer rate in photosynthetic reaction centers of Chromatium vinosum is modulated by fluctuations of the dielectric constant of the protein environment between the donor and acceptor site. The fluctuations enter the rate expression as the inverse of a Lamb–Mössbauer factor. The strong temperature dependence of the transfer rate can thus be related to protein specific dynamics. Experimental evidence about such dynamics is provided by recently recorded Mössbauer spectra of iron containing proteins [Parak et al., J. Mol. Biol. 161, 177 (1982)].
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 2741-2759 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We investigate spectral properties of random manifolds, which consist of a bright state coupled to mutually uncoupled dark states for an equal but otherwise arbitrary distribution of the couplings. Both Poisson and Wigner distributions of the energy spacings of the dark states are taken into account. The Poisson spacing model is solved exactly. The average spectrum is Lorentzian. The average dilution factor comes out to be a function alone of the mean coupling strength normalized to the mean neighbor spacing of the dark states. A simple expression for the explored fraction of the available phase space is obtained. Numerical studies indicate that the normalized coupling even controls the whole distribution of the dilution factor for the Poisson model. For weak mean coupling strength a secondary peak occurs in this distribution for both the Poisson and the Wigner model. A perturbational analysis shows that this peak leads back to accidental resonances of the bright state with single dark states. A simple tier model is suggested for treating the intermixing of vibrational dark basis states in molecules. Results are compared with experimental data. © 2000 American Institute of Physics.
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