The role of different reorganization energies within the Zusman theory of electron transfer

Casado-Pascual, Jesús; Morillo, Manuel; Goychuk, Igor; Hänggi, Peter
January 2003
Journal of Chemical Physics;1/1/2003, Vol. 118 Issue 1, p291
Academic Journal
We consider the kinetics of electron transfer reactions in condensed media with different reorganization energies for the forward and backward processes. The starting point of our analysis is an extension of the well-known Zusman equations to the case of parabolic diabatic curves with different curvatures. A generalized master equation for the populations as well as formal expressions for their long-time limit is derived. We discuss the conditions under which the time evolution of the populations of reactants and products can be described at all times by a single exponential law. In the limit of very small tunnel splitting, a novel rate formula for the nonadiabatic transitions is obtained. It generalizes previous results derived within the contact approximation. For larger values of the tunnel splitting, we make use of the consecutive step approximation leading to a rate formula that bridges between the nonadiabatic and solvent-controlled adiabatic regimes. Finally, the analytical predictions for the long-time populations and for the rate constant are tested against precise numerical solutions of the starting set of partial differential equations.


Related Articles

  • The primary steps of photosynthesis. Fleming, Graham R.; van Grondelle, Rienk // Physics Today;Feb94, Vol. 47 Issue 2, p48 

    Describes theoretical and experimental efforts aimed at understanding photosynthetic electron and energy transfer. Description of the electronic states of the system; Protein's role in electron transfer; Light trapping.

  • A hybrid model for particle transport and electron energy distributions in positive column electrical discharges using equivalent species transport. Huang, Fred Y.; Kushner, Mark J. // Journal of Applied Physics;11/15/1995, Vol. 78 Issue 10, p5909 

    Introduces a modeling technique designed to analyze the particle transport and electron energy distribution in low-pressure, low temperature electrical discharges. Approaches in investigating electron energy distribution; Description of the model; Plasma parameters of different electrical...

  • Modeling of particle and energy transport in the edge plasma of Alcator C-Mod. Umansky, M.V.; Krasheninnikov, S.I. // Physics of Plasmas;Jul99, Vol. 6 Issue 7, p2791 

    Analyzes the recycling and transport in the edge plasma of the Alcator C-Mod tokamak. Experimental plasma density profiles in the scrape-off layer; Significance of the energy flux carried by radial plasma convection and by charge-exchange neutrals.

  • Interplay of geminate and bimolecular reactions in multistage electron and energy transfer. Burshtein, A.I.; Frantsuzov, P.A. // Journal of Chemical Physics;8/22/1997, Vol. 107 Issue 8, p2872 

    Explores the interplay of geminate and bimolecular reactions in multistage electron and energy transfer. Universal integral formalism of encounter theory; Bimolecular quenching of singlet and triplet excitations parallel to an inter-system crossing (ISC); Shortage of near-contact excitations...

  • Relaxation processes in self-assembling triads based on porphyrin Zn-heterodimers. Sagun, E. I.; Zenkevich, É. I.; Knyukshto, V. N.; Shulga, A. M.; Ivashin, N. V. // Optics & Spectroscopy;Dec2009, Vol. 107 Issue 6, p959 

    The directional self-assembly of nanosized, structurally organized triads is implemented in methylcyclohexane at 295 K, which is based on the two-point extra coordination of nonsymmetric, covalently bound heterodimers of Zn porphyrins to bipyridyl-substituted porphyrin free-base extra ligands....

  • Intermolecular Processes in Excited Electronic States in the Gas Phase (Review). Zalesskaya, G.; Sambor, E. // Journal of Applied Spectroscopy;Jul2005, Vol. 72 Issue 4, p459 

    A brief review of works on the temperature dependences of the rate constants kq of the intermolecular processes proceeding in the excited electronic states in the gas phase is given. The dependences kq(T) for such biomolecular processes as intermolecular vibrational energy transfer in the...

  • Vibrational energy transfer of CO/Cu(100): Nonadiabatic vibration/electron coupling. Morin, M.; Levinos, N. J.; Harris, A. L. // Journal of Chemical Physics;3/1/1992, Vol. 96 Issue 5, p3950 

    Vibrational energy relaxation of the internal C–O stretching mode of carbon monoxide in the c(2×2) overlayer on the Cu(100) surface at 120 K is measured by picosecond pump–probe spectroscopy. A resonant 1.5 ps infrared pulse at ν=2085 cm-1 pumps the C–O stretching...

  • Recent Patents on Self-Quenching DNA Probes. Knemeyer, Jens-Peter; Marmé, Nicole // Recent Patents on DNA & Gene Sequences;Jun2007, Vol. 1 Issue 2, p145 

    In this review, we report on patents concerning self-quenching DNA probes for assaying DNA during or after amplification as well as for direct assaying DNA or RNA, for example in living cells. Usually the probes consist of fluorescently labeled oligonucleotides whose fluorescence is quenched in...

  • Photoinduced energy and electron transfer in oligo(p-phenylene vinylene)-fullerene dyads. Van Hal, P.A.; Meskers, S.C.J.; Janssen, R.A.J. // Applied Physics A: Materials Science & Processing;2004, Vol. 79 Issue 1, p41 

    The intramolecular photoinduced charge separation within an oligo(p-phenylene vinylene)–fulleropyrrolidine dyad with four phenyl rings (OPV4-C[sub 60]) has been investigated with femtosecond pump-probe spectroscopy in solvents of different polarity and in the solid state. In solution,...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics