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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 116 (2002), S. 1692-1699 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Translocation of protons across biological membranes is carried out by special membrane proteins, proton pumps. Surprisingly, the turnover rate of some proton pumps, such as cytochrome c oxidase (CcO), is higher than the bulk diffusion limit (i.e., the rate at which protons can be supplied to the entrance of the proton conducting channel via free bulk diffusion). It has been suggested that the diffusion of protons along the membrane surface that surrounds the entrance of the proton conducting channel can increase the supply of the protons and therefore explain the puzzling high turnover rates. Here we consider a phenomenological model of proton transport to a proton collecting channel. The model takes into account both the diffusion in the bulk and the coupled diffusion of protons along the membrane surface. In our model a homogeneous membrane surface, which mediates proton diffusion toward the channel entrance, is populated with protolytic groups that can exchange protons with a bulk solution. Equations which describe the coupled surface-bulk proton diffusion are derived and solved. The maximum (diffusion limited) rate at which protons can be delivered to the pump is examined. It is found that there are two regimes of surface-mediated proton transport, depending on the rate of proton exchange between the bulk and the surface. In both regimes proton transport is dominated by the contribution of surface diffusion. Due to two-dimensional character of the surface diffusion, the transport rate depends on the size of the channel entrance in a weak, logarithmic fashion. The theory also provides a simple expression for the maximum distance that a proton can migrate on the surface before it is fully equilibrated with the bulk. This result allows one to examine whether the chemiosmotic coupling between a proton source on a membrane surface, such as CcO, and a sink, such as ATP synthase, occurs via diffusion along the membrane, or involves equilibration with the bulk. © 2002 American Institute of Physics.
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 10438-10450 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A concerted electron–proton transfer reaction is discussed, in which proton tunneling occurs simultaneously with electronic transition. It is assumed that the potential in which the proton moves is formed by two electronic states, which in the absence of their interaction would cross in the region between the two minima of the proton adiabatic potential. The proton tunneling between the two wells is, therefore, coupled to a switch between the two electronic states. The later occurs only when the proton is in the tunneling region under the barrier. A simple analytical expression for the tunneling matrix element TDA is derived, which is uniformly correct for small and large values of the electronic coupling. For small electronic coupling our expression coincides with that obtained in the nonadiabatic theory of proton-coupled electron transfer reactions. For large electronic coupling the expression is reduced to that obtained in the Born–Oppenheimer approximation. The transition from nonadiabatic to adiabatic tunneling is governed by the magnitude of the Landau–Zener parameter defined for the tunneling process. The obtained result is discussed in the context of the proton tunneling time. © 2000 American Institute of Physics.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 3358-3369 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Electron transfer reaction rate constants at semiconductor/liquid interfaces are calculated using the Fermi Golden Rule and a tight-binding model for the semiconductors. The slab method and a z-transform method are employed in obtaining the electronic structures of semiconductors with surfaces and are compared. The maximum electron transfer rate constants at Si/viologen2+/+ and InP/Me2Fc+/0 interfaces are computed using the tight-binding type calculations for the solid and the extended-Hückel for the coupling to the redox agent at the interface. These results for the bulk states are compared with the experimentally measured values of Lewis and co-workers, and are in reasonable agreement, without adjusting parameters. In the case of InP/liquid interface, the unusual current vs applied potential behavior is additionally interpreted, in part, by the presence of surface states. © 2000 American Institute of Physics.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 6908-6918 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The migration of adsorbed atoms on crystal surfaces is considered. To describe the adatom motion one often uses a generalized Langevin equation (GLE). The time-dependent friction, which enters the GLE, is caused by the interaction with the crystal excitations. However, the explicit form of the time-dependent friction is not well known. We show that if the damping is associated with acoustic phonons and the coupling of the adatom with the surface is not too strong, then the friction is Ohmic. An explicit expression for the friction coefficient is given in terms of the basic physical parameters of the crystal and in terms of the activation energy of the adatom on the surface. We find that usually the diffusion occurs in the intermediate damping regime. In this regime nearest neighbor hops are most probable and transition state theory gives an excellent estimate for the rate of escape and for the diffusion coefficient. Using the recently developed turnover theory for surface diffusion [Phys. Rev. E 49, 5098 (1994)] we derive explicit expressions for the evolution of the time-dependent site distribution and compare it with an experiment where correlated hops have been observed. We conclude that even when the motion is one-dimensional, correlated hops are to be expected only for sufficiently high temperatures or for physisorbed atoms. © 1995 American Institute of Physics.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 3108-3120 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Kramers's model is applied to an electron transfer reaction in the inverted region. The reaction rate is considered at different values of the coupling matrix element and the damping, which is a measure of the interaction of the reaction coordinate with the other, nonreactive degrees of freedom of the system. The coupling characterizes overlap of the electron orbits of the donor and acceptor. It is shown that at the low/high damping the reaction rate is controlled by the slowest of the two rates. One is the thermally averaged transition rate (the reaction rate in the intermediate damping regime) and another one is the rate controlled by the energy/spatial diffusion. We demonstrate that the reaction rate as a function of the electron coupling shows a striking difference from the normal region case. The rate passes via maximum and decreases exponentially with the increase of the coupling. © 1996 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 5307-5317 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The effect of solvent fluctuations on the rate of electron transfer reactions is considered using linear response theory and a second-order cumulant expansion. An expression is obtained for the rate constant in terms of the dielectric response function of the solvent. It is shown thereby that this expression, which is usually derived using a molecular harmonic oscillator ("spin-boson") model, is valid not only for approximately harmonic systems such as solids but also for strongly molecularly anharmonic systems such as polar solvents. The derivation is a relatively simple alternative to one based on quantum field theoretic techniques. The effect of system inhomogeneity due to the presence of the solute molecule is also now included. An expression is given generalizing to frequency space and quantum mechanically the analogue of an electrostatic result relating the reorganization free energy to the free energy difference of two hypothetical systems [J. Chem. Phys. 39, 1734 (1963)]. The latter expression has been useful in adapting specific electrostatic models in the literature to electron transfer problems, and the present extension can be expected to have a similar utility. © 1999 American Institute of Physics.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 7356-7366 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The time-evolution of the fluorescence spectrum of a dissolved chromophore excited by an ultrafast pump pulse is considered. The average value of the energy difference of the solute in its excited and ground states is used to describe the relaxation of the maximum of the transient fluorescence spectrum to its equilibrium value (dynamic Stokes shift, DSS). A simple formula for the normalized DSS is obtained which generalizes an earlier standard classical expression and includes the effect of a pump pulse of finite duration. As an example, dielectric dispersion data are used for a dipolar solute in water to estimate the quantum correction to the standard DSS expression. The correction is negligible when the frequency of the pump pulse is close to the maximum in the absorption spectrum, but a deviation from the standard formula can be expected for the pump pulse tuned to a far wing of the absorption band of the chromophore. An expression is given for this deviation. © 1998 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 5251-5264 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A novel approach which allows one to treat the nonlinear dielectric response of the solvent in a general fashion is suggested to calculate the nonequilibrium solvation free energies along the reaction coordinate. A simple continuum model of the dielectric response of the solvent is used to investigate the effects of dielectric saturation on the solvation energies and on the activation energies of electron transfer reactions. A simple expression for the solvation energy of a lone spherical solute is obtained. To calculate the solvation energy of an ion pair the noninteracting redox centers approximation is used. This approximation is valid if the donor and acceptor are far enough from each other. The obtained expressions are in good agreement with the results of numerical simulations and allow one to explain the observed deviations from the linear response theory. The activation energies of the charge separation/recombination reaction A+B(arrow-right-and-left)A++B− are calculated. It is shown that the dependence of the activation energy on the driving force of the reaction must deviate from Marcus' formula in the strong saturation regime. General relations for the solvation free energies are derived, which are valid for most of the molecular models used in numerical simulations. © 1996 American Institute of Physics.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 8910-8920 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Escape of a particle from a metastable potential, whose motion is governed by the generalized Langevin equation, is a common model of many chemical and physical activated processes in condensed phase. In the intermediate-to-strong damping regime the rate of escape is controlled by the particle dynamics near the barrier top. Since Kramers, the parabolic barrier approximation is commonly used to get the expression for the rate in this regime. We consider the influence of anharmonic corrections to the potential barrier on the quantum rate and get leading order corrections in terms of the inverse barrier height. New terms appearing in the quantum expression for the rate are associated with tunneling through the barrier and become important at low temperatures. The analytic theory is compared with recent numerically exact quantum simulations [M. Topaler and N. Makri, J. Chem. Phys. 101, 7500 (1994)]. © 1995 American Institute of Physics.
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  • 10
    Publication Date: 1994-06-01
    Print ISSN: 1063-651X
    Electronic ISSN: 1095-3787
    Topics: Physics
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