Long-range electron transfer in proteins: A renormalized-perturbation-expansion approach

Goldman, Carla

doi:10.1103/physreva.43.4500

Cited by 48 publications

(38 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…One example is the RPE ͑renormalized perturbative expansion͒ which selects the ''skeleton'' ͑self-avoiding͒ paths and then adds ''decoration'' to make an arbitrary path. 14, 38 We consider the part of G that is needed to obtain the effective coupling strength, and denote it now by G (1,n) (n) (m 1 ,m n ). It consists of all possible paths from any orbital m 1 in the first site to any orbital m n in the last (n th) site.…”

Section: Graph Representationmentioning

confidence: 99%

A sequential formula for electronic coupling in long range bridge-assisted electron transfer: Formulation of theory and application to alkanethiol monolayers

Hsu

Marcus

1997

The Journal of Chemical Physics

View full text Add to dashboard Cite

A recursion relation is formulated for the Green's function for calculating the effective electron coupling in bridge-assisted electronic transfer systems, within the framework of the tight-binding Hamiltonian. The recursion expression relates the Green's function of a chain bridge to that of the bridge that is one unit less. It is applicable regardless of the number of orbitals per unit. This method is applied to the system of a ferrocenylcarboxy-terminated alkanethiol on the Au͑111͒ surface. At larger numbers of bridge units, the effective coupling strength shows an exponential decay as the number of methylene͑-CH 2 -͒ units increases. This sequential formalism shows numerical stability even for a very long chain bridge and, since it uses only small matrices, requires much less computer time for the calculation. Identical bridge units are not a requirement, and so the method can be applied to more complicated systems.

show abstract

Section: Graph Representationmentioning

confidence: 99%

A sequential formula for electronic coupling in long range bridge-assisted electron transfer: Formulation of theory and application to alkanethiol monolayers

Hsu

Marcus

1997

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…42 This regime of ET is known as superexchange, [43][44][45][46] and it is characterized by the absence of any population physically residing on the bridge during the ET process. In terms of the simple dynamical scheme for bridged charge separation reactions, DBA f D + B -A f D + BA -, the intermediate state D + B -A is a virtual state that is not physically populated.…”

Section: Introductionmentioning

confidence: 99%

Electron Transfer Rates in Bridged Molecular Systems 2. A Steady-State Analysis of Coherent Tunneling and Thermal Transitions

Segal¹,

Nitzan²,

Davis³

et al. 2000

J. Phys. Chem. B

317

371

View full text Add to dashboard Cite

The effect of dephasing and relaxation on electron transfer in bridged molecular systems is investigated using a simple molecular model. The interaction between the molecular system and the thermal environment is described on the level of the Redfield theory, modified when needed for the description of steady-state situations. Noting that transient as well as steady-state measurements are possible in such system, we discuss the relationship between the rates obtained from these different types of experiments and, in particular, the conditions under which these rates are the same. Also, a formal relation between the steady-state rate for electron transfer across a molecular bridge and the conductance of this bridge when placed between two metal contacts is established. The effect of dephasing and relaxation on the electron transfer is investigated, and new observations are made with regard to the transition from the superexchange to the thermal (hopping through bridge) regime of the transfer process. In particular, the rate is temperature-independent in the superexchange regime, and its dependence on the bridge length (N) is exponential, exp(-N). The rate behaves like (R 1 + R 2 N) -1 exp(-∆E/k B T) beyond a crossover value of N, where ∆E is the energy gap between the donor/acceptor and the bridge levels, and where R 1 and R 2 are characteristic times for activation onto the bridge and diffusion in the bridge, respectively. We find that, in typical cases, R 1 . R 2 , and therefore, a region of very weak N dependence is expected before the Ohmic behavior, N -1 , is established for large enough N. In addition, a relatively weak exponential dependence, exp(-RN), is expected for long bridges if competing processes capture electrons away from the bridge sites. Finally, we consider ways to distinguish experimentally between the thermal and the tunneling routes.

show abstract

“…Refs. [11,12,13,14,15,16,17]). The point of this approach is that an electron involved in a long range ET process, with a high probability follows a few primary tunneling pathways moving through the macromolecule.…”

Section: Introductionmentioning

confidence: 99%

Low-temperature electronic transport through macromolecules and characteristics of intramolecular electron transfer

Zimbovskaya

2005

The Journal of Chemical Physics

View full text Add to dashboard Cite

Long distance electron transfer (ET) plays an important part in many biological processes. Also, fundamental understanding of ET processes could give grounds for designing miniaturized electronic devices. So far experimental data on the ET mostly concern ET rates which characterizes ET processes in whole. Here, we develop a different approach which could provide more information about intrinsic characteristics of the long-range intramolecular ET. A starting point of the studies is an obvious resemblance between ET processes and electric transport through molecular wires placed between metallic contacts. Accordingly, the theory of electronic transport through molecular wires is applied to analyze characteristics of a long-range electron transfer through molecular bridges. Assuming a coherent electron tunneling to be a predominant mechanism of ET at low temperatures, it is shown that low-temperature current-voltage characteristics could exhibit a special structure, and the latter contains information concerning intrinsic features of the intramolecular ET. Using the Buttiker dephasing model within the scattering matrix formalism we analyze the effect of dephasing on the electron transmission function and current-voltage curves.

show abstract

Long-range electron transfer in proteins: A renormalized-perturbation-expansion approach

Cited by 48 publications

References 20 publications

A sequential formula for electronic coupling in long range bridge-assisted electron transfer: Formulation of theory and application to alkanethiol monolayers

A sequential formula for electronic coupling in long range bridge-assisted electron transfer: Formulation of theory and application to alkanethiol monolayers

Electron Transfer Rates in Bridged Molecular Systems 2. A Steady-State Analysis of Coherent Tunneling and Thermal Transitions

Low-temperature electronic transport through macromolecules and characteristics of intramolecular electron transfer

Contact Info

Product

Resources

About