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Fluctuations in biological and bioinspired electron-transfer reactions.

Publication ,  Journal Article
Skourtis, SS; Waldeck, DH; Beratan, DN
Published in: Annual review of physical chemistry
January 2010

Central to theories of electron transfer (ET) is the idea that nuclear motion generates a transition state that enables electron flow to proceed, but nuclear motion also induces fluctuations in the donor-acceptor (DA) electronic coupling that is the rate-limiting parameter for nonadiabatic ET. The interplay between the DA energy gap and DA coupling fluctuations is particularly noteworthy in biological ET, where flexible protein and mobile water bridges take center stage. Here, we discuss the critical timescales at play for ET reactions in fluctuating media, highlighting issues of the Condon approximation, average medium versus fluctuation-controlled electron tunneling, gated and solvent relaxation controlled electron transfer, and the influence of inelastic tunneling on electronic coupling pathway interferences. Taken together, one may use this framework to establish principles to describe how macromolecular structure and structural fluctuations influence ET reactions. This framework deepens our understanding of ET chemistry in fluctuating media. Moreover, it provides a unifying perspective for biophysical charge-transfer processes and helps to frame new questions associated with energy harvesting and transduction in fluctuating media.

Duke Scholars

Published In

Annual review of physical chemistry

DOI

EISSN

1545-1593

ISSN

0066-426X

Publication Date

January 2010

Volume

61

Start / End Page

461 / 485

Related Subject Headings

  • Proteins
  • Models, Theoretical
  • Electron Transport
  • Computer Simulation
  • Chemical Physics
  • 3407 Theoretical and computational chemistry
  • 3406 Physical chemistry
  • 0307 Theoretical and Computational Chemistry
  • 0306 Physical Chemistry (incl. Structural)
 

Citation

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Skourtis, S. S., Waldeck, D. H., & Beratan, D. N. (2010). Fluctuations in biological and bioinspired electron-transfer reactions. Annual Review of Physical Chemistry, 61, 461–485. https://doi.org/10.1146/annurev.physchem.012809.103436
Skourtis, Spiros S., David H. Waldeck, and David N. Beratan. “Fluctuations in biological and bioinspired electron-transfer reactions.Annual Review of Physical Chemistry 61 (January 2010): 461–85. https://doi.org/10.1146/annurev.physchem.012809.103436.
Skourtis SS, Waldeck DH, Beratan DN. Fluctuations in biological and bioinspired electron-transfer reactions. Annual review of physical chemistry. 2010 Jan;61:461–85.
Skourtis, Spiros S., et al. “Fluctuations in biological and bioinspired electron-transfer reactions.Annual Review of Physical Chemistry, vol. 61, Jan. 2010, pp. 461–85. Epmc, doi:10.1146/annurev.physchem.012809.103436.
Skourtis SS, Waldeck DH, Beratan DN. Fluctuations in biological and bioinspired electron-transfer reactions. Annual review of physical chemistry. 2010 Jan;61:461–485.

Published In

Annual review of physical chemistry

DOI

EISSN

1545-1593

ISSN

0066-426X

Publication Date

January 2010

Volume

61

Start / End Page

461 / 485

Related Subject Headings

  • Proteins
  • Models, Theoretical
  • Electron Transport
  • Computer Simulation
  • Chemical Physics
  • 3407 Theoretical and computational chemistry
  • 3406 Physical chemistry
  • 0307 Theoretical and Computational Chemistry
  • 0306 Physical Chemistry (incl. Structural)