Quantum interferences and electron transfer in photosystem i

Nicolas Renaud, Daniel Powell, Mahdi Zarea, Bijan Movaghar, Michael R Wasielewski, Mark A Ratner

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

We have studied the electron transfer occurring in the photosystem I (PSI) reaction center from the special pair to the first iron-sulfur cluster. Electronic structure calculations performed at the DFT level were employed to determine the on-site energies of the fragments comprising PSI, as well as the charge transfer integrals between neighboring pairs. This electronic Hamiltonian was then used to compute the charge transfer dynamics, using the stochastic surrogate Hamiltonian approach to account for the coherent propagation of the electronic density but also for its energy relaxation and decoherence. These simulations give reasonable transfer time ranging from subpicoseconds to nanoseconds and predict coherent oscillations for several picoseconds. Due to these long-lasting coherences, the propagation of the electronic density can be enhanced or inhibited by quantum interferences. The impact of random fluctuations and asymmetries on these interferences is then discussed. Random fluctuations lead to a classical transport where both constructive and destructive quantum interferences are suppressed. Finally it is shown that an energy difference of 0.15 eV between the on-site energies of the phylloquinones leads to a highly efficient electron transfer even in presence of strong random fluctuations.

Original languageEnglish
Pages (from-to)5899-5908
Number of pages10
JournalJournal of Physical Chemistry A
Volume117
Issue number29
DOIs
Publication statusPublished - Jul 25 2013

Fingerprint

Photosystem I Protein Complex
Hamiltonians
Charge transfer
electron transfer
Vitamin K 1
interference
Electrons
Sulfur
Discrete Fourier transforms
Electronic structure
phylloquinone
Iron
charge transfer
electronics
propagation
energy
sulfur
fragments
asymmetry
electronic structure

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Quantum interferences and electron transfer in photosystem i. / Renaud, Nicolas; Powell, Daniel; Zarea, Mahdi; Movaghar, Bijan; Wasielewski, Michael R; Ratner, Mark A.

In: Journal of Physical Chemistry A, Vol. 117, No. 29, 25.07.2013, p. 5899-5908.

Research output: Contribution to journalArticle

Renaud, Nicolas ; Powell, Daniel ; Zarea, Mahdi ; Movaghar, Bijan ; Wasielewski, Michael R ; Ratner, Mark A. / Quantum interferences and electron transfer in photosystem i. In: Journal of Physical Chemistry A. 2013 ; Vol. 117, No. 29. pp. 5899-5908.
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