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Topological analyses of time-dependent electronic structures: application to electron-transfers in methionine enkephalin

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Abstract

We have studied electron transfers (ET) between electron donors and acceptors, taking as illustrative example the case of ET in methionine enkephalin. Recent pulse and gamma radiolysis experiments suggested that an ultrafast ET takes place from the C-terminal tyrosine residue to the N-terminal, oxidized, methionine residue. According to standard theoretical frameworks like the Marcus theory, ET can be decomposed into two successive steps: i) the achievement through thermal fluctuations, of a set of nuclear coordinates associated with degeneracy of the two electronic states, ii) the electron tunneling from the donor molecular orbital to the acceptor molecular orbital. Here, we focus on the analysis of the time-dependent electronic dynamics during the tunneling event. This is done by extending the approaches based on the topological analyses of stationary electronic density and of the electron localization function (ELF) to the time-dependent domain. Furthermore, we analyzed isosurfaces of the divergence of the current density, showing the paths that are followed by the tunneling electron from the donor to the acceptor. We show how these functions can be calculated with constrained density functional theory. Beyond this work, the topological tools used here can open up new opportunities for the electronic description in the time-dependent domain.

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Authors and Affiliations

  1. Laboratoire de Chimie Théorique, UPMC Université Paris 06, UMR 7616, F-75005, Paris, France

    Julien Pilmé, Eleonora Luppi & Jacqueline Bergès

  2. Laboratoire de Chimie Théorique, UMR 7616, CNRS, F-75005, Paris, France

    Julien Pilmé, Eleonora Luppi & Jacqueline Bergès

  3. Laboratoire de Chimie-Physique, Université Paris Sud, CNRS, UMR 8000. 15, rue Jean Perrin, 91405, Orsay CEDEX, France

    Chantal Houée-Lévin & Aurélien de la Lande

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  1. Julien Pilmé
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  2. Eleonora Luppi
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Correspondence to Julien Pilmé, Jacqueline Bergès or Aurélien de la Lande.

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This paper belongs to Topical Collection QUITEL 2013

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Pilmé, J., Luppi, E., Bergès, J. et al. Topological analyses of time-dependent electronic structures: application to electron-transfers in methionine enkephalin. J Mol Model 20, 2368 (2014). https://doi.org/10.1007/s00894-014-2368-4

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