Concerted Electron-Nuclear Motion in Proton-Coupled Electron Transfer-Driven Grotthuss-Type Proton Translocation.

Autor:	Arsenault EA; Department of Chemistry, University of California, Berkeley, California 94720, United States.; Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.; Kavli Energy Nanoscience Institute at Berkeley, Berkeley, California 94720, United States., Guerra WD; School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States., Shee J; Department of Chemistry, University of California, Berkeley, California 94720, United States.; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States., Reyes Cruz EA; School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States.; The Biodesign Institute Center for Applied Structural Discovery (CASD), Tempe, Arizona 85287, United States., Yoneda Y; Department of Chemistry, University of California, Berkeley, California 94720, United States.; Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.; Kavli Energy Nanoscience Institute at Berkeley, Berkeley, California 94720, United States., Wadsworth BL; School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States.; The Biodesign Institute Center for Applied Structural Discovery (CASD), Tempe, Arizona 85287, United States., Odella E; School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States., Urrutia MN; School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States., Kodis G; School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States.; The Biodesign Institute Center for Applied Structural Discovery (CASD), Tempe, Arizona 85287, United States., Moore GF; School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States.; The Biodesign Institute Center for Applied Structural Discovery (CASD), Tempe, Arizona 85287, United States., Head-Gordon M; Department of Chemistry, University of California, Berkeley, California 94720, United States.; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States., Moore AL; School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States., Moore TA; School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States., Fleming GR; Department of Chemistry, University of California, Berkeley, California 94720, United States.; Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.; Kavli Energy Nanoscience Institute at Berkeley, Berkeley, California 94720, United States.
Jazyk:	angličtina
Zdroj:	The journal of physical chemistry letters [J Phys Chem Lett] 2022 May 26; Vol. 13 (20), pp. 4479-4485. Date of Electronic Publication: 2022 May 14.
DOI:	10.1021/acs.jpclett.2c00585
Abstrakt:	Photoinduced proton-coupled electron transfer and long-range two-proton transport via a Grotthuss-type mechanism are investigated in a biomimetic construct. The ultrafast, nonequilibrium dynamics are assessed via two-dimensional electronic vibrational spectroscopy, in concert with electrochemical and computational techniques. A low-frequency mode is identified experimentally and found to promote double proton and electron transfer, supported by recent theoretical simulations of a similar but abbreviated (non-photoactive) system. Excitation frequency peak evolution and center line slope dynamics show direct evidence of strongly coupled nuclear and electronic degrees of freedom, from which we can conclude that the double proton and electron transfer processes are concerted (up to an uncertainty of 24 fs). The nonequilibrium pathway from the photoexcited Franck-Condon region to the E2PT state is characterized by an ∼110 fs time scale. This study and the tools presented herein constitute a new window into hot charge transfer processes involving an electron and multiple protons.
Databáze:	MEDLINE
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