@article{42d502eb55394a9a999cb2fb5c24bfd1,
title = "Concerted Electron-Nuclear Motion in Proton-Coupled Electron Transfer-Driven Grotthuss-Type Proton Translocation",
abstract = "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.",
author = "Arsenault, {Eric A.} and Guerra, {Walter D.} and James Shee and {Reyes Cruz}, {Edgar A.} and Yusuke Yoneda and Wadsworth, {Brian L.} and Emmanuel Odella and Urrutia, {Maria N.} and Gerdenis Kodis and Moore, {Gary F.} and Martin Head-Gordon and Moore, {Ana L.} and Moore, {Thomas A.} and Fleming, {Graham R.}",
note = "Funding Information: This research was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division: G.R.F. (FWP 449A), M.H.-G. (DEAC02 05CH11231), T.A.M. and A.L.M. (DE-FG02-03ER15393), and G.F.M. (DE-SC0021186). Y.Y. appreciates the support of the Japan Society for the Promotion of Science (JSPS) Postdoctoral Fellowship for Research Abroad. E.A.A. acknowledges the support of the National Science Foundation Graduate Research Fellowship (Grant DGE 1752814). J.S. acknowledges funding from the National Institute of General Medical Sciences of the National Institutes of Health under Grant F32GM142231. G.F.M. acknowledges support from the Camille Dreyfus Teacher-Scholar Awards Program. Funding Information: This research was supported by the U.S. Department of Energy Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division: G.R.F. (FWP 449A), M.H.-G. (DEAC02 05CH11231) T.A.M. and A.L.M. (DE-FG02-03ER15393), and G.F.M. (DE-SC0021186). Y.Y. appreciates the support of the Japan Society for the Promotion of Science (JSPS) Postdoctoral Fellowship for Research Abroad. E.A.A. acknowledges the support of the National Science Foundation Graduate Research Fellowship (Grant DGE 1752814). J.S. acknowledges funding from the National Institute of General Medical Sciences of the National Institutes of Health under Grant F32GM142231. G.F.M. acknowledges support from the Camille Dreyfus Teacher-Scholar Awards Program. Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",
year = "2022",
month = may,
day = "26",
doi = "10.1021/acs.jpclett.2c00585",
language = "English (US)",
volume = "13",
pages = "4479--4485",
journal = "Journal of Physical Chemistry Letters",
issn = "1948-7185",
publisher = "American Chemical Society",
number = "20",
}