@article{1c968b6059ea44938b5f85a5b070f856,
title = "Electron-Nuclear Dynamics Accompanying Proton-Coupled Electron Transfer",
abstract = "Although photoinduced proton-coupled electron transfer (PCET) plays an essential role in photosynthesis, a full understanding of the mechanism is still lacking due to the complex nonequilibrium dynamics arising from the strongly coupled electronic and nuclear degrees of freedom. Here we report the photoinduced PCET dynamics of a biomimetic model system investigated by means of transient IR and two-dimensional electronic-vibrational (2DEV) spectroscopies, IR spectroelectrochemistry (IRSEC), and calculations utilizing long-range-corrected hybrid density functionals. This collective experimental and theoretical effort provides a nuanced picture of the complicated dynamics and synergistic motions involved in photoinduced PCET. In particular, the evolution of the 2DEV line shape, which is highly sensitive to the mixing of vibronic states, is interpreted by accurate computational modeling of the charge separated state and is shown to represent a gradual change in electron density distribution associated with a dihedral twist that occurs on a 120 fs time scale.",
author = "Yusuke Yoneda and Mora, {S. Jimena} and James Shee and Wadsworth, {Brian L.} and Arsenault, {Eric A.} and Diptarka Hait and Gerdenis Kodis and Devens Gust and Moore, {Gary F.} and Moore, {Ana L.} and Martin Head-Gordon and Moore, {Thomas A.} and Fleming, {Graham R.}",
note = "Funding Information: This research was supported by the Department of Energy, Office of Science, Chemical Sciences, Geosciences and Biosciences Division: G.R.F. (FWP 449A), M.H.-G. (DE-AC02-05CH11231), T.A.M. and A.L.M. (DE-FG02-03ER15393), G.F.M. (DE-SC0021186). This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. 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 Berkeley Fellowship and the National Science Foundation Graduate Research Fellowship (Grant No. DGE 1752814). G.F.M. acknowledges support from the Camille Dreyfus Teacher-Scholar Awards Program. The authors appreciate Dr. Eric Wu for his assistance with the experiments in the preliminary stages of this work. Publisher Copyright: {\textcopyright} 2021 The Authors. Published by American Chemical Society.",
year = "2021",
month = mar,
day = "3",
doi = "10.1021/jacs.0c10626",
language = "English (US)",
volume = "143",
pages = "3104--3112",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "8",
}