Author: ["Elisa Biasin","Zachary W. Fox","Amity Andersen","Kathryn Ledbetter","Kasper S. Kjær","Roberto Alonso-Mori","Julia M. Carlstad","Matthieu Chollet","James D. Gaynor","James M. Glownia","Kiryong Hong","Thomas Kroll","Jae Hyuk Lee","Chelsea Liekhus-Schmaltz","Marco Reinhard","Dimosthenis Sokaras","Yu Zhang","Gilles Doumy","Anne Marie March","Stephen H. Southworth","Shaul Mukamel","Kelly J. Gaffney","Robert W. Schoenlein","Niranjan Govind","Amy A. Cordones","Munira Khalil"]
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Abstract
It is well known that the solvent plays a critical role in ultrafast electron-transfer reactions. However, solvent reorganization occurs on multiple length scales, and selectively measuring short-range solute–solvent interactions at the atomic level with femtosecond time resolution remains a challenge. Here we report femtosecond X-ray scattering and emission measurements following photoinduced charge-transfer excitation in a mixed-valence bimetallic (FeiiRuiii) complex in water, and their interpretation using non-equilibrium molecular dynamics simulations. Combined experimental and computational analysis reveals that the charge-transfer excited state has a lifetime of 62 fs and that coherent translational motions of the first solvation shell are coupled to the back electron transfer. Our molecular dynamics simulations identify that the observed coherent translational motions arise from hydrogen bonding changes between the solute and nearby water molecules upon photoexcitation, and have an amplitude of tenths of ångströms, 120–200 cm−1 frequency and ~100 fs relaxation time. This study provides an atomistic view of coherent solvent reorganization mediating ultrafast intramolecular electron transfer. Solvent plays a critical role in electron-transfer reactions, but short-range solvation dynamics are challenging to observe. Now, femtosecond X-ray solution scattering has been used to directly monitor the reorganization of water upon ultrafast intramolecular electron transfer in a bimetallic complex. Coherent motions of the first-shell water molecules are observed, arising from changes in solute–solvent hydrogen bonding.Cite this article
Biasin, E., Fox, Z.W., Andersen, A. et al. Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer. Nat. Chem. (2021). https://doi.org/10.1038/s41557-020-00629-3 