Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer

Biasin, Elisa; Fox, Zachary W.; Andersen, Amity; Ledbetter, Kathryn; Kjær, Kasper S.; Alonso-Mori, Roberto; Carlstad, Julia M.; Chollet, Matthieu; Gaynor, James D.; Glownia, James M.; Hong, Kiryong; Kroll, Thomas; Lee, Jae Hyuk; Liekhus-Schmaltz, Chelsea; Reinhard, Marco; Sokaras, Dimosthenis; Zhang, Yu; Doumy, Gilles; March, Anne Marie; Southworth, Stephen H.; Mukamel, Shaul; Gaffney, Kelly J.; Schoenlein, Robert W.; Govind, Niranjan; Cordones, Amy A.; Khalil, Munira

doi:10.1038/s41557-020-00629-3

Title: Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer

Journal Article · Mon Feb 15 00:00:00 EST 2021 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-020-00629-3· OSTI ID:1777282

^[1]; Fox, Zachary W. ^[2]; Andersen, Amity ^[3];

^[1]; Kjær, Kasper S. ^[4];

^[5];

^[2]; Chollet, Matthieu ^[5]; Gaynor, James D. ^[2]; Glownia, James M. ^[5];

^[6]; Kroll, Thomas ^[5];

^[6]; Liekhus-Schmaltz, Chelsea ^[2];

^[1]; Sokaras, Dimosthenis ^[5]; Zhang, Yu ^[7];

^[8]; March, Anne Marie ^[8];

^[8] more »

SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Univ. of Washington, Seattle, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Technical Univ. of Denmark, Lynby (Denmark)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Ultrafast X-ray Science Lab.
Univ. of California, Irvine, CA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)

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. Overall, 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.

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Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; AC05-76RL01830; KC-030105066418; KC-030105172685; SC0012450; SC0019277; DGE-1256082; AC02-06CH11357; FG02-04ER15571; AC02-05CH11231

OSTI ID:: 1777282

Alternate ID(s):: OSTI ID: 1777367; OSTI ID: 1781810; OSTI ID: 1797398

Report Number(s):: PNNL-SA-153682; TRN: US2209435

Journal Information:: Nature Chemistry, Vol. 13, Issue 4; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer

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