Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency

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

doi:10.1021/acs.jpclett.1c03613

Title: Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency

Journal Article · 04 January 2022 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.1c03613 · OSTI ID:1840028

Liekhus-Schmaltz, Chelsea ^[1]; Fox, Zachary W. ^[1];

^[2]; Kjaer, Kasper S. ^[3]; Alonso-Mori, Roberto ^[4];

^[5]; Carlstad, Julia ^[1]; Chollet, Matthieu ^[4];

^[1]; Glownia, James M. ^[4];

^[6]; Kroll, Thomas ^[7]; Lee, Jae Hyuk ^[6]; Poulter, Benjamin I. ^[1]; Reinhard, Marco ^[5]; Sokaras, Dimosthenis ^[7]; Zhang, Yu ^[8];

^[9];

^[9]; Southworth, Stephen H. ^[9] more »

Univ. of Washington, Seattle, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Technical Univ. of Denmark, Lyngby (Denmark)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Univ. of California, Irvine, CA (United States)
Argonne National Lab. (ANL), Argonne, 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)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Quantifying charge delocalization associated with short-lived photoexcited states of molecular complexes in solution remains experimentally challenging, requiring local element specific femtosecond experimental probes of time-evolving electron transfer. In this study, we quantify the evolving valence hole charge distribution in the photoexcited charge transfer state of a prototypical mixed valence bimetallic iron–ruthenium complex, [(CN)₅Fe^IICNRu^III(NH₃)₅]-, in water by combining femtosecond X-ray spectroscopy measurements with time-dependent density functional theory calculations of the excited-state dynamics. We estimate the valence hole charge that accumulated at the Fe atom to be 0.6 ± 0.2, resulting from excited-state metal-to-metal charge transfer, on an ~ 60 fs time scale. Our combined experimental and computational approach provides a spectroscopic ruler for quantifying excited-state valency in solvated complexes.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; AC02-76SF00515; FG02-04ER15571; SC0012450; SC0019277

OSTI ID:: 1840028

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 1 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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