Ballistic ΔS = 2 intersystem crossing in a cobalt cubane following ligand-field excitation probed by extreme ultraviolet spectroscopy

Shari'ati, Yusef; Vura-Weis, Josh

doi:10.1039/d1cp04136c

Ballistic ΔS = 2 intersystem crossing in a cobalt cubane following ligand-field excitation probed by extreme ultraviolet spectroscopy

Journal Article · Wed Nov 24 00:00:00 EST 2021 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d1cp04136c· OSTI ID:1978760

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University of Illinois at Urbana-Champaign, IL (United States); OSTI
University of Illinois at Urbana-Champaign, IL (United States)

We report femtosecond M_2,3-edge X-ray absorption near-edge structure (XANES) spectroscopy is used to probe the excited-state dynamics of the cobalt cubane [Co^III₄O₄](OAc)₄(py)₄ (OAc = acetate, py = pyridine), a model for water oxidation catalysts. After ligand-field excitation, intersystem crossing (ISC) to a metal-centered quintet occurs in 38 fs. 30% of the hot quintet undergoes ballistic back-ISC directly to the singlet ground state, with the remainder relaxing to a long-lived triplet.

View Accepted Manuscript (DOE)

Research Organization:: University of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018904

OSTI ID:: 1978760

Alternate ID(s):: OSTI ID: 1832917

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 47 Vol. 23; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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