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

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d1cp04136c· OSTI ID:1978760
ORCiD logo [1]; ORCiD logo [1]
  1. University of Illinois at Urbana-Champaign, IL (United States)
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We report femtosecond M2,3-edge X-ray absorption near-edge structure (XANES) spectroscopy is used to probe the excited-state dynamics of the cobalt cubane [CoIII4O4](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.

Research Organization:
Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR)
Grant/Contract Number:
SC0018904; DGE-1746047; FA9550-14-1-0314
OSTI ID:
1978760
Alternate ID(s):
OSTI ID: 1832917
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 23, Issue 47; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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