Physical Chemistry

Ballistic ΔS=2 Intersystem Crossing in a Cobalt Cubane Following Ligand-Field Excitation Probed by Extreme Ultraviolet Spectroscopy

Authors

Abstract

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 to a metal-centered quintet occurs in 38 fs. 30% of the hot quintet undergoes ballistic back-ISC directly to the singlet ground stat, with the remainder relaxing to a long-lived triplet.

Content

Thumbnail image of Cobalt Cubane Paper v0.8b for Submission.pdf

Supplementary material

Thumbnail image of Cobalt Cubane Paper SI v0.6 for Submission.pdf
Electronic Supporting Information
Further details concerning the XUV spectrometer, sample preparation, LFM simulations, and DFT calculations.