Under pulsed laser excitation (ns), lanthanide-based metal-organic complexes exhibit a rich photochemistry derived from multi-photon fragmentation of the organic ligand. Optimization of the irradiance allows capture of reaction intermediates through mass spectrometry. However, elucidating the highly-branched and overlapping chemical pathways from the photo-fragmentation patterns is daunting. Density functional methods, including time-dependent excited-state molecular dynamics, TDESMD, have proved valuable, both in structural determination of reaction intermediates and in predicting or confirming reaction mechanisms. DFT has clearly shown that much of the photochemistry is initiated by ligand-to-metal charge-transfer (LMCT), followed by reaction of the transient ligand radical. We will show the results of photo-fragmentation/ionization time-of-flight mass spectrometry for several β-diketonate and cyclopentadienyl complexes in conjunction with DFT predictions of photo-induced changes in electronic structure and subsequent chemical reaction.

Role of density functional theory in interpreting photochemistry of metal-organic species

256th National Meeting (2018)

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