Empirical rules of molecular photophysics in the light of ultrafast spectroscopy

Chergui, Majed

In: Pure and Applied Chemistry, 2015, vol. 87, no. 6, p. 525-536

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    The advent of ultrafast laser spectroscopy has allowed entirely new possibilities for the investigation of the ultrafast photophysics of inorganic metal-based molecular complexes. In this review we show different regimes where non-Kasha behavior shows up. We also demonstrate that while ultrafast intersystem crossing is a common observation in metal complexes, the ISC rates do not scale with the magnitude of the spin-orbit coupling constant. Structural dynamics and density of states play a crucial role in such ultrafast ISC processes, which are not limited to molecules containing heavy atoms.