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We study the relaxation dynamics and intersystem-crossing to the metastablestate in laser-pumped tetra and hexa-coordinated nickel porphyrins. We use aligand-field model which takes into account the crystal field created by theporphyrin ring and axial ligands. By accounting for the energy redistributionof the lattice vibrations of the metal-ligand stretch mode we get anirreversible decay within the order of the hundreds of femtoseconds timescale.We show how non-equilibrium time-dependent x-ray absorption atthe Ni K-edgemeasurements can elucidate the nature of the intermediate states involved inthe decay. Understanding radiationless transitions in this system is ofinterest for their relevance in photocatalytic systems and photothermalsensitizers for cancer treatment.

Ultrafast intersystem crossing in nickel porphyrins