PNNL

Abstract

Mechanistic insights into photodissociation dynamics of transition metal carbonyls, like Fe(CO)5, are fundamental for understanding active catalytic intermediates. Although extensively studied, the ultrafast structural dynamics of these systems remain elusive. Using ultrafast X-ray scattering, we uncover the ultrafast photochemistry of Fe(CO)5 in real space and time, observing synchronous oscillations in atomic pair distances, followed by a prompt rotating CO release preferentially in the axial direction. This behavior aligns with simulations, reflecting the interplay between the axial Fe-C distances’ potential energy landscape and non-adiabatic transitions between metal-to-ligand charge-transfer states. Additionally, we characterize a secondary delayed CO release associated with a reduction of Fe-C steady state distances and structural dynamics of the formed Fe(CO)4. Our results quantify energy redistribution across vibration, rotation, and translation degrees of freedom, offering an ultrafast microscopic view of complex structural dynamics, enhancing our grasp on Fe(CO)5 photodissociation, and advancing our understanding of transition metal catalytic systems.