Berry pseudorotation enabled photodissociation of Fe(CO)5 observed by ultrafast electron diffraction
Haoran Ma1,2,3,4, J Pedro F Nunes5, Ambar Banerjee6,7
1Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing, China.
None:
The structural dynamics of metal carbonyls are central to processes ranging from catalysis to organometallic synthesis. Here we investigate the photodissociation of a prototypical transition metal carbonyl, Fe(CO)5, using mega-electron-volt ultrafast electron diffraction. By separately tracking structural evolution along the axial and equatorial directions, we provide an atomistic, angle-resolved view of the nuclear motions preceding CO dissociation and infer key features of the excited-state potential energy surface from the experimental observations. We further show that vibrational coupling before reaching the conical intersection facilitates the loss of a random carbonyl ligand via the Berry pseudorotation mechanism.
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