Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release.

ABSTRACT: Early excited state dynamics in the photodissociation of transition metal carbonyls determines the chemical nature of short-lived catalytically active reaction intermediates. However, time-resolved experiments have not yet revealed mechanistic details in the sub-picosecond regime. Hence, in this study the photoexcitation of ironpentacarbonyl Fe(CO)₅ is simulated with semi-classical excited state molecular dynamics. We find that the bright metal-to-ligand charge-transfer (MLCT) transition induces synchronous Fe-C oscillations in the trigonal bipyramidal complex leading to periodically reoccurring release of predominantly axial CO. Metaphorically the photoactivated Fe(CO)₅ acts as a CO geyser, as a result of dynamics in the potential energy landscape of the axial Fe-C d

SUBMITTER: Banerjee A 

PROVIDER: S-EPMC8921231 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature