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

Ambar Banerjee (), Michael R. Coates, Markus Kowalewski, Hampus Wikmark, Raphael M. Jay, Philippe Wernet and Michael Odelius ()
Additional contact information
Ambar Banerjee: Stockholm University, AlbaNova University Center
Michael R. Coates: Stockholm University, AlbaNova University Center
Markus Kowalewski: Stockholm University, AlbaNova University Center
Hampus Wikmark: Uppsala University
Raphael M. Jay: Uppsala University
Philippe Wernet: Uppsala University
Michael Odelius: Stockholm University, AlbaNova University Center

Nature Communications, 2022, vol. 13, issue 1, 1-10

Abstract: 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 distances and non-adiabatic transitions between manifolds of bound MLCT and dissociative metal-centered (MC) excited states. The predominant release of axial CO ligands and delayed release of equatorial CO ligands are explained in a unified mechanism based on the σ*(Fe-C) anti-bonding character of the receiving orbital in the dissociative MC states.

Date: 2022
References: View references in EconPapers View complete reference list from CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-022-28997-z Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-28997-z

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-022-28997-z

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().