Abstract
The photodissociation of Cr(CO)6 has been studied using direct dynamics including trajectory surface hopping. The dissociation takes place on a steep excited-state potential surface leading to ejection of a CO ligand within 100 fs in reasonable agreement with time-resolved studies by Fuβ et al.1-3 Our dynamics studies of the Cr(CO)5 photoproduct allow us to determine mechanistic details of the relaxation of the excited state of this species. We find that Cr(CO)5 decays to the ground state via a Jahn−Teller (symmetry-induced) conical intersection, at a trigonal bipyramid geometry. The molecule then oscillates in the well of the “moat” surrounding this conical intersection. Our results provide evidence for the dissociation mechanism proposed by Fuβ et al.1-3 Both the computed frequency of the coherent oscillation and the delay time until this motion is observed are in good agreement with experimental results.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
