Non-Adiabatic Direct Dynamics Study of Chromium Hexacarbonyl Photodissociation

Content Provider	Semantic Scholar
Author	Paterson, Martin J. Hunt, Patricia A. Robb, Michael A. Takahashi, Ohgi
Copyright Year	2002
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.
Starting Page	10494
Ending Page	10504
Page Count	11
File Format	PDF HTM / HTML
DOI	10.1021/jp026394t
Alternate Webpage(s)	https://homepage.univie.ac.at/mario.barbatti/papers/method/robb-surface-hopping.pdf
Alternate Webpage(s)	https://doi.org/10.1021/jp026394t
Volume Number	106
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article