Ultrafast photochemistry of metal carbonyls

Ultrafast photochemistry of metal carbonyls We investigated M(CO)6 (M = Cr, Mo, W), Fe(CO)5, Ni(CO)4 and M2(CO)10(M = Mn, Re) by femtosecond spectroscopy. The molecules were pumped by one photon at 267 nm and then probed by multiphoton ionization at 800 nm and mass selective detection of the resulting parent and fragment ions. Whereas it was previously believed that such metal carbonyls are excited to a repulsive potential, leading to elimination of one or several CO, we find that only one CO is photochemically split off in times typically below 100 fs and that this is already a multistep process involving relaxation between excited-state surfaces. The second elimination takes place in the S0 of the unsaturated carbonyl and requires much longer time (>1 ps with our pump wavelength of 267 nm). The unsaturated carbonyl is initially generated in its first excited singlet state S1. If this molecule has four- or fivefold coordination, it can relax from this S1 state to S0 within about 50 fs, the pathway leading through a symmetry-induced conical intersection involving pseudorotation of the ligands. Coherent oscillations along such coordinates were observed in several molecules. In the case of threefold coordination (Ni(CO)3), however, there is no such relaxation pathway. Therefore, this photofragment shows a beautiful luminescence with >10 μs lifetime. All processes only involve the singlet manifold. Intersystem crossing takes at least 500 ps. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Ultrafast photochemistry of metal carbonyls

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Publisher
Brill Academic Publishers
Copyright
Copyright © 2001 by VSP
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry; Catalysis
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/156856701104202093
Publisher site
See Article on Publisher Site

Abstract

We investigated M(CO)6 (M = Cr, Mo, W), Fe(CO)5, Ni(CO)4 and M2(CO)10(M = Mn, Re) by femtosecond spectroscopy. The molecules were pumped by one photon at 267 nm and then probed by multiphoton ionization at 800 nm and mass selective detection of the resulting parent and fragment ions. Whereas it was previously believed that such metal carbonyls are excited to a repulsive potential, leading to elimination of one or several CO, we find that only one CO is photochemically split off in times typically below 100 fs and that this is already a multistep process involving relaxation between excited-state surfaces. The second elimination takes place in the S0 of the unsaturated carbonyl and requires much longer time (>1 ps with our pump wavelength of 267 nm). The unsaturated carbonyl is initially generated in its first excited singlet state S1. If this molecule has four- or fivefold coordination, it can relax from this S1 state to S0 within about 50 fs, the pathway leading through a symmetry-induced conical intersection involving pseudorotation of the ligands. Coherent oscillations along such coordinates were observed in several molecules. In the case of threefold coordination (Ni(CO)3), however, there is no such relaxation pathway. Therefore, this photofragment shows a beautiful luminescence with >10 μs lifetime. All processes only involve the singlet manifold. Intersystem crossing takes at least 500 ps.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Jul 1, 2001

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