Cookies Policy
X

This site uses cookies. By continuing to browse the site you are agreeing to our use of cookies.

I accept this policy

Find out more here

Ultrafast photochemistry of metal carbonyls

No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
The full text of this article is not currently available.

Brill’s MyBook program is exclusively available on BrillOnline Books and Journals. Students and scholars affiliated with an institution that has purchased a Brill E-Book on the BrillOnline platform automatically have access to the MyBook option for the title(s) acquired by the Library. Brill MyBook is a print-on-demand paperback copy which is sold at a favorably uniform low price.

Access this article

+ Tax (if applicable)
Add to Favorites
You must be logged in to use this functionality

image of Research on Chemical Intermediates

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.

Affiliations: 1: Max-Planck-Institut fü Quantenoptic, D-8574 Garching, Germany; 2: Max-Planck-Institut fü Quantenoptic, D-8574 Garching, Germany; B.I. Stepanov Institute of Physics, Belarus Academy of Sciences, 220602 Minsk, Belarus

10.1163/156856701104202093
/content/journals/10.1163/156856701104202093
dcterms_title,pub_keyword,dcterms_description,pub_author
6
3
Loading
Loading

Full text loading...

/content/journals/10.1163/156856701104202093
Loading

Data & Media loading...

http://brill.metastore.ingenta.com/content/journals/10.1163/156856701104202093
Loading

Article metrics loading...

/content/journals/10.1163/156856701104202093
2001-07-01
2016-12-06

Sign-in

Can't access your account?
  • Tools

  • Add to Favorites
  • Printable version
  • Email this page
  • Subscribe to ToC alert
  • Get permissions
  • Recommend to your library

    You must fill out fields marked with: *

    Librarian details
    Your details
    Why are you recommending this title?
    Select reason:
     
    Research on Chemical Intermediates — Recommend this title to your library
  • Export citations
  • Key

  • Full access
  • Open Access
  • Partial/No accessInformation