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

Loading next page...
 
/lp/springer_journal/ultrafast-photochemistry-of-metal-carbonyls-0RCknjrxx4
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

There are no references for this article.

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 12 million articles from more than
10,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Unlimited reading

Read as many articles as you need. Full articles with original layout, charts and figures. Read online, from anywhere.

Stay up to date

Keep up with your field with Personalized Recommendations and Follow Journals to get automatic updates.

Organize your research

It’s easy to organize your research with our built-in tools.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

Monthly Plan

  • Read unlimited articles
  • Personalized recommendations
  • No expiration
  • Print 20 pages per month
  • 20% off on PDF purchases
  • Organize your research
  • Get updates on your journals and topic searches

$49/month

Start Free Trial

14-day Free Trial

Best Deal — 39% off

Annual Plan

  • All the features of the Professional Plan, but for 39% off!
  • Billed annually
  • No expiration
  • For the normal price of 10 articles elsewhere, you get one full year of unlimited access to articles.

$588

$360/year

billed annually
Start Free Trial

14-day Free Trial