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Phys. Rev. Lett. 103, 013001 (2009) [4 pages]

Real-Time Evolution of the Valence Electronic Structure in a Dissociating Molecule

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Ph. Wernet1,*, M. Odelius2, K. Godehusen1, J. Gaudin1,†, O. Schwarzkopf1, and W. Eberhardt1
1Helmholtz-Zentrum Berlin, Albert-Einstein-Strasse 15, D-12489 Berlin, Germany
2FYSIKUM, Stockholm University, AlbaNova, S-106 91 Stockholm, Sweden

Received 30 January 2009; published 29 June 2009

See accompanying Physics Synopsis

Time-resolved valence band photoelectron spectroscopy with a temporal resolution of 135 fs is used to map the entire occupied valence electronic structure of photoexcited gas-phase Br2 molecules during dissociation. The observed shifting and mixing of valence energy levels defines a transition period where the system appears to be intermediate between atoms and molecules. The surprisingly short bond breaking or dissociation time is determined by monitoring in real time how the photoelectron multiplet structure of the free atom arises from the valence states of the photoexcited molecule.

© 2009 The American Physical Society

URL:
http://link.aps.org/doi/10.1103/PhysRevLett.103.013001
DOI:
10.1103/PhysRevLett.103.013001
PACS:
32.80.Fb, 33.60.+q, 42.65.Ky, 82.53.Eb

*wernet@helmholtz-berlin.de

Permanent address: European XFEL/DESY, Notkestrasse 85, D-22607 Hamburg, Germany.