Abstract
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 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.
- Received 30 January 2009
DOI:https://doi.org/10.1103/PhysRevLett.103.013001
©2009 American Physical Society
Synopsis
Halfway between an atom and a molecule
Published 6 July 2009
Ultrafast laser measurements map out the electronic structure of a neutral molecule as it photoionizes and breaks apart, leading to new conclusions about the time it takes for dissociation to occur.
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