Computer Science
Scientific paper
Jun 2010
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2010mss..confere10m&link_type=abstract
"International Symposium On Molecular Spectroscopy, 65th Meeting, Held 21-25 June, 2010 at Ohio State University. http://molspec
Computer Science
Radicals And Ions
Scientific paper
For atomic anions the photoelectron angular distribution (PAD) is a signature of the bound excess electron wavefunction. However, even for relatively simple molecular anions the relationship between the detachment orbital and the PAD is more complicated. We demonstrate this with a series of near threshold photoelectron images for superoxide detachment, recorded over small photon energy increments. The highest occupied, π_g orbital has a strong resemblance to an atomic d-orbital. Detachment from the superoxide anion via the O_2(X ^3 Σ_g^-, v^') ← O_2^- (X ^2Π_g, v^'^' = 0) transitions reveals that the electron kinetic energy dependence of the PAD resembles that of atomic anions. However, there is also a clear dependence on the vibrational energy deposited in the neutral O_2. Comparison with theoretical calculations reveals that this dependence is not due to non-adiabatic effects. Instead it arises in the change of the electronic transition moment across the X-X band, a direct consequence of the parametric dependence of the π_g orbital function on the internuclear separation.
Cavanagh Steven
Gibson Stephen
Lewis Brenton R.
Mabbs Richard
Mbaiwa Foster
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