Electronic resonances commonly decay via internal conversion to vibrationally hot anions and subsequent statistical electron emission. We observed vibrational structure in such an emission from the nitrobenzene anion, in both the 2D electron energy loss and 2D photoelectron spectroscopy of the neutral and anion, respectively. The emission peaks could be correlated with calculated nonadiabatic coupling elements for vibrational modes to the electronic continuum from a nonvalence dipole-bound state. This autodetachment mechanism via a dipole-bound state is likely to be a common feature in both electron and photoelectron spectroscopies.

Department of Chemistry Durham University Durham DH1 3LE United Kingdom

Department of Chemistry Lomonosov Moscow State University 119991 Moscow Russia

J Heyrovský Institute of Physical Chemistry Czech Academy of Sciences Dolejškova 3 18223 Prague 8 Czech Republic

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