Relaxation mechanisms following inner-valence ionization of CN- are investi
gated using ab initio quantum chemistry methods. Due to a severe failure of
the molecular orbital picture, there is a relatively large number of elect
ronic states that are excited by ionization in the inner-valence regime. Mo
st of these states are found to decay by electron emission, resulting in th
e formation of vibrationally bound CN+. General conclusions can be drawn co
ncerning larger molecular anions. (C) 2000 Published by Elsevier Science B.