Inner-valence ionization of molecular anions and ultrafast relaxation by electron emission

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. V.