Electron correlation can be the driving force for ultrafast charge migration. Using ab initio calculations this is demonstrated in the present paper for the first time as a consequence of ionizing the outer-valence shell. The example studied is 2-phenylethyl-N,N-dimethylamine (PENNA) on which exciting pump-probe measurements have been recently carried out. (C) 2007 Elsevier B.V. All rights reserved.