S. Ring et al., PHOTOIONIZATION AND DISSOCIATION OF BF3-CENTER-DOT((CH3)(2)O)(N) MIXED AGGREGATES (N = 1, 2) STUDIED BY MASS-SPECTROMETRY AND AB-INITIO CALCULATIONS, Chemical physics letters, 280(3-4), 1997, pp. 251-259
Upon photoionization of mixed aggregates of boron trifluoride and dime
thyl ether, strong intermolecular and intramolecular fragmentation is
observed. The complexes and their fragments show similar appearance en
ergies; they exceed considerably the adiabatic ionization potentials.
Ab initio calculations of the ionic and neutral structures of the aggr
egates were performed in order to elucidate the ionization and fragmen
tation behaviour. The mixed aggregates contain neutral BF3 . (CH3)(2)O
units which are almost uninfluenced by the aggregation of a second et
her molecule. Ionization of the (CH3)(2)O . BF3 unit leads to intermol
ecular charge transfer before dissociation or fluorine abstraction to
form the cationic singlet molecule (CH3)(2)OBF2+. (C) 1997 Published b
y Elsevier Science B.V.