The effect of electron detachment on the structure and properties of the chlorine-acetonitrile anionic complex

The results of the theoretical study of ground state potential energy surfaces for the chlorine-acetonitrile anion and its photodetachment product are presented. The shallow potential surfaces allow for the nondefinitive position of the chlorine within the complex. The dissociation energy of the neu...

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Veröffentlicht in:The Journal of chemical physics 2004-10, Vol.121 (13), p.6277-6281
Hauptverfasser: Rode, Michal F, Roszak, Szczepan, Szymczak, Jaroslaw J, Sadlej, Joanna, Leszczynski, Jerzy
Format: Artikel
Sprache:eng
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Zusammenfassung:The results of the theoretical study of ground state potential energy surfaces for the chlorine-acetonitrile anion and its photodetachment product are presented. The shallow potential surfaces allow for the nondefinitive position of the chlorine within the complex. The dissociation energy of the neutral complex, estimated through the thermodynamic cycle, indicates significant structural changes due to the photodetachment process. The excess negative charge is localized mostly on the chlorine atom, and the electron detachment proceeds as an electron is removed from chlorine. The process leads to drastic changes in the electrostatic interactions within the complex. The first electronic excited state corresponds to the excess electron transfer from chlorine to acetonitrile fragment. This state is a precursor of the observed charge-transfer-to-solvent state.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1788653