Kinetic energy release in thermal ion-molecule reactions: Single charge-transfer reactions of V sup 2+ and Ta sup 2+ with benzene

• Published in: Journal of physical chemistry (1952) Vol. 95:21
• Main Authors: Gord, J.R., Freiser, B.S, Buckner, S.W.
• Format: Journal Article
• Language: English
• Published: United States 17.10.1991
• Subjects: 400201 - Chemical & Physicochemical Properties; AROMATICS; BENZENE; CATIONS; CHARGED PARTICLES; CHEMICAL REACTION KINETICS; COLLISIONS; DATA; ELEMENTS; ENERGY SPECTRA; EXPERIMENTAL DATA; HYDROCARBONS; INFORMATION; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ION COLLISIONS; ION CYCLOTRON RESONANCE SPECTROSCOPY; ION SPECTROSCOPY; ION-MOLECULE COLLISIONS; IONS; KINETICS; MASS SPECTROSCOPY; METALS; MOLECULE COLLISIONS; NUMERICAL DATA; ORGANIC COMPOUNDS; REACTION KINETICS; SPECTRA; SPECTROSCOPY; TANTALUM; TRANSITION ELEMENTS; VANADIUM
• ISSN: 0022-3654; 1541-5740
• DOI: 10.1021/j100174a048

Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) has been used to study the single charge-transfer reactions of V{sup 2+} and Ta{sup 2+} with benzene under thermal conditions. Thermal charge-transfer rate constants of 2.0 {times} 10{sup {minus}9} and 1.2 {times} 10{sup {minus}9} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} were measured for V{sup 2+} and Ta{sup 2+}, respectively. The total kinetic energy of the product ions was determined to be 1.91 {plus minus} 0.50 eV for the V{sup 2+} case and 2.82 {plus minus} 0.50 eV for the Ta{sup 2+} case. These results and a previous study of the Nb{sup 2+}-benzene single charge-transfer system suggest a simple long-distance electron-transfer mechanism proceeding by ionization of the 1a{sub 2u} orbital of benzene with significant internal excitation of the nascent C{sub 6}H{sub 6}{sup +} product.