Kinetic energy release in thermal ion-molecule reactions: The Nb2+ (benzene) single charge-transfer reaction

Article abstract of DOI:10.1063/1.460614

We have adapted the techniques originally developed to measure ion kinetic energies in ion cyclotron resonance (ICR) spectrometry to study the single charge-transfer reaction of Nb²⁺ with benzene under thermal conditions in a Fourier transform ion cyclotron resonance mass spectrometer (FTICRMS).The partitioning of reaction exothermicity among the internal and translational modes available is consistent with a long-distance electron-transfer mechanism, in which the reactants approach on an ion-induced dipole attractive potential and cross to a repulsive potential at a critical separation of ca. 7.5 Angstroem when electron transfer occurs.The reaction exothermicity, 5.08 eV, is partitioned to translation of Nb⁺, 0.81 +/- 0.25 eV, translation of C6H6⁺, 1.22 +/- 0.25 eV, and internal excitation of C6H6⁺ to produce the la_2u electronic state, which is ca. 3 eV above to ground state of the ion.We have also studied the kinetics of the reaction of Nb²⁺ with benzene and determined the rate constant, k = 1.4*10^-9 cm³ molecule^-1 s^-1, and the efficiency, 0.60, of the process.These also support the proposed charge-transfer mechanism.In addition to the charge-transfer pathway, which accounts for 95percent of the reaction products, Nb²⁺ is observed to dehydrogenate benzene to form Nb²⁺ (benzyne).This process implies D(Nb²⁺ -benzyne) above 79 kcal/mol.

Full text of DOI:10.1063/1.460614

Kinetic energy release in thermal ion–molecule reactions: The Nb2 +–(benzene)
single charge–transfer reaction
James R. Gord, Ben S. Freiser, and Steven W. Buckner
Citation: The Journal of Chemical Physics 94, 4282 (1991); doi: 10.1063/1.460614
View online: http://dx.doi.org/10.1063/1.460614
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/94/6?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
28.240.225.44 On: Thu, 18 Dec 2014 09:33:36
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
28.240.225.44 On: Thu, 18 Dec 2014 09:33:36
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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