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Revision of the second ionization energy of toluene

Jana Roithová 1 Detlef Schröder 1 Jessica Loos 1 Helmut Schwarz 1 Hans-Christian Jankowiak 1 Robert Berger 1 Roland Thissen 2 Odile Dutuit 2
1 Institut für Chemie
2 Laboratoire de Chimie Physique
Abstract : Charge stripping (CS) of the molecular ion of toluene, C7H8+-->C7H82++e, is often used as a reference for the determination of second ionization energies in energy-resolved CS experiments. For calibration of the kinetic energy scale, a value of IE(C7H8+)=(15.7+/-0.2) eV derived from the appearance energy of the toluene dication upon electron ionization has been accepted generally. Triggered by some recent discrepancies between CS measurements on the one hand and different experimental methods as well as theoretical predictions on the other, we have reinvestigated the photon-induced double ionization of toluene using synchrotron radiation. These photoionization measurements yield phenomenological appearance energies of AE(C7H8+)=(8.81+/-0.03) eV for the monocation and AE(C7H82+)=(23.81+/-0.06) eV for the dication. The former is in good agreement with a much more precise spectroscopic value, IE(C7H8)=(8.8276+/-0.0006) eV. Explicit consideration of the Franck-Condon envelopes associated with photoionization to the dication in conjunction with the application of the Wannier law leads to an adiabatic ionization energy IEa(C7H8+)=(14.8+/-0.1) eV, which is as much as 0.9 eV lower than the previous value derived from electron ionization. Because in many previous CS measurements the transition C7H8+-->C7H82++e was used as a reference, the energetics of several gaseous dications might need some readjustment.
Keywords : PHOTOIONIZATION CROSS-SECTION MULTIPLY-CHARGED IONS DENSITY-FUNCTIONAL THEORIES GAS-PHASE DOUBLE-IONIZATION ELECTRONIC-STRUCTURE THRESHOLD BEHAVIOR MASS-SPECTROMETRY BENZENE DICATION REDOX PROPERTIES
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https://hal-insu.archives-ouvertes.fr/insu-00356487
Contributor : Béatrice Pibaret-Bourdon <>
Submitted on : Tuesday, January 27, 2009 - 3:49:28 PM
Last modification on : Wednesday, December 23, 2020 - 3:04:03 PM

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Jana Roithová, Detlef Schröder, Jessica Loos, Helmut Schwarz, Hans-Christian Jankowiak, et al.. Revision of the second ionization energy of toluene. Journal of Chemical Physics, American Institute of Physics, 2005, 122 (9), pp.094306. ⟨10.1063/1.1856916⟩. ⟨insu-00356487⟩

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