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22 April 1993 Spectroscopy and dynamics of ionic complexes: N2+-He and N2O+-Ar
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Proceedings Volume 1858, Laser Techniques for State-Selected and State-to-State Chemistry; (1993)
Event: OE/LASE'93: Optics, Electro-Optics, and Laser Applications in Scienceand Engineering, 1993, Los Angeles, CA, United States
This paper describes investigations of fundamental photophysical processes in the small inorganic ionic complexes N2+-He and N2O+-Ar. Studies were carried out by observing the wavelength dependent photofragment yield of mass selected ionic species in a guided ion beam apparatus. Spectra of the N2+-He complex exhibit several bands in the near UV that correspond with those of the N2+ chromophore. By measuring the relative intensities of the B $IMP X origin and 111 hot bands as a function of ion flight time from ion source to the laser, a vibrational predissociation lifetime of 220 +/- 30 microsecond(s) has been determined for the (v equals 1) state of the N2+-He complex. For the N2O+-Ar complex, vibrationally structured electronic bands were observed which arise from charge transfer type transitions. In the ground state of the complex the charge is localized principally on N2O. Lying above this ground state by the difference in the N2O and Ar ionization potentials are several excited states where the charge is localized on Ar. Photodissociation to produce both N2O+ and Ar+ fragments occurs. While the former fragment probably arises via vibrational predissociation from vibrationally excited levels in the ground state, the appearance of Ar+ fragments is evidence for rapid vibrational predissociation on the excited state surface. Dissociation energies (D0 values) of 690 cm-1 for the X state of the N2O+-Ar complex and 1340 cm-1 for the lowest charge transfer state dissociation energy were inferred from the appearance thresholds for N2O+ and Ar+ fragments. Various possible dissociation routes are discussed.
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E. J. Bieske, A. M. Soliva, A. Friedmann, and John P. Maier "Spectroscopy and dynamics of ionic complexes: N2+-He and N2O+-Ar", Proc. SPIE 1858, Laser Techniques for State-Selected and State-to-State Chemistry, (22 April 1993);

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