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By Harnwell G. P.

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82 83 83 ABSTRACT The use of high-pressure mass spectrometric (HPMS) and Fourier transform ion cyclotron resonance (FTICR) techniques is described for the elucidation of unimolecular dissociation of gaseous ions. (1) The kinetics of clustering of CH30- onto CH3OH in the HPMS system are used to deduce the thermal unimolecular dissociation rate constant of the proton-bound methoxide ion. In addition a second, more weakly bound electrostatic complex is implicated as an entrance channel complex on this potential energy surface.

The theoretical treatment of the ionization process has been seen as a complex problem with the involvement of three charged particles in the exit channel. 4~ Even for atomic hydrogen, the simplest ionization case, the long-range Coulomb force restricts free movement of the particles even at very large interparticle separations. 4~ Quantum methods use a partial wave approximation. The Born approximation 35 considers the incident electron as a plane wave with limited interaction with the molecule, and it has had limited s u c c e s s .

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