High Pressure Mass Spectrometry
The technique of High Pressure Mass Spectrometry (HPMS) was pioneered by Kebarle[l]. The original intent was to replicate the environment in which radiolysis experiments were carried out in order to elucidate the precise mechanisms by which the final observed radiolysis products had been formed. In this early version of the HPMS experiment a gas confined at high pressure (100–300 torr) was irradiated continuously by an a particle emitter–. The ions emerging from a small ion exit aperture were then sampled by a mass spectrometer and attempts were made to deduce the role of the ions observed in the formation of the neutral products by conventional radiolysis techniques. The application of these high pressure techniques to radiation chemistry of hydrocarbons proved unsatisfactory but, more importantly, it was noted that multiply solvated protons dominated the mass spectrum when either water or ammonia were present in the ion source. This quickly led to the realization that the successive solvation equilibria, eqn. (1), could readily be studied and a prolific era of the study of gas phase ion energetics was born–.
KeywordsProton Affinity Black Body Radiation Potential Energy Profile Dissociative Electron Attachment Unimolecular Dissociation
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