Atmospherically relevant ion chemistry of ozone and its cation

Abstract

The importance of ionic processes that occur in terrestrial, planetary, and stellar atmospheres is receiving increasing recognition. Actually, ions play important, often crucial, roles in a variety of atmospheric processes throughout the universe, and a strong link with the neutral chemistry is also apparent. In the terrestrial atmosphere, the ionic reactions are most relevant in those transient and fleeting events, e.g., lightning, coronas (in thunderstorm clouds and along power lines), where the local ion density is much higher than in unperturbed air, and the chemical systems are typically far from equilibrium. In such cases, ozone, a key molecule for the terrestrial atmosphere, is also present in high local concentrations; it is formed from O(2) by the same transient event. Accordingly, this review provides a survey of the positive ion chemistry of ozone with several of the most important "atmospheric" species: the reactions, the products, and the importance of the examined processes are discussed also in the light of the local thermodynamic disequilibrium (LTD) approach to the chemistry of transient atmospheric events. In all such studies, mass spectrometry is traditionally, and remains today, the experimental technique of choice. The novel application of mass spectrometry to the study of neutral species (NRMS), highly successful for the preparation and positive detection of long-sought, otherwise inaccessible, short-lived neutrals, makes mass spectrometry the most powerful tool now available for the study of the species and processes that are relevant to atmospheric chemistry. Selected examples of the interlink between the neutral and the ionic chemistry are also illustrated.

Three-Body Breakup in the Dissociative Recombination of the Covalent Triatomic Molecular IonO3+

“…This has spurred a search for reactions having a low quantum yield but with the potential of significantly impacting the ozone budget [2]. It has also been realized that the ozone cation and anion deserve attention since the ozone neutral, positive, and negative chemistry could affect each other in unanticipated ways [3]. In comparison with the vast literature on neutral ozone, not least its photochemical properties (see, e.g., [4,5]), work on the ozone cation is sparse [6], but definitely needed for an understanding of the O 3 ion chemistry in the stratosphere and lower ionosphere.…”

Isotope exchange in disulfur monoxide-water charged complexes: A mass spectrometric and computational study

“…As an example, the small CAD peak at m/z 33 hints at fragmentations occurring from species where the sulfur atom is the hydrogen-bearing site such as OSS ( These findings raise the question of whether S 2 O˙ϩ displays any S˙ϩ-transfer ability, in comparison to O 3 ·ϩ , which is a good O˙ϩ donor [22]. Actually, under high-resolution conditions the source-generated m/z 50 ion (Figure 2b) proves to be a mixture of two isobaric species: S 18 O˙ϩ and [H 2 ,S,O]˙ϩ.…”

High-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopic study of the two lowest electronic states of the ozone cation O3+

“…Tunable XUV radiation in the range 101 000-104 000 cm Ϫ1 was generated by resonanceenhanced sum-frequency mixing in a xenon gas beam using the (5p) 5 ( 2 P 3/2 )6p͓1/2͔(Jϭ0)←(5p) 6 Ozone was generated by a discharge of oxygen ͑purity 99.999%, Pangas͒ in a homemade ozonizer ͑Southampton͒ and stored on nonindicating silica gel in a U-tube at Ϫ79°C. To transfer the substance into the measurement chamber, the U-tube was attached to the gas inlet of the spectrometer using glass and teflon-coated stainless steel tubing.…”