Potential role of methyl-radical adducts with carbon dioxide in the Martian atmosphere

Eur. J. Mass Spectrom. 9, 287–294 (2003)
DOI: 10.1255/ejms.552

Potential role of methyl-radical adducts with carbon dioxide in the Martian atmosphere

Detlef Schröder,^* Marija Semialjac and Helmut Schwarz
Institut für Chemie der Technischen Universität Berlin, 10623 Berlin, Germany. E-mail: df@www.chem.tu-berlin.de

ABSTRACT:

Neutralization reionization (NR) and charge reversal (CR) mass spectra of [CH₃/CO₂]^–/+ ions are used to examine the behavior of the transient neutral radicals CH₃OCO^· and CH3COO^·. While neutralization of the ionic species is associated with considerable changes of the geometries resulting in unfavorable Franck–Condon factors for vertical electron transfer in high-energy collisions, NR experiments nevertheless demonstrate the existence of both radicals in the gas phase. Analysis of the NR and CR spectra provides insight into the decomposition reactions of CH₃OCO^· and CH₃COO^·. For the former, loss of either CO or CO₂ can occur at the neutral stage, whereas decarboxylation prevails in the latter case.

Keywords: acetoxy radical, carbon dioxide, density functional theory, Martian atmosphere, mass spectrometry, methoxyformyl radical

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