Dynamics of the F-2+CH3SCH3 reaction: A molecule-molecule reaction without entrance barrier

Abstract

The F-2+CH3SCH3 reaction was studied with crossed molecular beam techniques and high level ab initio calculations. Significant reactivity was observed even at low collision energies, consistent with the negligible barrier height obtained from the ab initio calculations. All experimental findings are consistent with a weakly bound reaction intermediate of F-F-S(CH3)(2) structure, which possesses a special type of three-center four-electron bonding. Analogous intermediates can also explain the reactions of F-2 with CH3SH and CH3SSCH3.