Understanding the Infrared Spectrum of Bare CH 5 +

Abstract

Protonated methane, CH 5 + , continues to elude definitive structural assignment, as large-amplitude vibrations and hydrogen scrambling challenge both theory and experiment. Here, the infrared spectrum of bare CH 5 + is presented, as detected by reaction with carbon dioxide gas after resonant excitation by the free electron laser at the FELIX facility in the Netherlands. Comparison of the experimental spectrum at ∼110 kelvin to finite-temperature infrared spectra, calculated by ab initio molecular dynamics, supports fluxionality of bare CH 5 + under experimental conditions and provides a dynamical mechanism for exchange of hydrogens between CH 3 tripod positions and the three-center bonded H 2 moiety, which eventually leads to full hydrogen scrambling. The possibility of artificially freezing out scrambling and internal rotation in the simulations allowed assignment of the infrared spectrum despite this pronounced fluxionality.