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Understanding the Infrared Spectrum of Bare CH₅⁺

Author:
Asvany, Oskar, P, Padma Kumar, Redlich, Britta, Hegemann, Ilka, Schlemmer, Stephan, Marx, Dominik
Source:
Science 2005 v.309 no.5738 pp. 1219-1222
ISSN:
0036-8075
Subject:
carbon dioxide, freezing, hydrogen, methane, molecular dynamics
Abstract:
Protonated methane, CH₅⁺, continues to elude definitive structural assignment, as large-amplitude vibrations and hydrogen scrambling challenge both theory and experiment. Here, the infrared spectrum of bare CH₅⁺ 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 [approximately]110 kelvin to finite-temperature infrared spectra, calculated by ab initio molecular dynamics, supports fluxionality of bare CH₅⁺ under experimental conditions and provides a dynamical mechanism for exchange of hydrogens between CH₃ tripod positions and the three-center bonded H₂ 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.
Agid:
1530653