Criegee intermediates are pivotal in atmospheric chemistry, yet their cationic forms remain poorly understood. This study presents the infrared spectra of cationic Criegee intermediates, specifically syn- and anti-CHCHOO, using vacuum ultraviolet photoionization coupled with IR photon dissociation spectroscopy. Combined with quantum chemistry calculations, we explore conformer-specific infrared spectra and identify distinct unimolecular reaction pathways for each conformer. Our method reveals structural differences between neutral and cationic CHCHOO, including a lower isomerization barrier in the cationic form. This approach enables the investigation of conformer-specific IR spectroscopy for cationic species, which is challenging using direct IR absorption methods. By exploiting these distinct reaction pathways, we can conduct conformer-specific spectroscopic studies, advancing our ability to trace specific molecular conformations in complex chemical processes in both atmospheric and interstellar contexts.
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| http://dx.doi.org/10.1038/s41467-025-57670-4 | DOI Listing |
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