The origin of enhanced O2+ production from photoionized CO2 clusters

CO2-rich planetary atmospheres are continuously exposed to ionising radiation driving major photochemical processes. In the Martian atmosphere, CO2 clusters are predicted to exist at high altitudes motivating a deeper understanding of their photochemistry. In this joint experimental-theoretical stud...

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Detalles Bibliográficos
Autores: Ganguly, Smita, Barreiro Lage, Dario, Walsh, Noelle, Oostenrijk, Bart, Sorensen, Stacey L., Díaz-Tendero Victoria, Sergio, Gisselbrecht, Mathieu
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/706807
Acceso en línea:http://hdl.handle.net/10486/706807
https://dx.doi.org/10.1038/s42004-022-00629-z
Access Level:acceso abierto
Palabra clave:CO₂
X-ray ionisation
Martian atmosphere
Photochemical processes
Química
Descripción
Sumario:CO2-rich planetary atmospheres are continuously exposed to ionising radiation driving major photochemical processes. In the Martian atmosphere, CO2 clusters are predicted to exist at high altitudes motivating a deeper understanding of their photochemistry. In this joint experimental-theoretical study, we investigate the photoreactions of CO2 clusters (≤2 nm) induced by soft X-ray ionisation. We observe dramatically enhanced production of O2+ from photoionized CO2 clusters compared to the case of the isolated molecule and identify two relevant reactions. Using quantum chemistry calculations and multi-coincidence mass spectrometry, we pinpoint the origin of this enhancement: A size-dependent structural transition of the clusters from a covalently bonded arrangement to a weakly bonded polyhedral geometry that activates an exothermic reaction producing O2+. Our results unambiguously demonstrate that the photochemistry of small clusters/particles will likely have a strong influence on the ion balance in atmospheres