Ion-molecule reactions in CO₂ clusters induced by low-energy electron attachment

Abstract Dissociative electron attachment (DEA) process in molecular clusters is inherently complex, and elucidating the underlying mechanisms presents significant challenges. This study builds upon our previous research by investigating DEA in the larger and more numerous CO 2 clusters, and extending the electron attachment energy to 15 eV. This enhanced approach allows for the detection of anionic species such as O <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:msubsup> <mml:mrow/> <mml:mrow> <mml:mn>2</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>−</mml:mo> </mml:mrow> </mml:msubsup> </mml:math> and (CO 2 ) n O <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:msubsup> <mml:mrow/> <mml:mrow> <mml:mn>2</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>−</mml:mo> </mml:mrow> </mml:msubsup> </mml:math> . We recorded the production efficiency curves and kinetic energy distributions of the fragment anions, revealing that the O <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:msubsup> <mml:mrow/> <mml:mrow> <mml:mn>2</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>−</mml:mo> </mml:mrow> </mml:msubsup> </mml:math> anions can be formed via the DEA process of CO 2 monomers, consistent with previously reported observations. Additionally, O <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:msubsup> <mml:mrow/> <mml:mrow> <mml:mn>2</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>−</mml:mo> </mml:mrow> </mml:msubsup> </mml:math> may also be produced through a cascade reaction process involving ion-molecule/atom interactions within the clusters, even when the attachment energy exceeds the DEA threshold of O <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:msubsup> <mml:mrow/> <mml:mrow> <mml:mn>2</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>−</mml:mo> </mml:mrow> </mml:msubsup> </mml:math> production from CO 2 monomers. Furthermore, the stabilization of these detected anions (CO 2 ) n O <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:msubsup> <mml:mrow/> <mml:mrow> <mml:mn>2</mml:mn> </mml:mrow> <mml:mrow> <mml:mo>−</mml:mo> </mml:mrow> </mml:msubsup> </mml:math> is attributed to energy dissipation via molecular evaporative cooling, as previously proposed. This study offers new insights into the underlying mechanisms of DEA in molecular clusters, thereby enhancing our understanding of electron-induced reactions in atmospheric and astrochemical contexts.