Multiphoton breakdown of acetylene; formation of organic building block fragments

• Published in: Physical chemistry chemical physics : PCCP Vol. 25; no. 3; pp. 169 - 174
• Main Authors: Jiang, Meng-Xu, Giannakidis, Ioannis C, Samartzis, Peter C, Kvaran, Ágúst
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 18.01.2023
• Subjects: Acetylene; Breakdown; Data analysis; Energy distribution; Excitation; Fragmentation; Fragments; Interstellar chemistry; Interstellar space; Ion velocity; Kinetic energy; Molecular ions; Organic chemistry; Photodissociation; Photoionization; Photons; Rydberg states
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d2cp04467f

Mass resolved REMPI spectra and electron and ion velocity map images were recorded for REMPI of acetylene in the case of two-photon resonant excitations to low lying 3p and 4p Rydberg states. Combined data analysis of ion signal intensities and electron and ion kinetic energy release distribution revealed multiphoton-fragmentation processes in terms of photodissociation and photoionization channels to form the molecular ion, C 2 H 2 + and the fragment ions H + , C + , CH + , CH 2 + , C 2 + and C 2 H + . The ratio of fragment ion formation over the parent ion formation increases with excitation energy. To a large extent, multiphoton-fragmentation involves the initial breakdown of the molecule into ground and excited state neutral fragments by two-, three- and four-photon dissociation processes prior to multiphoton ionization. The three-photon dissociation processes via superexcited molecular state(s) are found to be the most important and electronically excited fragment species playing a significant role in the overall multiphoton-fragmentation. Furthermore, the data are indicative of the involvement of secondary photodissociation processes and provide information on fragment energetics as well as state interactions. The question, whether acetylene could be an important source of building block fragments for the formation of organic molecules in interstellar space, is addressed. Multiphoton-fragmentation (photodissociation and photoionization) processes of acetylene via resonant excitations to Rydberg states; fragment formation.