Size-dependent stabilities and intracluster reactions of potassium atom and acrylonitrile molecules (AN; clusters were investigated. Previously reported magic numbers (intensity anomalies) of n=3k (k=1–4) using photoionization mass spectrum of and size-specific elimination reactions (HCN elimination from clusters of and elimination from n=3 and 6 clusters) were explained by a cyclohexane derivative formation in an intracluster trimeric cyclization (anionic oligomerization) initiated by electron transfer from a K atom in To elucidate larger structures, unimolecular metastable dissociations of photoions were observed using a reflectron time-of-flight mass spectrometer. A metastable dissociation pathway of n→n−1 (AN-loss) was predominantly observed for all parent sizes; furthermore, for parent ions with n=6, 9, and 12, pathway of n→n−3 -loss] was also observed. These size-dependent dissociation pathways of photoions are related to structures of neutral clusters since intramolecular bonds are expected to be formed in the oligomerization reactions in neutrals and to be conserved in the photoionization process. Parent clusters that cause the n→n−1 dissociations have structures in which at least one AN monomer can coordinate without forming any chemical bonds. The observation of n→n−3 pathways corresponds to the existence of isomers of n= 3k (k=2–4) clusters having k cyclohexane derivatives, which are formed by intracluster multiple trimeric cyclization reactions with 3k AN molecules in neutral clusters. The existence of at least two types of structural isomers (including reacted AN or unreacted AN) in these clusters is shown from these experimental results, and is further supported by calculations of the microcanonical dissociation rate constants for each pathway based on the Rice–Ramsperger–Kassel–Marcus theory.
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15 September 2002
Research Article|
September 15 2002
Intracluster multiple trimeric cyclization of acrylonitrile clusters initiated by electron transfer from a potassium atom: Size-dependent pathways in metastable dissociation of photoions
Keijiro Ohshimo;
Keijiro Ohshimo
Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
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Fuminori Misaizu;
Fuminori Misaizu
Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
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Koichi Ohno
Koichi Ohno
Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
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J. Chem. Phys. 117, 5209–5220 (2002)
Article history
Received:
March 07 2002
Accepted:
June 25 2002
Citation
Keijiro Ohshimo, Fuminori Misaizu, Koichi Ohno; Intracluster multiple trimeric cyclization of acrylonitrile clusters initiated by electron transfer from a potassium atom: Size-dependent pathways in metastable dissociation of photoions. J. Chem. Phys. 15 September 2002; 117 (11): 5209–5220. https://doi.org/10.1063/1.1500732
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