Formation of C4H4•+ from the pyridine radical cation: A theoretical mechanistic and kinetic study

Min Kyoung Yim, Joong Chul Choe

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Abstract

The potential energy surface (PES) for the formation of C4H 4•+ from the pyridine radical cation by loss of HCN was determined from quantum chemical calculations using the G3//B3LYP method. The complete reaction pathways for the formation of the low-energy C 4H4•+ isomers, radical cations of methylenecyclopropene (MCP•+), vinylacteylene (VA •+), cyclobutadiene, and butatriene were obtained. Based on the PESs, a Rice-Ramsperger-Kassel-Marcus model calculation was performed to investigate the dissociation kinetics. The calculated dissociation rate constants agreed with the previous experimental data. It was predicted that a mixture of MCP•+ and VA•+ was formed by loss of HCN. The formation of MCP•+ was more favored near the dissociation threshold and at high energies, whereas the formation of VA •+ was more favored at the low energies corresponding to the ion lifetime of microseconds.

Original languageEnglish
Pages (from-to)3087-3094
Number of pages8
JournalJournal of Physical Chemistry A
Volume115
Issue number14
DOIs
StatePublished - 14 Apr 2011

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