Photodissociation dynamics of pyridine

Ming Fu Lin, Yuri A. Dyakov, Chien-Ming Tseng, Alexander M. Mebel, Sheng Hsien Lin, Yuan T. Lee, Chi Kung Ni*

*Corresponding author for this work

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Abstract

Photodissociation of pyridine, 2,6- d2 -pyridine, and d5 -pyridine at 193 and 248 nm was investigated separately using multimass ion imaging techniques. Six dissociation channels were observed at 193 nm, including C5 N H5 → C5 N H4 +H (10%) and five ring opening dissociation channels, C5 N H5 → C4 H4 +HCN, C5 N H5 → C3 H3 + C2 N H2, C5 N H5 → C2 H4 + C3 NH, C5 N H5 → C4 N H2 +C H3 (14%), and C5 N H5 → C2 H2 + C3 N H3. Extensive H and D atom exchanges of 2,6- d2 -pyridine prior to dissociation were observed. Photofragment translational energy distributions and dissociation rates indicate that dissociation occurs in the ground electronic state after internal conversion. The dissociation rate of pyridine excited by 248-nm photons was too slow to be measured, and the upper limit of the dissociation rate was estimated to be 2× 103 s-1. Comparisons with potential energies obtained from ab initio calculations and dissociation rates obtained from the Rice-Ramsperger-Kassel-Marcus theory have been made.

Original languageEnglish
Article number054309
JournalJournal of Chemical Physics
Volume123
Issue number5
DOIs
StatePublished - 5 Sep 2005

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    Lin, M. F., Dyakov, Y. A., Tseng, C-M., Mebel, A. M., Lin, S. H., Lee, Y. T., & Ni, C. K. (2005). Photodissociation dynamics of pyridine. Journal of Chemical Physics, 123(5), [054309]. https://doi.org/10.1063/1.1994849