Isomerization of cyanopropyne in solid argon

Cyanopropyne, CH 3 -C&z.tbd;C-CN, is a simple molecule whose photochemistry is still unexplored. Here we investigate the UV photolysis of this astrophysically significant nitrile trapped in solid argon. The FTIR study was assisted with 15 N-isotopic substitution data and with DFT-level computati...

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Published in:Physical chemistry chemical physics : PCCP 2019-06, Vol.21 (25), p.13668-13678
Main Authors: Custer, Thomas, Szczepaniak, Urszula, Gronowski, Marcin, Piétri, Nathalie, Couturier-Tamburelli, Isabelle, Guillemin, Jean-Claude, Turowski, Micha, Ko os, Robert
Format: Article
Language:English
Subjects:
Absorption spectra
Argon
Chemical Sciences
Cyanide process
Infrared absorption
Infrared spectra
Isomerization
Photochemistry
Photolysis
Potential energy
Signal processing
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Summary:Cyanopropyne, CH 3 -C&z.tbd;C-CN, is a simple molecule whose photochemistry is still unexplored. Here we investigate the UV photolysis of this astrophysically significant nitrile trapped in solid argon. The FTIR study was assisted with 15 N-isotopic substitution data and with DFT-level computations including the analyses of ground- and excited-state potential energy surfaces. Cyanopropyne was found to decay mainly via a two-step isomerization process. Infrared absorption spectra evolved to show signals from allenyl cyanide, CH 2 &z.dbd;C&z.dbd;CH-CN, which then further convert into propargyl cyanide, H-C&z.tbd;C-CH 2 -CN. Some evidence for the presence of allenyl isocyanide, propargyl isocyanide, 3-cyanocyclopropene, and 1,2,3-butatrien-1-imine under particular experimental conditions was also observed. Although cyano/isocyano interconversion has been observed during photolysis of other closely related species in solid argon matrices, including H-C&z.tbd;C-CN, no evidence could be found for production of 1-isocyano-1-propyne, CH 3 -C&z.tbd;C-NC for these experiments. Cyanopropyne, CH 3 -C&z.tbd;C-CN, is a simple molecule whose photochemistry we have explored. UV photolysis of this molecule in an Ar matrix was performed and quantum chemical calculations used to better understand photoproduct production.
ISSN:1463-9076
1463-9084
DOI:10.1039/c8cp06739b