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A theoretical study of the reaction of HCO + with C 2 H 2
Author(s) -
del Río E.,
López R.,
Menéndez M. I.,
Sordo T. L.
Publication year - 2000
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(20000115)21:1<35::aid-jcc4>3.0.co;2-6
Subject(s) - acetylene , chemistry , protonation , interstellar cloud , dissociative recombination , interstellar medium , gibbs free energy , potential energy surface , transition state , computational chemistry , atomic physics , photochemistry , thermodynamics , recombination , physics , ion , molecule , organic chemistry , quantum mechanics , catalysis , biochemistry , galaxy , gene
A theoretical study was performed for the reaction of formyl cation and acetylene to give C 3 H 3 + +O in flames and C 2 H 3 +(nonclassical)+CO, both in flames and in interstellar clouds. The corresponding Potential Energy Surface (PES) was studied at the B3LYP/cc‐pVTZ level of theory, and single‐point calculations on the B3LYP geometries were carried out at the CCSD(T)/cc‐pVTZ level. Our results display a route to propynal evolving energetically under C 2 H 3 +(nonclassical)+CO and, consequently, accessible in interstellar clouds conditions. This route connects the most stable C 3 H 3 O + isomer (C2‐protonated propadienone) with a species from which propynal may be produced in a dissociative electron recombination reaction. The reaction channel to produce the C 3 H 3 + +O evolves basically through two TSs and presents an endothermicity of 63.9 kcal/mol at 2000 K. According to our Gibbs energy profiles, the C2‐protonated propadienone is the most stable species at low–moderate temperatures and, consequently, could play a certain role in interstellar chemistry. On the contrary, in combustion chemistry conditions (2000 K) the C 2 H 3 +(nonclassical)+CO products are the most thermodynamically favored species. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 35–42, 2000