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Title: The Formation of Monosubstituted Cyclopropenylidene Derivatives in the Interstellar Medium via Neutral–Neutral Reaction Pathways

Five substituted cyclopropenylidene derivatives (c-C3HX, X=CN, OH, F, NH2), all currently undetected in the interstellar medium (ISM), are found herein to have mechanistically viable, gas-phase formation pathways through neutral–neutral additions of ·X ontoc-C3H2. The detection and predicted formation mechanism ofc-C3HC2H introduces a need for the chemistry ofc-C3H2and any possible derivatives to be more fully explored. Chemically accurate CCSD(T)-F12/cc-pVTZ-F12 calculations provide exothermicities of additions of various radical species toc-C3H2, alongside energies of submerged intermediates that are crossed to result in product formation. Of the novel reaction mechanisms proposed, the addition of the cyano radical is the most exothermic at -16.10 kcal mol−1. All five products are found to or are expected to have at least one means of associating barrierlessly to form a submerged intermediate, a requirement for the cold chemistry of the ISM. The energetically allowed additions arise as a result of the strong electrophilicity of the radical species as well as the product stability gained through substituent-ring conjugation.

Publication Date:
Journal Name:
The Astrophysical Journal
Page Range or eLocation-ID:
Article No. 15
DOI PREFIX: 10.3847
Sponsoring Org:
National Science Foundation
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