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• W2008039923 abstract "Negative ions of cyanoacetylene and cyanovinylidene are generated simultaneously via the competing 1,1-H2+ and 1,2-H2+ abstraction channels of O− reaction with acrylonitrile. The two stable isomeric forms of the anion, CCHCN− and HCCCN−, are separated by a large (∼2 eV) potential energy barrier. Their photodetachment provides access to both the reactant and the product sides of the neutral cyanovinylidene → cyanoacetylene rearrangement reaction, predicted to involve only a very small barrier. Using photoelectron imaging spectroscopy at 532 and 355 nm, the adiabatic electron affinity of the reactive intermediate :C═CHCN (X1A′), is determined to be 1.84 ± 0.01 eV. The photoelectron spectrum of CCHCN− exhibits a vibrational progression attributed to the excitation of the CCH bending mode. The observed spectral features are reproduced reasonably well using a Franck−Condon simulation under the parallel-mode approximation. In contrast to unsubstituted acetylene, cyanoacetylene has a stable anionic state, which is adiabatically weakly bound, but has an experimentally determined vertical detachment energy of 1.04 ± 0.05 eV. This measurement, along with the broad, structureless photoelectron spectrum of HCCCN− (with no identifiable origin), reflects the large geometry difference between the w-shaped structure of the anion and the linear equilibrium geometry of HCCCN." @default.
• W2008039923 created "2016-06-24" @default.
• W2008039923 creator A5021940253 @default.
• W2008039923 creator A5030749866 @default.
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• W2008039923 date "2010-01-21" @default.
• W2008039923 modified "2023-09-24" @default.
• W2008039923 title "Photoelectron Imaging of Cyanovinylidene and Cyanoacetylene Anions" @default.
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• W2008039923 doi "https://doi.org/10.1021/jp9106102" @default.
• W2008039923 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/20092319" @default.
• W2008039923 hasPublicationYear "2010" @default.
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