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Journal of Chemical Physics / Volume 131 / Issue 16 / COMMUNICATIONS
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J. Chem. Phys. 131, 161102 (2009); http://dx.doi.org/10.1063/1.3257174 (3 pages)

Laboratory observation of the valence anion of cyanoacetylene, a possible precursor for negative ions in space

Daniel J. Goebbert, Dmitry Khuseynov, and Andrei Sanov

Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721-0041, USA

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(Received 22 September 2009; accepted 9 October 2009; published online 23 October 2009)

Valence anions of cyanoacetylene, HCCCN−, are synthesized by the 1,2-H2+ abstraction reaction of O− with acrylonitrile, H2C = CHCN, while the competing 1,1-H2+ channel of the same reaction yields the cyanovinylidene anions, CCHCN−. The key to the formation of the elusive, adiabatically weakly bound HCCCN− is the bent −math = math–C ≡ skeleton of the reactant. The photoelectron spectrum of HCCCN−, measured by means of photoelectron imaging at 532 nm, consists of a broad structureless band with a vertical detachment energy of 1.04±0.05 eV. The observed anions are stable counterparts of the low-lying anionic resonances of cyanoacetylene, which may contribute (by way of dissociative attachment) to the formation of carbon-rich and CN-containing negative ions in extraterrestrial environments.

© 2009 American Institute of Physics

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KEYWORDS and PACS

Keywords

astrochemistry, chemical exchanges, electron attachment, negative ions, organic compounds, photoelectron spectra, resonant states, valency

PACS

  • 82.30.Hk

    Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)

  • 95.30.Ft

    Molecular and chemical processes and interactions

  • 34.80.Ht

    Dissociation and dissociative attachment

  • 33.60.+q

    Photoelectron spectra

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3257174

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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Figures (click on thumbnails to view enlargements)

FIG.1
The chemical structure of acrylonitrile H2C = CHCN, with the shaded circles marking the hydrogen centers abstracted via the three possible channels of the O−+H2C = CHCN→C3HN−+H2O reaction, as follows: (a) the trans-1,2-H2+ abstraction reaction, yielding nascent trans-HCCCN− products; (b) the cis-1,2-H2+ abstraction pathway, yielding nascent cis-HCCCN− products; and (c) the 1,1-H2+ abstraction channel, yielding the cyanovinylidene anion CCHCN−.

FIG.1 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.2
The photoelectron image and the corresponding spectrum of HCCCN− and CCHCN− obtained at 532. The laser polarization axis is vertical in the plane of the image. Band A (shaded) is assigned to HCCCN−, while band B corresponds to CCHCN−. The corresponding equilibrium anion geometries are shown schematically above the corresponding bands in the photoelectron spectrum. The geometric parameters of the planar HCCCN− structure, as determined by Sommerfeld and Knecht (Ref. 5) at the CCSD(t)/aug-cc-pVDZ level of theory, are as follows: R(H–C1) = 1.1103 Å, R(C1–C2) = 1.3306 Å, R(C2–C3) = 1.4157 Å, R(C3–N) = 1.1958 Å, ∠HC1C2 = 123.08°, ∠C1C2C3 = 133.07°, ∠C2C3N = 172.60°. The geometry of CCHCN− is described elsewhere (Ref. 13).

FIG.2 Download High Resolution Image (.zip file) | Export Figure to PowerPoint


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