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Theoretica chimica acta

, Volume 23, Issue 3, pp 278–284 | Cite as

The electronic spectrum of acrylonitrile

  • P. A. Mullen
  • M. K. Orloff
Commentationes

Abstract

The vapor absorption spectrum of acrylonitrile CH2CHCN has been measured in the vacuum ultraviolet region. In addition, an all-valence-electron molecular orbital calculation has been used to calculate the electronic structure and spectrum of the molecule. On the basis of the MO calculation, as well as a vibrational analysis of the observed spectrum, several electronic transitions are assigned. The lowest energy absorption band (2107Å, ɛ = 150) is assigned as an n→π* transition. Absorption bands at 2030Å (ɛ=1600), 1725Å (ɛ = 2100), and 1570Å (ɛ = 1920) are assigned as 0–0 bands associated with transitions that are, respectively,π→π*,σ→σ*, and π→π* in character.

Keywords

Absorption Band Phase Vapeur Electronic Spectrum Energy Absorption Acrylonitrile 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Zusammenfassung

Das UV-Absorptionsspektrum von dampfförmigen Acrylnitril wurde gemessen und eine CNDO/2-Rechnung für die Elektronenstruktur durchgeführt. Auf dieser Basis konnten unter Zuhilfenahme der Analyse der Schwingungsstruktur im beobachteten Spektrum mehrere Banden zugeordnet werden: die 2107-Å-Bande (ɛ = 150) einem n→π*-Übergang, die drei Banden bei 2030Å (ɛ = 1600), 1725Å (ɛ = 2100) und 1570 Å (ɛ = 1920)0-0-Übergängen von π→π*-, σ→σ*- bzw. π→π*-Banden.

Résumé

Mesure du spectre d'absorption en phase vapeur de l'acrilonitrile CH2CHCN dans la région de l'ultraviolet. Par ailleurs, la structure électronique et le spectre de la molécule ont été calculés à l'aide d'une méthode des orbitales moléculaires semi-empirique pour tous les électrons de valence. Sur cette base, ainsi que sur une analyse vibrationnelle du spectre expérimental, on procède à l'attribution de plusieurs transitions électroniques. La bande d'absorption de plus basse énergie (2107 Å, ɛ = 150) est attribuée à une transition n→π*. Les bandes d'absorption à 2030Å (ɛ = 1600), 1275Å (ɛ = 2100) et 1570Å (ɛ = 1920) sont considérées comme des bandes 0 - 0 associées à des transitions π→π*, σ→σ* et π→π* respectivement.

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Copyright information

© Springer-Verlag 1971

Authors and Affiliations

  • P. A. Mullen
    • 1
  • M. K. Orloff
    • 1
  1. 1.Stamford, Research LaboratoriesAmerican Cyanamid CompanyStamford

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