Production of Vibrationally Excited CN(B<sup>2</sup>Σ<sup>+</sup>) via Superexcited Ion-Pair State of Triatomic Alkali-Metal Cyanides by Ar(<sup>3</sup>P<sub>2,0</sub>) Impact

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Emission spectra from CN(B2Σ+) produced by dissociative excitation of MCN (M = Rb, K, Na) in collision with Arm(3P2,0) were observed, and the mechanism of the energy partition between the two fragments was elucidated. The vibrational distribution of the CN(B2Σ+) product is composed of two distinct components, PL and PH, ranged in the vibrational levels of v‘ = 0−3 and 11−19, respectively, where v‘ is the vibrational quantum number of CN(B2Σ+). The components, PL and PH, arise from direct dissociation and predissociation of MCN by Arm(3P2,0) impact, respectively. The direct dissociation proceeds on a repulsive potential energy surface correlating diabatically to M(ns2S) + CN(B2Σ+) (n = 5, 4, 3 for M = Rb, K, Na, respectively). This mechanism was further supported by a molecular dynamics simulation. The predissociation, on the other hand, proceeds via a superexcited ion-pair state, M+·[CN-]**, having a much longer equilibrium C−N internuclear distance than that of CN(B2Σ+), so that more than 90% of the exce...

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Details 詳細情報について

  • CRID
    1870865117618499200
  • DOI
    10.1021/jp981295u
  • ISSN
    15205215
    10895639
  • Data Source
    • OpenAIRE

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