The European Physical Journal D

, Volume 45, Issue 2, pp 235–246 | Cite as

Lifetime vibrational interference during the NO 1s-1π* resonant excitation studied by the NO+(A 1Π → X 1Σ+) fluorescence

  • A. Ehresmann
  • W. Kielich
  • L. Werner
  • Ph. V. Demekhin
  • D. V. Omel'yanenko
  • V. L. SukhorukovEmail author
  • K.-H. Schartner
  • H. Schmoranzer
Molecular Physics and Chemical Physics


Dispersed fluorescence from fragments formed after the de-excitation of the 1s-1π* resonances of N*O and NO* has been measured in the spectral range of 118–142 nm. This range is dominated by lines of atomic nitrogen and oxygen fragments and by the \(A ~^{1}{\rm \Pi} \left(v^{\prime}\right) \rightarrow X ~^{1}{\rm \Sigma}^{+}\left(v^{\prime \prime}\right)\) bands in the NO+ ion which result from the participator Auger decay of the 1s-1π* resonances. Ab-initio calculations of the transition probabilities between vibrational levels during the reaction NO \(X~^{2}{\rm \Pi}\left(v_{0}=0\right) \rightarrow \) N*O\(\left( {\rm NO}^{\ast}\right) \) \(1s^{-1}\pi ^{\ast }\left( v_{r}\right) \) ⇒ NO\(^{+}~A~^{1}{\rm \Pi} \left(v^{\prime}\right) \rightarrow X~^{1}{\rm \Sigma}^{+}\left(v^{\prime \prime}\right)\) were used to explain the observed intensity dependence for the \(A\left(v^{\prime }\right) \rightarrow X\left(v^{\prime \prime}\right)\) fluorescence bands on the exciting-photon energy across the resonances and on both v and v′′ vibrational quantum numbers. The multiplet structure of the 1s-1π* resonance and lifetime vibrational interference explain the observed exciting-photon energy dependence of the \(A\left( v^{\prime}\right) \rightarrow X\left(v^{\prime \prime}\right)\) fluorescence intensity. A strong spin-orbit coupling between singlet and triplet states of NO+ is proposed to reduce additional cascade population of the \(A~^{1}{\rm \Pi}\) state via radiative transitions from the \(W~^{1}{\rm \Delta}\) and \(A^{\prime}~^{1}{\rm \Sigma}^{-}\) states and to explain remaining differences between measured and calculated integral fluorescence intensities.


32.80.Hd Auger effect and inner-shell excitation or ionization 33.80.-b Photon interactions with molecules 33.50.Dq Fluorescence and phosphorescence spectra 


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Copyright information

© EDP Sciences/Società Italiana di Fisica/Springer-Verlag 2007

Authors and Affiliations

  • A. Ehresmann
    • 1
  • W. Kielich
    • 1
  • L. Werner
    • 1
  • Ph. V. Demekhin
    • 1
    • 2
  • D. V. Omel'yanenko
    • 2
  • V. L. Sukhorukov
    • 2
    • 3
    Email author
  • K.-H. Schartner
    • 4
  • H. Schmoranzer
    • 5
  1. 1.Institute of Physics and CINSaT, University of KasselKasselGermany
  2. 2.Rostov State University of Transport CommunicationsRostov-on-DonRussia
  3. 3.Institute of Physics, Southern Federal UniversityRostov-on-DonRussia
  4. 4.I. Institute of Physics, Justus-Liebig University GiessenGiessenGermany
  5. 5.Department of PhysicsKaiserslautern University of TechnologyKaiserslauternGermany

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