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    Spectroscopic characterization of excited Ca(4s4dδ 3DJ)RG(3Δ1,2) states (RG=Ar, Kr, Xe): No “heavy-atom” mixing of RG(ndδ) character into the wave functions


    Leung, Allen W.K. and Kaup, John G. and Bellert, D. and McCaffrey, John G. and Breckenridge, W.H. (1999) Spectroscopic characterization of excited Ca(4s4dδ 3DJ)RG(3Δ1,2) states (RG=Ar, Kr, Xe): No “heavy-atom” mixing of RG(ndδ) character into the wave functions. Journal of Chemical Physics, 111 (3). pp. 981-987. ISSN 0021-9606

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    Abstract

    The excited Ca(4s4dδ 3DJ)RG[3Δ1,2] states (RG=Ar, Kr, Xe) have been characterized spectroscopically by R2PI (resonance-enhanced two-photon ionization) spectroscopy. The main vibrational progressions, assigned to Ca(4s4dδ 3D1)RG[3Δ1]←Ca(4s4pπ 3P0)⋅RG[3Π⎯0] transitions, have weak subbands 3.7±0.5 cm−1 to the blue which have been assigned to analogous transitions to the 3Δ2 upper states. For CaAr and CaKr, rotational analysis has confirmed this assignment. The 3Δ2/3Δ1 splitting is within experimental error the value expected if the molecular spin-orbit coupling constant is derived entirely from the Ca(4s4d 3DJ) atomic contribution. This indicates that there is no “heavy-atom” mixing of RG(ndδ) character into the wave functions of the CaRG(3Δ) states.

    Item Type: Article
    Keywords: Ionization spectroscopy; Wave functions; Multiphoton excitation; Multiphoton ionization; Excited states;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 7858
    Identification Number: https://doi.org/10.1063/1.479380
    Depositing User: Dr. John McCaffrey
    Date Deposited: 03 Feb 2017 17:13
    Journal or Publication Title: Journal of Chemical Physics
    Publisher: American Institute of Physics
    Refereed: Yes
    URI:

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