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    Quenching of excited 1 P 1 state atomic zinc by molecular nitrogen: A matrix-isolation spectroscopy/quantum chemical calculation study

    Colmenares, Fernando and McCaffrey, John G. and Novaro, Octavio (2001) Quenching of excited 1 P 1 state atomic zinc by molecular nitrogen: A matrix-isolation spectroscopy/quantum chemical calculation study. Journal of Chemical Physics, 114 (22). pp. 9911-9918. ISSN 0021-9606

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    A concentration study is used to identify the optical absorption of zinc atoms isolated in solid nitrogen. Photoexcitation of the threefold-split, atomic 4p 1P1 singlet absorption band did not produce any emission from either the singlet or triplet states. Hartree–Fock (relativistic effective core potentials) plus variational and multireference perturbational configuration-interaction calculations are performed to analyze this very efficient quenching of excited state atomic zinc by molecular nitrogen. Of the two geometries considered in energy calculations of the approach of Zn(1P1) to N2, the collinear exhibited a slightly greater stabilization than the perpendicular approach. However, the collinear is identified as of no significance in the excited state quenching due to the absence of low energy crossings with the ground state. In contrast, for the perpendicular approach a crossing between the repulsive ground 1A1(1S0) state and the strongly attractive 1B2(1P1) state occurs close to the energy minimum of the 1B2 state. The efficiency of crossing between these states is analyzed in the framework of one-dimensional Landau–Zener (LZ) theory. A hopping probability of 0.07 is obtained for a single crossing, considered important in a rapidly relaxing solid state system, such as present in a low temperature matrix. Crossings found between the repulsive 3B1(3P1) and 3A1(3P1) states with the strongly bound 1B2(1P1) state are expected to play a role in gas phase Zn(1P1) quenching leading to the production of Zn(3PJ) states. LZ calculations indicate a small hopping probability for these crossings, consistent with the small 1P1→3PJ quenching cross sections observed in the gas phase work.

    Item Type: Article
    Keywords: concentration study; excited 1 P 1 state atomic zinc; molecular nitrogen; matrix-isolation; spectroscopy; quantum chemical calculation study;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 7834
    Identification Number:
    Depositing User: Dr. John McCaffrey
    Date Deposited: 30 Jan 2017 16:46
    Journal or Publication Title: Journal of Chemical Physics
    Publisher: American Institute of Physics
    Refereed: Yes
    Use Licence: This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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