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A computational study of photoisomerization in Al3O3- ­clusters

Cui, XY, Morrison, I and Han, JG 2002, 'A computational study of photoisomerization in Al3O3- ­clusters' , Journal of Chemical Physics, 117 (3) , pp. 1077-1084.

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    Abstract

    Ab initio calculations are employed to understand the photoisomerization process in small Al3O3- clusters. This process is the first example of a photoinduced isomerization observed in an anion cluster gas-phase system. Potential energy surfaces for the ground state and the excited state (S1 and T1) are explored by means of B3LYP, MP2, CI-singles, and CASSCF methods. We demonstrate that the isomerization process occurs between the global minimum singlet state Book structure (C2v,1A1) and the triplet state Ring structure (C2v,3B2). The calculated vertical excitation energy is 3.62 eV at the CASSCF level of approximation, in good agreement with the experimental value (3.49 eV). A nonplanar conical intersection, which hosts the intersystem crossing between the S1 and T1 surfaces is identified at the region of around R(1,6)=2.4 Å. Beyond the experimental results, we predict, that this isomerization is reversible upon absorption of a phonon with energy of 1.92 eV. Our results describe a unique system, whose structure depends on its spin multiplicity; it exists as the Book structure on singlet states and as the Ring structure on triplet states.

    Item Type: Article
    Uncontrolled Keywords: aluminium compounds, negative ions, isomerisation, photochemistry, configuration interactions, density functional theory, potential energy surfaces, nonradiative transitions, molecular clusters, SCF calculations
    Themes: Subjects / Themes > Q Science > QD Chemistry
    Subjects / Themes > Q Science > QC Physics
    Subjects outside of the University Themes
    Schools: Colleges and Schools > College of Science & Technology
    Colleges and Schools > College of Science & Technology > School of Computing, Science and Engineering
    Colleges and Schools > College of Science & Technology > School of Computing, Science and Engineering > Materials & Physics Research Centre
    Journal or Publication Title: Journal of Chemical Physics
    Publisher: American Institute of Physics
    Refereed: Yes
    ISSN: 00219606
    Related URLs:
    Depositing User: H Kenna
    Date Deposited: 23 Aug 2007 10:47
    Last Modified: 20 Aug 2013 16:46
    URI: http://usir.salford.ac.uk/id/eprint/322

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