A computational study of photoisomerization in Al3O3- ­clusters

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 A. 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 st...

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