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The Hartree-Fock level optimizations were done on the octasilsesquioxane(Si_8O_12H_8)of double four-ring(D4R)cage, the trapped atomic hydrogen in D4R cage(H@D4R),and the transition state of detrapping... process from H@D4R to D4R. Both of D4R and H@D4R were optimized with O_h molecular symmetry and the cage conformations in D4R and H@D4R were very similar. On H@D4R trapped H atom was located at the center of D4R cage. From one point calculations with Mφller-Plesset Second-Order perturbation(MP2)1evel on each optimized structure, the activation and reaction energies of this detrapping process were +106.3 and -16.1kJ/mo1, respectively. The value of activation energy was in good agreement with Stösser’s experimental data(+109.6±3.lkJ/mol). The small interaction between D4R cage and trapped H atom in H@D4R was represented by Singly Occupied Molecular Orbital(SOMO)[8a_1g]of H@D4R which was constructed from antレbonding interaction between Lowest Unoccupied Molecular Orbital(LUMO)[8a_lg]of D4R and 1s radical orbital of trapped H atom. On the transition state, the positions of all Si atoms were unchanged, and four O atoms in the single four-ring were displaced so as to open one of one-side windows on D4R cage from the influence of detrapping of H atom.続きを見る
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