Li 3 – O – Li 3 molecule: A metal-nonmetal-metal sandwichlike compound with a distending electron cloud

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The D3d and D2d isomers of the Li3-O-Li3 molecule are metal-nonmetal-metal sandwichlike structures that contain two Li3 superalkali atoms. Their geometries and the real frequencies are obtained at the CCSD(T)/aug-cc-pVDZ level. They are different from the traditional types of the nonmetal-metal-nonmetal sandwich compounds. The natural bond orbital calculation and the topological property nabla2rho(r) calculation indicate that they are typical ionic compounds. In two isomers, the O2- anion is sandwiched in between two Li3+ cation rings. However, the different orientations of two Li3+ planes give the D3d isomer its own special characteristics. Under the action of the O2- anion in the center, the valence electrons of the D3d isomer are pushed out from two Li3+ triangle rings. This special interaction causes three phenomena. First, the valence electron clouds are distended. Second, the vertical ionization energy of the D3d isomer is considerably low, 4.39 eV, so that it may also be viewed as a superalkali atom. Third, we find that the D3d isomer owns the out-of-plane aromaticity and the largest negative nucleus-independent chemical shift value (-10.8 ppm) exists at 2.5 A above the center of the Li3+ ring, not at the center of the Li3+ ring like the isolated aromatic Li3+ cation.