On the electronic structures and s/p-orbital aromaticity in the Hg3Al3+/ −, Hg3Al3Li, and Hg3Al3Be+ clusters

Publication date: 15 April 2017 Source:Computational and Theoretical Chemistry, Volume 1106 Author(s): Biao Jin, Qiao Jin, Fu-Kai Jin The equilibrium geometries, harmonic vibrational frequencies, stabilities, and chemical bonding of the low-lying states for all-metal Hg3Al3 +/−, Hg3Al3Li, and Hg3Al3Be+ clusters are investigated using 2nd order Møller–Plesset perturbation theory. The extensive search for the global minimum structures of Hg3Al3 +/− at the MP2 level of theory with 6-311++G∗ basis set for Al and CEP-121G basis set for Hg reveals that the ground states of the Hg3Al3 + and Hg3Al3 − clusters are all singlet state 1A′ with Cs symmetry. A detailed molecular orbital (MO) analysis reveals that the Hg3Al3 + (Cs, 1A′) cation and Hg3Al3 − (Cs, 1A′) anion possess double aromaticity (simultaneous presence of σ- and π-aromaticity). The hexagonal pyramidal-type Hg3Al3Li and Hg3Al3Be+ complexes containing the Hg3Al3 − ligand reveal that the Hg3Al3 − structural units are preserved in the Hg3Al3Li and Hg3Al3Be+ complexes, which also possess corresponding aromatic characters. Graphical abstract

Source: Computational and Theoretical Chemistry - March 10, 2017 Category: Chemistry Source Type: research