Si6Tip6: the Largest and Most Complicated Ever Experimental Gas Phase Molecular Structure

The largest (ra = 19.9 A) and by far the most complicated (234 atoms, C1 symmetry, 696 independent geometrical parameters, 27261 interatomic terms) experimental molecular structure of a cage-type Si6Tip6 (Tip = 2,4,6-iPr3C6H2) isomer has been investigated in the gas phase by the electron diffraction method supplemented with theoretical simulations. A detailed analysis of the current possibilities for experimentally investigating of large molecular structures is performed. A series of density functional theory (DFT) approximations and the role of dispersion interactions have been benchmarked using the obtained data. Based on the refined geometry of Si6Tip6 various quantum-chemical methods have been applied for investigation of the electronic structure of its Si6 core. In particular, natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM), interacting quantum atoms (IQA), fractional occupation number weighted density (FOD) and complete active space self-consistent field (CASSCF) methods were utilized. Diradical character of the molecule has been assessed by the UHF and CASSCF approximations. The problem of bonding between the hemispheroidal silicon atoms has been investigated.