Determination of the symmetry of the highest occupied molecular orbitals of SF6

Rui-Qi Wu; Ying-Chun Guo; Bing-Bing Wang

doi:10.7498/aps.68.20182231

Abstract

Quantum chemical calculation is an important method to investigate the molecular structures for multi-atom molecules. The determination of electronic configurations and the accurate description of the symmetry of molecular orbitals are critical for understanding molecular structures. For the molecules belonging to high symmetry group, in the quantum chemical calculation the sub-group is always adopted. Thus the symmetries of some electric states or some molecular orbitals, which belong to different types of representations of high symmetry group, may coincide in the sub-group presentations. Therefore, they cannot be distinguished directly from the sub-group results. In this paper, we provide a method to identify the symmetry of molecular orbitals from the theoretical sub-group results and use this method to determine the symmetry of the highest occupied molecular orbitals (HOMO) of the sulfur hexafluoride SF₆ molecule as an example. Especially, as a good insulating material, an important greenhouse gas and a hyper-valent molecule with the high octahedral

$ O_h $

symmetry, SF₆ has received wide attention for both the fundamental scientific interest and practical industrial applications. Theoretical work shows that the electronic configuration of ground electronic state

$ ^1{\rm A_{1g}} $

of SF₆ is

${({\rm {core}})^{22}}{(4{\rm a_{1\rm g}})^2}{(3{{\rm t}_{1\rm u}})^6}{(2{{\rm e}_{\rm g}})^4}{(5{{\rm a}_{1\rm g}})^2}{(4{{\rm t}_{1\rm u}})^6}{(1{{\rm t}_{2\rm g}})^6}{(3{{\rm e}_{\rm g}})^4}{(1{{\rm t}_{2\rm u}})^6}{(5{{\rm t}_{1\rm u}})^6}{(1{{\rm t}_{1\rm g}})^6} $

and the symmetry of the HOMOs is

$ T_{1g} $

. However, in some literature, the symmetry of HOMOs of SF₆ has been written as

$ T_{2g} $

instead of

$ T_{1g} $

. The reason for this mistake lies in the fact that in the ab initial quantum chemical calculation used is the Abelian group

$ D_{2h} $

, which is the sub-group of

$ O_h $

Keywords

molecule with high symmetry group orbital''s symmetry SF₆ the highest occupied molecular orbitals

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