Study on the Structures and Properties of Molecular Clusters Sc6Sn (n = 1–12) and Their Anions with DFT Theory

Abstract

Transition metal doped sulfur clusters have long been attracting great attention due to their unique structures and interesting physicochemical properties. In this work, the ground state configurations of molecular clusters Sc₆S_n (n = 1–12) and their anions are screened out by using the global search artificial bee colony (ABC) ABCluster combined with density functional theory (DFT) calculations. The structural evolution pattern for neutral clusters can be described as follows: when n ≤ 8, the octahedral geometry of Sc₆ remains unchanged. As the number of S atoms increases, the S atoms attach onto different faces of the Sc₆ octahedron with a preference for attaching onto meta-faces, followed by para-faces, and finally the ortho-faces. When n ≥ 9, the Sc₆ octahedron transforms into a nearly planar six-membered ring. For anions, the structures differ significantly from their neutral counterparts when n ≥ 10. Their relative stabilities, HOMO-LUMO gaps, and electron affinities have been reported. Simulated photoelectron spectroscopy (PES), Infrared, and Raman spectra have been provided for their structural identification.