Size evolution relativistic DFT-QTAIM study on the gold cluster complexes Au4-S-CnH2n-S′-Au4′ (n = 2–5)

• DOI: 10.1016/j.cplett.2016.08.038
• Publication Date: 2016-08-22T20:31:51Z
• Authors: Juan I. Rodríguez; Emilbus A. Uribe; María I. Baltazar...; Jochen Autschbach; F.L. Castillo-Alv...; Israel Gutiérrez-...
• Keywords: 01 natural sciences; 0104 chemical sciences

Abstract We introduce relativistic density functional theory (DFT) calculations on the gold cluster complexes (cluster-molecule-cluster) Au4-S-CnH2n-S′-Au4′ (n = 2–5). The structural, electronic and relativistic (ZORA) Bader's quantum theory of atoms in molecules (QTAIM) properties of the two lowest-energy complex isomers were computed as a function of the alkanedithiol size (n). The lowest-energy isomer is a triplet spin state independently of the complex size. According to QTAIM, the Au-Au and S-Au bonds are classified as closed shell (non-covalent) type. The HOMO-LUMO gap of the cluster complexes shows a zigzag behavior typical of gold nanoclusters with respect to the size of the alkanedithiol chain (n).