Coordination of Ethylamine on Small Silver Clusters: Structural and Topological (ELF, QTAIM) Analyses

Amine ligands are expected to drive the organ-ization of metallic centers as well as the chemical reactivity of silverclusters early growing during the veryfirst steps of the synthesis ofsilver nanoparticlesviaan organometallic route. Density functionaltheory (DFT) computational studies have been performed tocharacterize the structure, the atomic charge distribution, and theplanar two-dimensional (2D)/three-dimensional (3D) relativestability of small-size silver clusters (Agn,2 <= n <= 7), with orwithout an ethylamine (EA) ligand coordinated to the Ag clusters.The transition from 2D to 3D structures is shifted fromn= 7 to 6in the presence of one EA coordinating ligand, and it is explainedfrom the analysis of the Ag-N and Ag-Ag bond energies. For fullyEA saturated silver clusters (Agn-EAn), the effect on the 2D/3D transition is even more pronounced with a shift betweenn= 4 and5. Subsequent electron localization function (ELF) and quantum theory of atoms in molecules (QTAIM) topological analyses allowfor thefine characterization of the dative Ag-N and metallic Ag-Ag bonds, both in nature and in strength. Electron transfer fromethylamine to the coordinated silver atoms induces an increase of the polarization of the metallic core

Automated summary

Amine ligands are expected to drive the organization of metallic centers and the chemical reactivity of silver clusters during the synthesis of silver nanoparticles. Computational studies using density functional theory have characterized the structure and stability of small-size silver clusters with or without ethylamine ligands. The analysis of the Ag-N and Ag-Ag bond energies explains the transition from 2D to 3D structures. Electron transfer from ethylamine to the silver atoms increases the polarization of the metallic core.