Structure and chemical bonding in high-pressure potassium silver alloys

Abstract

Abstract The high-pressure structures of K-Ag alloys were examples of pressure-induced electron transfer from the electropositive potassium to the electronegative silver. We re-examined the crystal and electronic structures of KAg2, K2Ag, and K3Ag using powder X-ray diffraction and theoretical calculations. Our findings establish a connection between the morphologies of these three phases and the precursor face-centered cubic Ag. For K2Ag, we discovered a disordered structure that better matches the X-ray pattern. Valence electron density distributions obtained from the maximum entropy method, along with charge density calculations, provide a comprehensive understanding of the evolution of chemical bonding in these systems. It was found that K atoms share their valence electrons during alloy formation, contributing to K-Ag and Ag-Ag bonds in K2Ag and KAg2, while no Ag-Ag bonds are present in K3Ag. These results indicate the Zintl-Klemm model may be too simplistic to describe the structure and bonding in high-pressure binary intermetallic compounds.