Closed-shell interaction in silver and gold chlorides

TL;DR

This study uses advanced quantum chemical calculations to analyze the nature of closed-shell interactions in silver and gold chlorides, providing insights into their structural stability and the strength of aurophilic interactions.

Contribution

It presents the first quantitative analysis of aurophilic Au(I)-Au(I) interactions in solids using high-level computational methods.

Findings

Cohesive energies and lattice constants match experiments well for AgCl.

For AuCl, the observed structure is energetically favored over the cubic form.

Electron-correlation effects significantly influence lattice constants, especially in AuCl.

Abstract

Hartree-Fock and coupled-cluster calculations have been performed for cubic AgCl and for AuCl having a cubic or the observed structure with space group I4_1/amd. Cohesive energies and lattice constants are in excellent agreement with experiment for AgCl; for AuCl we find good agreement, and the experimental structure is correctly predicted to be lower in energy than the cubic one. Electron-correlation effects on lattice constants are very large, of up to 0.8 \AA for cubic AuCl. We especially discuss the strength of the closed-shell interactions, and for the first time a quantitative analysis of the so-called "aurophilic" Au(I)-Au(I) interaction is presented in solids.