Atomic Gold Ions Clustered with Noble Gases: Helium, Neon, Argon, Krypton, and Xenon

TL;DR

This study investigates noble gas cluster ions doped with gold, revealing stable structures and solvation shell patterns through high-resolution mass spectrometry and theoretical analysis.

Contribution

It provides new insights into the stability, structure, and solvation behavior of noble gas-Au cluster ions, including unexpected abundance maxima.

Findings

Stable covalent Au-noble gas cluster ions identified.

Solvation shell sizes correlate with ion-ligand size ratios.

Unexpected abundance of Ne₂Au⁺ despite low predicted stability.

Abstract

High-resolution mass spectra of helium droplets doped with gold and ionized by electrons reveal He$_n$Au$^+$ cluster ions. Additional doping with heavy noble gases results in NenAu+, Ar$_n$Au$^+$, Kr$_n$Au$^+$, and Xe$_n$Au$^+$ cluster ions. The high stability predicted for covalently bonded Ar$_2$Au$^+$, Kr$_2$Au$^+$, and Xe$_2$Au$^+$ is reflected in their relatively high abundance. Surprisingly, the abundance of Ne$_2$Au$^+$ which is predicted to have zero covalent bonding character and no enhanced stability features a local maximum, too. The predicted size and structure of complete solvation shells surrounding ions with essentially non-directional bonding depends primarily on the ratio $\sigma$* of the ion-ligand $versus$ the ligand-ligand distance. For Au$^+$ solvated in helium and neon the ratio $\sigma$* is slightly below 1, favoring icosahedral packing in agreement with a maximum observed in the corresponding abundance distributions at $n$ = 12. He$_n$Au$^+$ appears to adopt two additional solvation shells of $I_h$ symmetry, containing 20 and 12 atoms, respectively. For Ar$_n$Au$^+$, with $\sigma$* $\approx$ 0.67, one would expect a solvation shell of octahedral symmetry, in agreement with an enhanced ion abundance at $n$ = 6. Another anomaly in the ion abundance at Ar$_9$Au$^+$ matches a local maximum in its computed dissociation energy.