Electronic Structure, Stability, and Electrical Mobility of Cationic Silver Oxide Atomic Clusters.

Silver oxide cluster cations (Ag n O m + ) can readily be produced by a number of methods including atmospheric-pressure spark ablation of pure silver electrodes when trace amounts of oxygen are present in the carrier gas. Here we determine the equilibrium geometries of Ag n O m + clusters ( n = 1-4; m = 1-5) using accurate coupled cluster with singles and doubles (CCSD) method, while the stabilization energies are calculated with additional perturbative triples correction (CCSD(T)). Although a number of stable states have been identified, our results show that the Ag n O m + clusters with m = 1 are more stable than those with m ≥ 2 due to the absence of the terminally attached O 2 molecule, corroborating recent observations by mass spectrometry. Using the computed structures, we calculate the electrical mobilities of the Ag n O m + clusters and label the values on a respective experimentally determined spectrum in an attempt to better interpret the occurrence of the peaks and troughs in the measurements.