The potential of using atmospheric-pressure spark ablation for production of atomic clusters has been shown in the recent past. In this study we used this method to produce atomic clusters in Argon and investigated their chemical composition with an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF-MS). Both anionic and cationic silver and gold clusters were generated and characterised. The carrier gas was used directly from the gas cylinder without the application of any additional gas purification. As a result, the carrier gas stream contained trace impurities of N2, O2, and H2O, as well as radicals such as O, OH, and H and their ionized forms resulting from the plasma created by the sparks. The experimental results show that different reactivities towards oxygen and water traces can be observed depending on the number of metal atoms in the clusters, their polarity, as well as their compositions; e.g., Aun− shows less reactive behaviour towards oxygen and hydrogen compared to Agn−. The results also show that certain cluster types can be generated at large enough quantities by atmospheric-pressure spark ablation, which considering the low installation and operating cost of the technique can pave the way towards its exploitation for numerous technological applications.@en

Silver oxide cluster cations (AgnOm+) 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 AgnOm+ 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 AgnOm+ clusters with m = 1 are more stable than those with m ≥ 2 due to the absence of the terminally attached O2 molecule, corroborating recent observations by mass spectrometry. Using the computed structures, we calculate the electrical mobilities of the AgnOm+ 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. @en

Experimental evidence shows that hydroxylated metal ions are often produced during cluster synthesis by atmospheric pressure spark ablation. In this work, we predict the ground state equilibrium structures of AgOkHm± clusters (k and m = 1–4), which are readily produced when spark ablating Ag, using the coupled cluster with singles and doubles (CCSD) method. The stabilization energy of these clusters is calculated with respect to the dissociation channel having the lowest energy, by accounting perturbative triples corrections to the CCSD method. The interatomic interactions in each of the systems have been investigated using the frontier molecular orbital (FMO), natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) methods. Many of the ground states of these ionic clusters are found to be stable, corroborating experimental observations. We find that clusters having singlet spin states are more stable in terms of dissociation than the clusters that have doublet or triplet spin states. Our calculations also indicate a strong affinity of the ionic and neutral Ag atom towards water and hydroxyl radicals or ions. Many 3-center, 4-electron (3c/4e) hyperbonds giving rise to more than one resonance structure are identified primarily for the anionic clusters. The QTAIM analysis shows that the O–H and O–Ag bonds in the clusters of both polarities are respectively covalent and ionic. The FMO analysis indicates that the anionic clusters are more reactive than the cationic ones. Using the cluster structures predicted by the CCSD method, we calculate the collision cross sections of the AgOkHm± family, with k and m ranging from 1 to 4, by the trajectory method. In turn, we predict the electrical mobilities of these clusters when suspended in helium at atmospheric pressure and compare them with experimental measurements.@en