Electronic properties and electrical mobilities of cationic silver hydride clusters

Abstract

Cationic silver hydride clusters (Ag_nH⁺) can be formed by a number of physical and chemical processes, holding great promise for a range of applications including photonics, catalysis, sensing, and biomedicine, among others. Here, we present a comprehensive theoretical investigation of Ag_nH⁺ clusters (n = 1−7) using highly accurate Coupled-Cluster (CC) theory. Multiple low-lying isomers are identified using CC theory with Single and Double excitations (CCSD), whereas their relative stabilities are determined with the more accurate CCSD(T) method. The CCSD(T) results predict a pronounced odd-even alternation in relative stabilities, with Ag₂H⁺ being the most stable species, which is consistent with experimental mass spectrometry measurements. Ab initio molecular dynamics simulations show that all low-energy isomers remain structurally rigid at room temperature, whereas bonding analyses (frontier molecular orbitals, natural bond orbital, molecular electrostatic potential, quantum theory of atoms in molecules, non-covalent interaction) indicate strong ionic Ag−H interactions, weak non-covalent Ag−Ag interactions, and significant donor-acceptor stabilization in larger clusters. Electrical mobilities of these clusters, computed by the trajectory method, were labelled on experimental spectra, improving their interpretation. Overall, our results resolve inconsistencies from prior theoretical predictions, provide a rigorous description of cationic silver hydride clusters, and are used to improve the interpretation of earlier observations.